THE UNIVERSITY OF MICHIGAN COLLEGE OF ENGINEERING Department of Meteorology and Oceanography Technical Report AREA-WIDE DISTRIBUTION OF LEAD, COPPER, CADMIUM, AND BISMUTH IN ATMOSPHERIC PARTICLES IN CHICAGO AND NORTHWEST INDIANA: A MULTI-SAMPLE APPLICATION AND ANODIC STRIPPING VOLTAMMETRY Paul R. Harrison John W. Winchester Project Director ORA Project 01173 sSvipoDrte by: DEPARTMENT OF HEALT'H,. EDUCAT ION,,AEND.ELFARE U. S. PUB.LIC':HEALTIJH'SERVICE., NATIONAL INSTITUTES-'OF'" HEALT'H. GRANT NO.AP-OO582O-'" BETHESDA, MARYIAND administered through: OFFICE OF RESEARCH ADMINISTRATION ANN ARBOR May 1970

ACKNOWLEDGMENTS I wish to gratefully acknowledge the many people and agencies who have been instrumental in the success of this work. First of all I would like to thank the local agencies in the Northwest Indiana Air Resource Management Association consisting of Carl Weigand of Hammond, Dennis Karas and Manuel Bedella of East Chicago, Russ Boger and Dennis McGuire of Gary, Tom Myslinski of Michigan City, and Howard Ulrich of Lake County. In addition, Prof. El-Naggar of Porter County (Valparaiso University), and Berny McGuiness and Harry Williams of the State of Indiana were instrumental in the <sampling program. I also wish to thank Sam Borras and the Department of Environmental Control of the City of Chicago for providing a part of their Hi-Vol filter papers for this analysis. Wayne R. Matson, who discovered the analytical instrumentation used and who set up the laboratory, made this work possible. In addition, his consultation was invaluable in the analysis of the samples. Also to my fellow graduate students I would like to express my sincere appreciation for their advice and consideration during both my good and bad days at the laboratory. Specifically Jack Kaitala, Ken Davidson, Dale Gillette (whose long nights and sympathetic ear was always in evidence) and -ii

Ken Rahn who has been instrumental in the interpretation of both myself and the data, are appreciated. John Robbins was helpful in data reduction and presentation and is much appreciated. Also I must thank my friend and colleague, Dr. Dams, visiting us from Belgium, who was very helpful with needed advice and information. I wish to thank E. Wendell Hewson for his initial guidance in directing my interest into the field of air pollution and aerosols. His contribution to this work is primary and I am deeply indebted to him for it. The Department of Meteorology and Oceanography Faculty and Staff are acknowledged for their contributions. Prof. Ed Epstein is especially appreciated. My committee, Prof. John Winchester (Chairman), Prof. William Kuhn, Prof. Alan Cole, and Prof. K. H. Mancy, were all very helpful in their contributions and advice. This work stands as evidence of their endeavors. I am especially appreciative to Prof. Winchester, without whose advice this document would not have been possible. This work was supported in part by an Air Pollution Training Grant 2TO1AP 00007-0652, by the U.S. Public Health Service grant AP-00585, and through a Thesis Parts program with Argonne National Laboratory (A.E.C.). To my father for his invaluable advice in designing the improvements in the multiple ASV apparatus, I also owe my appreciation. -1i1

My typist Karen Young has been of infinite help in patiently typing and editing the final draft. Finally, to my wife Carolsue, who has helped in the typing and corrections and endured my trials and tribulations for almost three years, I cannot thank enough. -iv

TABLE OF CONTENTS Page ACKNOWLEDGMENTS ii LIST OF ILLUSTRATIONS ix LIST OF TABLES xv ABSTRACT xix 1.0 STATEMENT OF THE PROBLEM 1 1.1 Introduction 1 1.2 Importance of Trace Metals in Metabolism and Ecology 2 1.3 Previous Recent Surveys of Trace Metals in Atmospheric Aerosols from Available Literature 4 1.3.1 Junge 4 1.3.2 Nashville Study 8 1.3.3 Atkins 9 1.3.4 Lundgren 10 1.3.5 McMullen, Faro, and Morgan 11 1.3.6 Kneip, Eisenbud, Strehlo, and Freadenthal 15 1.3.7 Lee and Jervis 17 1.3.8 Tabor and Warner 17 1.3.9 Brar, Nelson et al. 17 1.3.10 Research Suggested by Literature Surveyed 19 1.4 Necessity and Desirability for Sampling Grid Networks 19 1.5 The Need for More Sensitivie Analytical Methods for Analyzing Trace Metals 21 1.6 Evidence of Long Range Advection by Ragweed Pollen Studies 23 2.0 THE EXPERIMENT 27 2.1 The Experimental Study of Lead, Copper and Cadmium and Related Information in the Southern Lake Michigan Basin (Chicago and Northwest Indiana) 27 2.2 Purpose of the Investigation 32 2.3 Analysis Procedures 33 2.3.1 Sample Preparation and Handling 33 2.3.2 Method of Analysis 34 -V

Page 2.3.3 Data Reduction 39 3.0 RESULTS 43 3.1 Representation of Data 43 3.2 21, 22 May 1968 50 3.2.1 21 May 1968, Chicago 51 3.2.2 22 May 1968, Northwest Indiana 52 3.3 6 June 1968 53 3.4 20 June 1968 55 3.5 9 July 1968 58 3.6 8 August 1968 59 3.7 29 August 1968 61 4.0 INTERPRETATION 131 4.1 Summations and Averages of the Data 131 4.2 Transport and Diffusion 131 4.3 Removal Processes 139 4.4 Suggested Sources —Comparison with Existing Data 142 4.5 Ecological Effects —Toxicology 152 4.6 Conclusions and Suggestions for Further Investigations 155 APPENDIX I. SUPPLEMENTAL TRACE METAL DATA 163 I.1 Research Ship Inland Seas —May 20-23, 1968 164 1.2 Marietta, Ohio, 1969 168 1.3 Mexico City 170 I.4 Rainfall 170 I.5 Fallout 173 APPENDIX II. TIME VARIATIONS OF LEAD, COPPER, AND CADMIUM CONCENTRATIONS IN AEROSOLS IN ANN ARBOR, MICHIGAN 181 II.1 Abstract 182 II.2 Introduction 183 11.3 Sample Collection and Analysis 184 II.4 Meteorology 186 11.5 Results and Discussion 189 11.6 Conclusions 197 11.7 Acknowledgments 198 11.8 Literature Cited 198 APPENDIX III. AREA WIDE DISTRIBUTION OF LEAD, COPPER, AND CADMIUM IN AIR PARTICULATES FROM CHICAGO AND NORTHWEST INDIANA 199 -vi

Page APPENDIX IV. DATA TABULATIONS AND RATIOS 229 IV.1 Meteorological Data 231 IV.1.1 East Chicago, Indiana 232 IV.1.2 Midway Airport, Chicago 234 IV.1.3 O'Hare Airport, Chicago 236 IV.1.4 Michigan City, Indiana 238 IV.1.5 Porter County, Indiana 242 IV.1.6 Surface Synoptic Weather Maps 244 IV.2 Ratios of Element Pairs, Supporting Computer Programs, and Data Location Table 253 IV.2.1 Ratios of Element Pairs 254 IV.2.2 Fortran Program for Computing Ratios and Histograms 276 IV.2.3 Raw Data Sets —Computer Input (CDC 160-A) 280 IV.2.4 Key to Data Location 302 IV.2.5 Flow Rates 306 IV.3 Data Analysis 309 IV.3.1 Data Reduction Program (160-A) 311 IV.3.2 Calibration Factors 313 IV.3.3 Program for Editing Cd Peak Heights 314 IV.3.4 Corrected Values for Cd Peak Heights 315 IV.3.5 Program for Calculating Correlation Coefficients 316 IV.4 Histograms of Data 321 IV.4.1 Pass Number 1 322 IV.4.2 Pass Number 5, 6% Significance Limits 328 IV.5 Calibrations and Responses 334 IV.5.1 Finding Calibrations and Correction Factors 334 IV.5.2 Sample Calculation 338 IV.5.3 Sample Plots of Spike Runs 1-4 340 IV.5.4 Sample Calibration Runs 345 APPENDIX V. ANODIC STRIPPING VOLTAMMETRY —THEORY AND OPERATIONS 353 V.1 Description of ASV and Basic Theory 354 V.1.1 Description of ASV 354 V.1.2 Theory of ASV Operation 355 V.1.3 Description of Physical Cell Design and Modifications 358 -vii

Page V.1.4 Comparison of Holed and Solid Electrodes 361 V.2 Operation of ASV Apparatus 363 V.2.1 Stripping Potentials 363 V.2.2 Preparation of Hg 363 V.2.3 Preparation of Spikes 364 V.2.4 New Cells 365 V.2.5 Plating of Mercury 365 V.2.6 Electrode Charging 367 V.2.6.1 Rate of Change 367 V.2.6.2 Exposure 369 V.2.7 Drawing of Base Lines 372 V.2.8 Flat Peaks 376 V.2.9 Diagnostics from the Traces 376 V.3 Running Procedures 379 V.3.1 Procedure for Cutting Filters 379 V.3.2 Procedure for Cleaning Flasks 379 V.3.3 Procedure for Digesting Samples 379 V.3.4 Codes for Flasks 380 V.3.5 Procedure for Transferring Samples to the ASV Rig 380 V.3.6 Running Procedure 381 V.3.7 Procedure for Minimizing Carry-over and Cross Contamination: Cleaning the Cells of the ASV Rig 383 V.4 Reproducibility 383 V.4.1 Static Reproducibility 383 V.4.2 Repeatability Within the Same Filter Pad 391 V.5 Calibrations: Concentration Curves, Concentration vs. Peak Area and Height 391 APPENDIX VI. DETAILS OF SAMPLING SITES 401 BIBLIOGRAPHY 411 INSERT - Metropolitan Chicago Distribution and Concentration of Industry -viii

LIST OF ILLUSTRATIONS Figure Page 1.1 A time series of pollen concentrations at 2000 ft. over Willow Run Airport (1962). 26 2.1 Lake Michigan and sampling area. 28 2.2 Key to high volume air sampling locations. 29 2.3 Key to locations of sources of meteorological data. 31 2.4 Complete ASV system, including a five module unit, plating amplifiers, stripping unit, and recorder. The cleaning units are in the background. 36 2.5 ASV cell, with pointed tip electrode. 37 2.6 Sample response curve for ASV in chloride (0.2 M). 38 2.7 Sample concentration vs. response curves, cells 1 to 4. 41 3.2.1 Wind rose for 21 and 22 May 1968. 63 3.2.2 Suspended particulate isopleths for 21 and 22 May 1968. 64 3.2.3 Suspended particulate data points for 21 and 22 May 1968. 65 3.2.4 SO2 isopleths for 21 and 22 May 1968. 66 3.2.5 SO2 data points for 21 and 22 May 1968. 67 3.2.6 Cd isopleths for 21 and 22 May 1968. 68 3.2.7 Cd data points for 21 and 22 May 1968. 69 3.2.8 Pb isopleths for 21 and 22 May 1968. 70 3.2.9 Pb data points for 21 and 22 May 1968. 71 3.2.10 Cu isopleths for 21 and 22 May 1968. 72 -ix

Figure Page 3.2.11 Cu data points for 21 and 22 May 1968. 73 3.2.12 Bi isopleths for 21 and 22 May 1968. 74 3.2.13 Bi data points for 21 and 22 May 1968. 75 3.3.1 Wind rose for 6 June 1968. 76 3.3.2 Suspended particulate isopleths for 6 June 1968. 77 3.3.3 Suspended particulate data points for 6 June 1968. 78 3.3.4 SO2 isopleths for 6 June 1968. 79 3.3.5 SO2 data points for 6 June 1968. 80 3.3.6 Cd isopleths for 6 June 1968. 81 3.3.7 Cd data points for 6 June 1968. 82 3.3.8 Pb isopleths for 6 June 1968. 83 3.3.9 Pb data points for 6 June 1968. 84 3.3.10 Cu isopleths for 6 June 1968. 85 3.3.11 Cu data points for 6 June 1968. 86 3.4.1 Wind rose for 20 June 1968. 87 3.4.2 Suspended particulate isopleths for 20 June 1968. 88 3.4.3 Suspended particulate data points for 20 June 1968. 89 3.4.4 SO2 isopleths for 20 June 1968. 90 3.4.5 S02 data points for 20 June 1968. 91 3.4.6 Cd isopleths for 20 June 1968. 92 3.4.7 Cd data points for 20 June 1968. 93 3.4.8 Pb isopleths for 20 June 1968. 94 3.4.9 Pb data points for 20 June 1968. 95 3.4.10 Cu isopleths for 20 June 1968. 96,-x

Figure Page 3.4.11 Cu data points for 20 June 1968. 97 3.5.1 Wind rose for 9 July 1968. 98 3.5.2 Suspended particulate isopleths for 9 July 1968. 99 3.5.3 Suspended particulate data points for 9 July 1968. 100 3.5.4 S02 isopleths for 9 July 1968. 101 3.5.5 S02 data points for 9 July 1968. 102 3.5.6 Cd isopleths for 9 July 1968. 103 3.5.7 Cd data points for 9 July 1968. 104 3.5.8 Pb isopleths for 9 July 1968. 105 3.5.9 Pb data points for 9 July 1968. 106 3.5.10 Cu isopleths for 9 July 1968. 107 3.5.11 Cu data points for 9 June 1968. 108 3.6.1 Wind rose for 8 August 1968. 109 3.6.2 Suspended particulate isopleths for 8 August 1968. 110 3.6.3 Suspended particulate data points for 8 August 1968. 111 3.6.4 S02 isopleths for 8 August 1968. 112 3.6.5 S02 data points for 8 August 1968. 113 3.6.6 Cd isopleths for 8 August 1968. 114 3.6.7 Cd data points for 8 August 1968. 115 3.6.8 Pb isopleths for 8 August 1968. 116 3.6.9 Pb data points for 8 August 1968. 117 3.6.10 Cu isopleths for 8 August 1968. 118 3.6.11 Cu data points for 8 August 1968. 119 3.7.1 Wind rose for 29 August 1968. 120 -xi

Figure Page 3.7.2 Suspended particulate isopleths for 29 August 1968. 121 3.7.3 Suspended particulate data points for 29 August 1968. 122 3.7.4 S02 isopleths for 29 August 1968. 123 3.7.5 SO2 data points for 29 August 1968. 124 3.7.6 Cd isopleths for 29 August 1968. 125 3.7.7 Cd data points for 29 August 1968. 126 3.7.8 Pb isopleths for 29 August 1968. 127 3.7.9 Pb data points for 29 August 1968. 128 3.7.10 Cu isopleths for 29 August 1968. 129 3.7.11 Cu data points for 29 August 1968. 130 4.1 Locations of fossil fuel burning industries. 144 1.1 Trajectory of research vessel Inland Seas, 20-23 May 1968. 166 1.2 Wind rose for August 1969. 175 1.3 Lead fraction of total dust fall. 176 1.4 Copper fraction of total dust fall. 177 1.5 Estimation of traffic densities. 179 II.1 Location of sampling area in relation to Detroit. 185 11.2 T, RH, Td versus sample time. 188 11.3 Wind speed and direction versus sample time. 188 II.4 Total concentrations of Pb, Cd and Cu vs. time. 190 11.5 Average particle size distributions of Pb, Cd, and Cu. 191 IV.1.6.1 Synoptic analysis for May 21, 1968 (ESSA). 245 IV.1.6.2 Synoptic analysis for May 22, 1968 (ESSA). 246 -xii

Figure Page IV.1.6.3 Synoptic analysis for June 6, 1968 (ESSA). 247 IV.1.6.4 Synoptic analysis for June 20, 1968 (ESSA). 248 IV.1.6.5 Synoptic analysis for July 9, 1968 (ESSA). 249 IV.1.6.6 Synoptic analysis for August 8, 1968 (ESSA). 250 IV.1.6.7 Synoptic analysis for August 29, 1968 (ESSA). 251 IV.5.3.1 Spike runs, 1835-1912, Cell 1. 341 IV.5.3.2 Spike runs, 1835-1912, Cell 2. 342 IV.5.3.3 Spike runs, 1835-1912, Cell 3. 343 IV.5.3.4 Spike runs, 1835-1912, Cell 4. 344 IV.5.4.1 Sample calibration runs, Cells 1-4, Run No. 952, Peak Height, Cd. 346 IV.5.4.2 Sample calibration runs, Cells 1-4, Run No. 952, Peak Area, Cd. 347 IV.5.4.3 Sample calibration runs, Cells 1-4, Run No. 952, Peak Height, Pb. 348 IV.5.4.4 Sample calibration runs, Cells 1-4, Run No. Peak Area, Pb. 349 IV.5.4.5 Sample calibration runs, Cells 1-4, Run No. 952, Peak Height, Cu. 350 IV.5.4.6 Sample calibration runs, Cells 1-4, Run No. 952, Peak Area, Cu. 351 V.1 Simplified plating circuitry. 357 V.2 Cell cross section and equivalent electronic circuitry. 360 V.3 Comparison of holed versus solid electrode response. 362 V.4 The change of charging current at 0.2 volts with time. 368 V.5 Drawing of base lines. A-B represents the slant line method and A'-B the horizontal method. 379 -xiii

Figure Page V.6 Static reproducibility, Cd. 388 V.7 Static reproducibility, Pb. 389 V.8 Static reproducibility, Cu. 390 V.9 Concentration versus peak height, Pb. 394 V.10 Concentration versus peak area, Pb. 395 V.11 Plating time constants versus response. 398 VI.1 Suspended particulate Monitoring Network, Chicago, Illinois. 402 VI.2 Telemetered data stations, Chicago, Illinois. 407 VI.3 Typical high volume air sampler with wooden shelter. 410 -xiv

LIST OF TABLES Table Page 1.1 Junge (1963) 6 1.2 Junge (1963) 7 1.3 Selected Particulate Constituents as Percentages of Gross Suspended Particulates (1966-1967) 14 1.4 Analysis of Wind Transport of Pollen from Wisconsin, over Lake Michigan and Southern Michigan, to Ann Arbor, as Observed by Airplane Concentration Measurements at Ann Arbor, August 27-30, 1962 25 3.1 Atmospheric Concentrations of Cadmium, ng/m3 44 3.2 Atmospheric Concentrations of Lead, ng/m3'45 3.3 Atmospheric Concentrations of Copper, ng/m3 46 3.4 Atmospheric Concentrations of Bismuth, ng/m3 47 3.5 Atmospheric Concentrations of Total Suspended Particulate, pg/m3 48 3.6 Atmospheric Concentrations of SO2, ppb 49 4.1 Average Meteorological Characteristics 132 4.2 Average Concentrations for Each Day in Chicago and Northwest Indiana 133 4.3 Average Values of Selected Ratios for Each Day in Chicago and Northwest Indiana 134 4.4 Correlation Coefficients 135 4.5 Contributions of Fuels to Lead, Cadmium, and Copper to Chicago Area Suspended Particulate 145 -xv

Table Page 4.6 Comparisons of Average Ratios from This Study to Independent Data 146 4.7 Comparison with NASN 1963 Data, ng/m3 151 4.8 Comparison to Toxic Levels 153 1.1 Inland Seas Data for 20-23 May 1968 165 1.2 Hi-Vols Taken of Marietta, Ohio, Region, 1969 169 1.3 Mexico City Hi-Vol, 1964, and Low Vol, 1968 171 1.4 Rainfall, June 26, 1968 172 2 1.5 Dust Fall for August 1969, mg/m -month 174 II.1 Meteorological Data 187 11.2 Average of 21 Runs Minus Blank Stages 192 11.3 Gross Sum of All Stages for Each Run 193 11.4 Lead on Individual Stages 194 IV.1.1 Meteorological Data for East Chicago, Indiana, 1968 233 IV.1.2 Wind Data - Midway Airport, Chicago, Illinois, 1968 235 IV.1.3 Wind Data - O'Hare Airport, Chicago, Illinois, 1968 237 IV.1.4 Meteorological Data - Michigan City, Indiana, 1968 239 IV.1.5 Porter County Wind Data, 1968 243 IV.2.4 Locations of raw data points 303 IV.2.5 Average Flow Rates 307 IV.5.1 % Decrease per Sample Run 336 V.1 Charging Current as a Function of Various Conditions 370 V.2 Final Charging Current at 0.2 V, mm 371 -xvi

Table Page V.3 Slant vs. Horizontal Base Line - Cd 375 V.4 Carry-over Using Wash-Bottle Stream 384 V.5 Static Repeatability 386 V.6 Static Repeatability - 10 Minute Plating 387 V.7 Reproducibility within the Same Filter Pad 392 V.8 Concentration vs. Peak Area and Peak Height 393 V.9 Plating Time Constants: 200 ng Pb Spike 397 VI.1 Station Key for Northwest Indiana Air Sampling Network 403 VI.2 City of Chicago, Department of Air Pollution Control - Technical Services Division, Suspended Particulate, Sulfur Dioxide and Dust Fall Monitoring Network, Sampling Stations 405 VI.3 Meteorological Stations, Northwest Indiana 406 VI.4 Northwest Indiana Sampling Network Random Sampling Schedule, 1968 408 VI.5 Northwest Indiana Sampling Network Random Sampling Schedule, 1969 409 -xvii

ABSTRACT AREA-WIDE DISTRIBUTION OF LEAD, COPPER, CADMIUM, AND BISMUTH IN ATMOSPHERIC PARTICLES IN CHICAGO AND NORTHWEST INDIANA: A MULTI-SAMPLE APPLICATION OF ANODIC STRIPPING VOLTAMMETRY by Paul Roger Harrison Chairman: John W. Winchester Standard air pollutant measurements such as dust fall, SO2, and total suspended particulate for certain regions in the United States have been well documented for several years, but few measurements of elemental composition of airborne particulates have been reported. This study attempts to extend the list of basic monitoring parameters into the realm of elemental composition of aerosols on an area-wide, simultaneous basis in the southern Lake Michigan region in order to exhibit the feasibility and usefulness of such studies. In addition, more sensitive analysis techniques are further developed. As a first attempt to exhibit the usefulness of areawide surveys of elemental composition in aerosols in the Chicago and Northwest Indiana region, lead, copper, cadmium, and bismuth were analyzed from standard fiber glass filters obtained from the local high volume sampling networks. The sampling periods consisted of six weekdays selected from the summer months (May - August) of 1968 at nearly 50 stations which were well dispersed throughout the region. -xix

During the analysis of these samples the highly sensitive techniques of anodic stripping voltammetry (ASV) were documented, and the physical characteristics of the cell design and hardware were further improved for routine use with multiple analysis. Small variations in the distributions of these elements were found throughout the area except for an anomalous concentrated source of copper in East Chicago, Indiana, which 3 reached values of greater than 10 pg/m. The total average 3 concentrations were 19, 1900 and 1000 ng/m for Cd, Pb and Cu respectively. The average copper concentration in the 3 Chicago area was 230 ng/m and represents the non-anomalous average. The source of the anomalous copper is not yet conclusively known. Comparisons with diffusion models where possible resulted in satisfactory results and an estimated source strength of 13 metric tons per year was proposed. When comparisons with estimations of source strengths and distributions were tried the results suggested that lead aerosols were emanating almost completely from automobiles; whereas most of the cadmium and non-anomalous copper aerosols can be explained by fuel-burning sources. However, comparisons of the sulfur dioxide with the estimated inventories predict that the concentrations of these trace elements are higher than expected, or that the sulfur dioxide values reported by the local agencies are too low by a factor of 10, which is unlikely. This problem is not satisfactorily explained as yet although plausible arguments can be given. -xx

Further studies in this area can be suggested and facilitated by the data and supporting information presented in this work. -xxi

1.0 STATEMENT OF THE PROBLEM 1.1 INTRODUCTION From the academic point of view, we sometimes justify our research by the faith that something useful will result from our initial endeavors. There are some areas in which the importance and immediate need for investigation, and application of those results, are clearly in evidence. One such area is that of environmental management in general, and trace metals in particular. The importance of trace metals in the metabolic process of all living organisms is obvious, in a broad sense, but not always well documented as to cause and effect relationships, especially at low levels of chronic exposure. It is not my purpose to review the literature of trace metals and their effect on organisms; indeed, to do so would be to review thousands of articles concerning lead alone. The purpose of this study is to investigate the concentrations and sources of three trace metals as found in atmospheric aerosols in a heavily industrialized region, their transport to some of the adjacent rural areas, and their possible effect on the trace metal content of southern Lake Michigan waters. In additinn, very sensitive analytical devices and techniques are further developed and used. Finally, some suggestions concerning the usefulness of some of the present day methods of monitoring trace metals in aerosols can be drawn from the data -1

-2and remedial action is suggested. 1.2 IMPORTANCE OF TRACE METALS IN METABOLISM AND ECOLOGY An interesting observation is that man is now passing through the metal age and is already entering a new age —the age of organics. The "plastic age" is a probable pseudonym with plastic money and other plastic substitutes being in abundance. This digression is useful only to point out how little we know about the effects of present pollutants as compared to the future problems from a, potentially, vastly larger variety of organic compounds and their possible combinations with trace elements. Many trace metals are highly toxic to the organism, but others are necessary for life functions and without them we could not continue to exist. Simply looking at the table on a vitamin bottle will show many of the more necessary trace elements needed in man's metabolism. Phosphorus, iron, magnesium, zinc, calcium, iodine, and copper are found in the more expensive vitamin pills. What these metals contribute to the more efficient metabolic process is not completely known. In fact, larger amounts of these same elements are debilitating if not toxic. A few examples of toxic elements being emitted directly into the environment are lead in automobile gasoline, thallium in some rat poisons, lanthanum as a defoliant, and copper as an algicide. Most are used in combination with other elements or as organic complexes.

-3The three metals we studied, lead, copper and cadmium, are classified in a broader unit called heavy metals, or those with a density greater than five. There are 40 elements so classified, and they are biologically important due to their inability to combine with a wide variety of organic molecules. In the organisms they can be thought of as "enzyme inhibitors," because they often combine more firmly with biologically important molecules than do the lighter metals. In fact, all the enzyme systems can be shown to be inactivated by heavy metals. In many cases the necessary amount of heavy metal needed to inhibit the system is very low (Passow et al., 1961). The three trace metals studied can be classified as toxic in sufficient amounts (Threshold Limit Values for 1966). Their specific effects are still open to question and the reader is referred to the literally thousands of references (Flury et al., 1934) found on the subject. More recently cadmium is under new investigations. It is an important fact to keep in mind that the ecological effects of heavy metals found in the environment depend very much on their chemical forms. For example, if the element is tightly bound to another element or molecule it is less accessible to interactions with other chemical systems. If the element is in a neutral state and not ionized, it is more likely to react because of the diffusion barrier of the cell membrane to ionized molecules. Mercury is a good example. Valence and solubility are similarly important. Thus it is not sufficient to comment on toxicity of pollutants

-4alone, but we must know their form in order to ascertain the transport mechanism, the likely location of deposition, and their final effect on the particular part or system of the organism (receptors) involved. This problem will become more evident as we further understand the toxicity of various forms of trace metals. An excellent introduction to the subject of heavy metals and biological processes has been written by Passow et al. (1961). 1.3 PREVIOUS RECENT SURVEYS OF TRACE METALS IN ATMOSPHERIC AEROSOLS FROM AVAILABLE LITERATURE 1.3.1 Junge The literature prior to 1960 is thoroughly reviewed in the classical work of Junge (1963). In this text are studies of many areas concerning aerosols including both chemical and physical properties, such as formation and size distribution. Two sections are of primary interest concerning trace metals. In section 2.3, "Chemical Composition of Tropospheric Aerosols," there are references to Chambers et al. (1955). These data were taken from a United States Public Health Service study of 30 cities using glass fiber filters for a period of more than one year. These filters were analyzed for several trace metals. The study was broken into two parts. The first is concerned with urban areas of populations between 5,000,000 and 2,000,000, including seven major cities. In the second classification are five nonurban areas (nonurban defines as suburban as opposed to rural). Data are presented for sulfate,

-5nitrate and ten metals: iron, lead, fluorine, manganese, copper, vanadium, titanium, tin, arsenic, and beryllium; see Junge's tables 33 and 34 in Tables 1.1 and 1.2. In section 5.2 of the Junge text, "Composition of Polluted Atmospheres," calcium, aluminum, iron, magnesium, lead, manganese, copper, zinc, and titanium were studied for 30 metropolitan areas in the United States and Alaska. Averages were calculated for each of these elements. From this 1956 study, the average copper value measured was 0.1 microgram per cubic meter (0.1 Pg/m ), and the lead value was 2.0 pg/m. There are no data for cadmium and we can probably assume that it was present only in very low quantities. It is important to note that all of these data came from single point sampling in each area or, at very best, the averaged values of just a few stations. The state of are-wide sampling of trace metals in aerosols is best seen by noting the length of the discussion, "On the Area of Influence Around the Centers of Pollution." This discussion is less than two pages long and cites only sulfur dioxide data. As far as Junge is concerned, there had been little area-wide trace metal study prior to 1960. Two significant exceptions are Tabor and Warmer (1958, Section 1.9) in Toronto and the International Joint Commission in Detroit-Windsor (1960). Of the three metals presented in this paper the most extensively investigated was lead. In the last decade there have been numerous articles concerning lead content of atmospheric aerosols. It was found in these studies that the

Table 1.1 Junge (1963) TABLE 33 PARTICULATE ANALYSES IN.g/m3 FnoM CITIES HAVING POPULATIONS BETWEEN 500,000 AND 2,000,000 Cinciinati Kansas City Portland Atlanta Houston San Francisco Minneapolis (Oregon) Total load 176 146 143 137 129 104 120 Acetone soluble 31.4 18.4 32.1 24.2 18.5 19.4 i5.8 Fe 4.5 4.1 5.1 3.3 4.0 2.4 4.4 Pb 1.6 1.0 1.2 1.8 1.0 2.4 0.5 F- 0.21 0.01 Nil 0.05 Nil 0.37 0.06 Mn 0.24 0.08 0.23 0.12 0.23 0.11 0.08 Cu 0.18 0.04 0.05 0.01 0.02 0.07 0.60 V 0.09 0.002 0.009 0.024 0.001 0.002 0.002 Ti 0.06 0.21 0.24 0.12 0.29 0.04 0.11 Sn 0.03 0.03 0.01 0.03 0.02 0.02 0.01 As 0.02 0.02 0.02 <0.01 0.01 001 0.01 Be 0.0002 0.0003 0.0003 0.0002 0.0002 0.0001 0.0002 So4 5.6 1.5 0.8 1.0 2.4 1.8 0.8 NO- 1.0 0.6 0.2 0.8 1.0 3.4 1.3 a Chambers et alz. (1955).

-7Table 1.2 Junge (1963) TABI3E 34 PAkIRTIWULArTE AN;ArLYSES IN /lg/rnz1 FROM NI ONUIPBAN AlEAS a Salt.Lake.Portland Boonsboro Altlanta Cincinnati City (Oregon) Total load 68 55 71 45 86 Acetone soluble 8.7 6.2 9.3 9.0 12.6 FIe 3.7 4.1 2.7 2.4 3.6 Pb 0.1 0.1 0.9 0.4 0.3 F- - - Nil 0.26 - Mn 0.00 0.04 0.11 0.07 0.04 Cu Nil 0.28 0.01 0.19 <0.01 V' 0.003 Nil 0.004 <0.001 0.002 Ti 0.26 lTil 0.13 0.01 Nil Sn1 <. 01 <0.01.1 0.01 0.01 <0.01 As 0.01 0.03 0.01 <0.01 0.04 Be 0.0001 <0.0001 0.0002 0.0001 0.0001 SO' 0.3 <0.01 0.5 1.9 0.4 N03 - - - 0.7 - a Chambers et al (1955).

-8probable source of lead in the atmosphere is due to emission of lead halide particles from motor exhaust. Each gallon of gasoline contains two grams of lead as tetraethyl lead which is carried out of the exhaust system by halogens, also added to gasoline as ethylene dichloride and dibromide in the ethyl fluid mixture. Almost all of the studies cited were taken from a single point sampling or were not simultaneous. Recently there have been a few papers concerning more than one simultaneous sample. 1.3.2 Nashville Study In 1960 and 1961 there were several articles presented concerning a study in the Nashville, Tennessee, area (Nashville, 1960-61). This study is probably one of the most thorough attempts at discerning the density of sampling stations and the sampling gate that is optimum for a compromise between number of stations and sample period. The concept is that the larger the number of stations the shorter the sampling time needed to realize a representative description of the area. One hundred and nineteen stations were well distributed within Nashville and surrounding districts. Several subsets of stations were selected for the use of various criteria. Virtually no trace metals were analyzed in this study, however, and the information is applicable to our work in that if one is designing such experiments he could do well to read these articles and design his experiment according to the results of this study, as opposed to using sampling stations already in existence.

-91.3.3 Atkins Atkins (1970) used a three point sampling network in the San Francisco Bay region, of which one point was very close to traffic, the second was two and one half miles from a freeway, and the third was five miles from a freeway. At each station, high volume sampling of suspended particulate, dry fallout, and rainfall were measured, and lead was extracted by the dithizone technique. Atkins stated that he was able to measure as little as five minute samplings close to the highway, that is, ten cubic meters of air. However, his data were presented only as 30 minute averages. This work is timely but has some severe limitations. First the sampling was not done over a 24 hour period. Most of the data were taken during waking hours of 5 a.m. to approximately 6 p.m. As most meteorologists know, and have shown quite explicitly, this is probably insufficient to show the diurnal variations as well as the dependence upon climatological factors. In addition, it is obvious that insufficient meteorological data were taken. A topographical map of the region was not presented nor was wind direction. The study did show that less lead was found when farther from the source of lead aerosols, both in rainfall and fallout, and in suspended particulate. Also, a dependence on traffic flow and atmospheric mixing was shown; however, proper parameters were not measured and these data cannot be sorted out easily. It is interesting to note that the solubility of lead particulate increased as one got further from the source,

-10that is, the traffic. Since rainfall intensities were not taken, any conclusions concerning condensation nuclei by lead particulate or of the scavenging process is highly suspect. An additional and potentially serious problem found in many other papers presenting lead values is that a chloroform method of extraction was used with subsequent use of a dithizone indicator. (The lower limit of sensitivity in this study is said to be 0.5 pg.) In some cases, this method seems to be in error and may underestimate the amount of lead present (NASN, 1966; Kneip, 1970). We will discuss this matter more extensively later in the paper. 1.3.4 Lundgren An additional, pertinent reference to lead monitoring is by Lundgren (1969). In this study samples were taken for four hour sampling periods during a 15 day period at a station located 50 miles from Los Angeles, California. This would imply that the aerosol would be aged somewhat if one neglects any local sources. The samples were taken on glass fiber filters, and total particulate, particulate sulfate, nitrate, and lead concentrations were measured. In addition, size distributions were measured for a 16 hour period between 4 p.m. and 8 a.m. The lead was analyzed by atomic absorption spectroscopy. A 24 hour total suspended particulate and total sample was run for control with some losses found. In addition, a four stage impactor followed by a filter was used for lead and the other measurements listed above. The average suspended 3 particulate value was 100 pg/m, and the average lead

-113 concentration was 0.6 pg/m. One significant factor to observe is a variation in the lead concentration between the four hour time gates, and the mass-median diameter also seems larger than the average values observed near the sources. This is explained by the author to be the coagulation effects due to the aging of aerosols. The average mean diameter is 0.5 microns for this study. Several days were observed having a particulate lead mass mean diameter of 1.0 microns and disagrees somewhat with recent data in our sample area (Gillette, 1970). This larger than average mean diameter occurred mostly during the summer days of high smog. Again, this was single point sampling. 1.3.5 McMullen,Faoro, and Morgan One cannot discuss trace metals in atmospheric aerosols without mentioning the National Air Sampling Network (NASN) analysis (USPHS, 1968). These data provide averages and frequency distributions for about 30 pollutants including 17 trace metals as well as gases and solids. There is little information available from these studies concerning the seasonal effects of trace elements and the effects of the station location within the urban areas. A more recent supplement to this work is presented by McMullen,Faoro and Morgan (1969) of the United States Department of Health, Education, and Welfare. Their approach was to average a three month period, consisting of 30 nonurban stations and 117 urban stations. Analyses of ammonium, nitrate and sulfate ions, and metals were completed. A significant

-12change in procedure was that a low temperature ashing process was used with the metals. Previous analysis used a high temperature procedure to free the metal ions. The authors state that the loss was decreased by a factor of five for some metals, especially for volatile materials such as lead, zinc, and cadmium. Thus they indicate that there is a possibility of lack of sensitivity, if not accuracy, in previous studies. Copper, lead, titanium, and vanadium are outstanding insofar as both the urban and nonurban stations seem to have two overlapping but distinct groups of concentrations. The distinct vanadium concentrations are said to be geographical, probably because of the variability of domestic fuels used in heating. That is, imported fuels often contain a higher percentage of vanadium than do those of local or domestic origins. Aside from monitoring seasonal variations, the classification of stations was broken down into two large areas named "urban and nonurban." The nonurban stations were further broken down into three areas: "remote, intermediate, and proximate." Proximate stations are technically nonurban but are obviously influenced by their closeness to large urban centers, intermediate stations are relatively close to populated areas but are also located in agricultural communities, and remote stations are furthest from large population and industrial centers. Their significant conclusions concerning trace metals are that nickel, iron, manganese, ammonium ions, and nitrate ions are present at constant percentages in the remote and intermediate categories, the implication being that

-13these materials are probably present in the background. Copper and sulfate ions seem to be in constant amounts in the proximate and urban categories, and indicate that these substances are probably from urban areas and are advected to the proximate areas. In their final remarks McMullen et al. point out that the nonurban stations have ranges of materials in airborne aerosols from one half to one tenth those found in urban stations. However, the proximate stations nearest the cities range from two to ten times the concentrations of those of the remote stations. This is the same ratio given for urban versus nonurban. From these values we can gain insight into the rate decrease in values of pollution materials from urban areas as they advect to the nonurban areas. For two of the metals studied we can see that this is probably true. See Table 1.3. The copper values are the same in the urban and proximate stations, decreasing markedly to the intermediate and remote. Lead decreases fairly rapidly at an increasing rate from the urban to the nonurban areas. Although the filter pads were analyzed for quarterly values or averages, they were not presented as seasonal values. The value of this paper to our study is that one can gain additional perspective into the drop off values of various pollutants, in this case trace metals, as one progresses from urban to nonurban to rural locations, as well as giving us real numbers to compare.

Table 1. 3 SELECTED PARTICULATE CONSTiTUENTS AS PERCENTAGES OF GROSS SUSPENDED PARTICULATES (1966 -1967).1,URBAB-N j NONURBAN (217 Staltions) j Proximacte (5) Intermediat (15) j Remote (OC) ___3 | _ _!C pg/m% P3f % K i/m3 % Suspnded Pcricaes 102.0 45.0 40. Benzene Soiuble Or;. 1 6.7 6.6 | 2.5 5.6 2.2 5.4. 5. Arrmondum,?cn 0.9 0.9 1.22 2.7 0.28 0.7 0.15 0.7 rc. a c) n I":~~~, 8`5 I2~ 0.46 12.2 2.4 2.4 1.40 3.1 0.5 2.1 0.46 1.2! ~ ~~~~~~~~~~ I l10.0 2 A2.2 O.70 Su jrct e ion j 10.1 9. 9 1. 2.25 9 13 12.51 11.8 Copper S0.16 O. i5 [ 0.16 0.36 0..060.2 Copper 9~~~~~~~~.a8i~.? 0,060 0. 28 I!on I 1.43 1.38 3 0.56 1.24 0C.27 0.67 0.15 0.71 MnrZjne ~Se 0.0 0,0 > 0.2 0.07 6026 0.06 I 0.03 0.0050.02 Nickef 0.017 0.02 0.008 0.02 0.004| 0.01 0.002 0.01 Leqd 1.11 1.07 0.21 0.47 0.096 0.24 0.022 0.10 After McMullen et al. (1969).

-151.3.6 Kneip, Eisenbud, Strehlo, and Freudenthal A recent study, and probably one of the more complete works, is by Kneip, Eisenbud, Strehlo, and Freudenthal of the New York Medical Center (1969). The researchers took weekly samples for a full year using 20 x 25 cm (8 x 10 inch) glass fiber filters (Hi-Vol) at three and sometimes four stations located on Manhattan Island, New York. Again, an ash method was used for the trace metals and the analysis was by atomic absorption. The trace metals involved were lead, vanadium, cadmium, chromium, copper, manganese, nickel and zinc. Lead210, total particulate, and benzene and acetone soluble organic materials were also determined. A fair amount of meteorological data was also used and seasonal, and source influences were examined. Significant inverse correlations of temperature with suspended particulate, vanadium, and nickel; and of average wind speed with lead, copper and cadmium; and direct correlation of temperature with lead, copper, and cadmium; point out the great necessity of properly measuring and presenting meteorological data with any of these urban studies. Urban areas are so complicated with respect to meteorological conditions and the profusion of source strengths and locations as to make it difficult to readily determine the source of trace metal pollutants by simply measuring trace metals alone. In this study, meteorological variables may not be quite as important because of the time gate of one week. However, observations that lead, copper, and cadmium seem to be higher in the summer than in the winter can be explained by the

-16higher ventilation of the city in the winter than in the summer. In fact, their data bear out this conclusion. A variable not presented in any of these papers is ratios. That is, even though the ventilation rates may be different, if the sources are the same and are unique, such as coal or oil, the ratios should remain constant for all seasons. This would be true even if the rates of consumption of the materials at the pollution source were different. In fact, taking the cadmium to copper ratio we find a value of 0.1. This is within the error limits of the ratio of cadmium to copper present in fossil coal fuel. This average is represented within 75% at all three stations and is within the error limits of the determination of the metals themselves. The average concentrations of lead, copper, and cadmium are 3.1, 0.2, and 3 0.02 pg/m3, respectively, for the three Manhattan Island stations. A significant development in this work is that the lead concentrations seem to be 2 to 2.6 times higher than those of the NASN studies. This is an observation that we have made especially for low level rural areas. In a few hundred values, both in urban and nonurban areas, and in an intrusion 3 of polar air we have found no less than 0.1 pg/m of air taken over as little as a two hour average. This may be due to the extraction and ashing methods mentioned previously by McMullen et al. (1969). From this study some conclusions can be made, but isopleths of concentrations cannot be drawn nor can a realistic comparison with rural or "non-polluted" areas be

-17made. In other words, to this date there have been very few simultaneous studies of adjacent areas containing industrial, urban and rural areas. 1.3.7 Lee and Jervis In 1968, Lee and Jervis published results for 13 elements in 30 samples in Toronto measured by neutron activation analysis using a NaI crystal. These metals are calcium, iron, sodium, zinc, bromine, arsenic, copper, silver, antimony, cobalt, scandium, mercury, and lanthanum, ranked in order of decreasing average concentration. 1.3.8 Tabor and Warner An earlier study by Tabor and Warner (1958) is a study of 28 cities for 17 metals: antimony, barium, beryllium, bismuth, cadmium, chromium, nickel, tin, titanium, vanadium, and zinc. Iron, zinc, copper, lead, and manganese as presented represent an order of decreasing concentrations; that is, iron is the most abundant in the city study. The technique of analysis used was emission spectrometry. The criticism, again, is that the samples were not simultaneous and adjacent. In this study 3 cadmium ranged from 2 to 100 ng/m, lead from 0.33 to 17.0 Pg/m3, and copper from 0.05 to 30 pg/m3 1.3.9 Brar, Nelson et al. Brar, Nelson et al. (1969,1970) published the results of a study involving over 20 stations in the city of Chicago in which several trace elements were measured by neutron

-18activation analysis. By virtue of using neutron activation analysis two presentations were secured, one for short-lived isotopes of trace metals and the other for longer-lived isotopes of trace metals. Twenty-one metals in all were presented. The samples were taken in one simultaneous 24 hour period in April, 1968. All stations, except that at Argonne National Laboratory, were in the urban or industrial regions of Chicago. Although isopleths were not drawn, the data could lend themselves to the drawing of a few. No meteorological data are presented with the papers. The significant points made in the Brar et al. paper are that (1) area-wide samples need to be made to show the variations and true concentration within an urban and industrial region, and (2) that simultaneous measurements are also necessary. Since no highly localized sources were found, and since only one day was presented, there could not be much meteorological analysis. Despite this limitation, this paper is an excellent presentation of a pioneering work to attempt simultaneous area-wide surveys throughout a metropolitan area. It should be pointed out that a severe limitation for this type of study is the inability to find suitable, clean filter paper to be used on standard 20 x 25 cm high volume samplers that are commonly used throughout the United States. If suitable filter paper was available we could easily find many trace elements from pollution and natural sources by distributing these filter papers to local control officials for exposures, and thus minimize the sampling program for the researcher.

-19Since the institution of our program in May of 1968, contacts between the University of Michigan and Argonne National Laboratory have been made, and this and other problems concerning simultaneous area-wide sampling have been explored (Harrison et al., 1970). 1.3.10 Research Suggested by Literature Surveyed The previous paragraphs discussing work presented in papers and journals to this date point out three major needs. One is for sampling grids or networks as opposed to the relatively few National Air Sampling Network and CAMP stations in each metropolitan area. Second is the need for more sensitive methods of analysis, and third is the careful monitoring of meteorological parameters pertinent to the transport and removal process. 1.4 NECESSITY AND DESIRABILITY FOR SAMPLING GRID NETWORKS It is clear from the discussions by Kneip, McMullen and others that there is a great desirability by researchers and control personnel to gain a more detailed knowledge of the areas under study. For example, Jutze and Foster (1967), in their article concerning the recommended standard method for atmospheric sampling of particulate matter by high volume filters, recommended a compromise between urban areas and industrial areas; the placement should be as representative as possible for the total area, and so forth. In other words, most National Air Sampling Network stations, but not all, are

-20placed to procure the most representative rather than the most severe concentrations of atmospheric pollutants in atmospheric aerosols. This attempt probably satisfies some receptor criteria, and due to the practical considerations of economics, is most likely the best compromise from all points of view. However, as analytical methods become more sensitive and more available to the control officers and local air pollution officials, there should be a re-examination of this concept as a national monitoring network. In this following work it will be shown that the National Air Sampling Network is not detecting some important pollution sources in an urbanindustrial area, and that, in some cases, even the data obtained may be suspect due to the lack of sensitivity of the analytical procedure, e.g., lead. It is suggested that when a method becomes available studies should be instituted using a reasonably sensitive grid over a reasonable number of days under various meteorological conditions and should be done periodically and in great detail. The impetuses for this type of study are (1) it will find sources deleterious to the health of adjacent urban areas, or rural areas for that matter, (2) it will provide detailed information with which to model air pollution incident contingency plans, and (3) it will also be available for both industrial and scientific analysis and for reference for legal liability or lack thereof. A severe drawback is the chance that certain industries will change their process during the sampling periods, or that the processes may not be continuous in the first place and would be missed.

-21However, most industries of any size cannot, and probably will not, change their methods of production even for a pollution study unless the study shows that there is pollution in sufficient amounts to suspect their emission of some unpleasant or undesirable trace metal or other pollutant. If this is the case, I am sure, perhaps naively so, that industry and government and the general public would like to know as soon as possible. Some National Air Sampling Network stations can be relocated as a result of these studies in order to monitor any changes, especially increases, in certain types of trace metals. In other words, the stations should be located according to this type of survey in order to sample the desired parameters or pollutants, rather than based upon some good but subjective criteria. One of the major problems with the National Air Sampling Network and CAMP stations for that matter, is that the method of analysis used is usually not very sensitive and requires long periods of preparation. The presentation of the following results will probably illuminate and support this argument. 1.5 THE NEED FOR MORE SENSITIVE ANALYTICAL METHODS FOR ANALYZING TRACE METALS We have mentioned previously the prevalent use of neutron activation analysis for trace metals. We have also discussed the problem of the lack of clean filter papers for routine use, as the glass fiber filters are used in the high volume sampling networks. What is desired is a clean filter paper

-22for neutron activation analysis (or any other type of analysis), and a method of great sensitivity that can be used with the present glass fiber filters. Neutron activation analysis is more sensitive for some trace metals than for others, but, again, is not generally available because of the necessity for special filter papers and a nuclear reactor. Since atomic absorption and wet chemistry were not used in our study, we will not discuss them except to say that these methods are usually more time consuming and less sensitive. Three to six trace metals can be measured by a relatively new development in anodic stripping voltammetry (ASV). This method (instrument) using a composite mercury graphite electrode can measure bismuth, indium, lead, copper, cadmium, and zinc (plus a few others with special reagents) to sensitivities of less than one nanogram in situ (Matson, 1968). Routinely we have analyzed less than one half a cubic meter of air for urban areas with adequate sensitivity. We have the capability of measuring only a few trace metals, but with minimum preparation and great sensitivity. It is, however, a great step forward for these three to five trace metals. In addition, we have discovered, and are reinforced by Kneip et al. (1969), that the chloroform extraction and dithizone technique for lead is, in all probability, in error and is giving lead values that are too low. The probable cause for this error is that a great deal of sample preparation is required prior to using the indicator. This is not to criticize the analyst but to criticize the method of analysis. We

-23will discuss both method and sensitivity and sample preparation of anodic stripping later in the text and Appendix V. Thus one of the most severe restrictions in the study of airborne trace elements is the unavailability of sufficiently sensitive analytical techniques, and problems with high blanks in the sampling materials. We propose, therefore, to offer ASV as a solution for at least four trace elements using regular glass fiber filters and many more elements by neutron activation analysis if a suitable filter paper is found (Brar and Nelson, 1969; Dams et al., 1970). Finally, the question arises as to whether urban pollutants really do influence the adjacent areas and to what extent. The answer can lie within some studies involving ragweed pollens exhibiting evidence of their advection over large distances. 1.6 EVIDENCE OF LONG RANGE ADVECTION BY RAGWEED POLLEN STUDIES If advection of pollen does indeed occur over substantial distances, with west winds the effect of Lake Michigan should be discernible to the east. On days with high pollen emission the morning peak of emission will occur over Wisconsin and over lower Michigan, but not over Lake Michigan. As these concentrations are advected eastward, the effect of the lake should appear at Ann Arbor as an afternoon minimum (no pollen from Lake Michigan) followed by a rise in the early evening as the morning peak of Wisconsin pollen arrives. A series of

-24airplane soundings taken at Ann Arbor during the period of August 27-31, 1962, were analyzed for evidence of this lake effect. The measured pollen concentrations at 2000 ft. for August 27, 28 and 30 are shown in Figure 1.1; unfortunately no flight was made at about 20 h on August 29 so the earlier observations for that are not shown. The advection distances are as follows: Milwaukee to Ann Arbor - 330 km, Muskegon or Holland, Michigan, to Ann Arbor - 210 km The wind speeds and directions given are an average of the 850 mb values for Green Bay, Wisconsin, and Flint, Michigan. The results of the analysis are given in Table 1.4 Figure 1.1 shows that an afternoon minimum did indeed occur on each of the three days for which appropriate concentration measurements were available. The wind data and other information in Table 1.4 are entirely consistent with the thesis that the afternoon minima are due to the absence of pollen emission over Lake Michigan. It should be emphasized that the time of maximum concentrations in Figure 1.1, being for 2000 ft., need not and do not agree with the times of surface high values given in Table 1.4. The table thus indicates that for this period of W to WSW winds an afternoon maximum in pollen concentrations attributed to Lake Michigan did indeed occur. No such maximum should occur, on this basis, with S or SE winds, but unfortunately no airplane observations were made with such winds.

-25Table 1.4 Analysis of Wind Transport of Pollen from Wisconsin, over Lake Michigan and southern Michigan, to Ann Arbor as Observed by Airplane Concentration Measurements at Ann Arbor, August 27-30, 1962 Date Wind Advection Time of Time of Speed Dir. Time to morning Advection (km hr-1) (deg.) Ann Arbor High Conc. High Conc. (hrs) at surface Calc. Obs. 1962 Aug.27 29 280 11 0930 2030 20 Augg.28 29 280 11 0930 2030 20 Aug.29 32 273 10 1000 2000 no data Aug.30 32 241 10 1030 2030 20

800 go~ 600-~ ~ 9~;~?\AUGUST 30, 1962 Uj6O -j _AUGUST 27, 1962\ I 400 0 N) ~~tea z 200 200 AUGUST 28,1962 0 04 06 08 10 12 14 16 18 20 22 HOUR OF DAY Figure 1.1: A time series of pollen concentrations at 2000 ft. over Willow Run Airport (1962).

2.0 THE EXPERIMENT 2.1 THE EXPERIMENTAL STUDY OF LEAD, COPPER, AND CADMIUM AND RELATED INFORMATION IN THE SOUTHERN LAKE MICHIGAN BASIN (CHICAGO AND NORTHWEST INDIANA) Figure 2.1 shows the area under study and Figure 2.2 presents a greater detail of this area plus the sampling locations and the station key. The most important differentiating factor for the Chicago —Northwest Indiana area as compared to other metropolitan areas is that it is adjacent to one of the major fresh water sources in the United States. Because of their proximity to Lake Michigan, Chicago and Northwest Indiana are subject to unique meteorological and, thereby, pollution conditions. In the Chicago area alone there are approximately 6.25 million persons, and in Northwest Indiana about 0.75 million, relative to the 1960 census. This represents about 7 million persons in an area of about 200 square miles, supporting about 5,000 major industries as listed in the Metropolitan Chicago Industrial Development Guide (1968), many of which are shown in the foldout in Appendix VI. Noting the industrial areas and the station key (Figures 2.1 and 2.2), we can see that the sampling network covers the area quite well. One criticism of the network is that most of the outlying stations are found in small cities and towns. This would prejudice the lead data, especially, and would make us say that the outlying -27

-28LAKE MICHIGAN Michigan N -j-_.! 0 10 20miles 0 10 20 30Km Sampling Area I a Illinois Indiana Figure 2.1: Lake Michigan and sampling area.

+^^^,TJV f^~ ~Air Sampling Locations B N 6 F LAKE MICHIGAN CHICAGO + + + r-r'jr 0 Hc^"MDIGAN CTY + R 17 la3 2 15 24 Illinois 19 Indiana x 25 x29 i* ~~~>~i ~~~ | * 10 km 20 Figure 2.2: Key to high volume air sampling locations.

-30areas are probably not rural, but then again not urban or industrial; we would then probably call them proximate stations as per McMullen et al. (1969) (a crude estimate of the traffic density is presented in Appendix 1.6 in order to roughly predict the areas of maximum lead emission). This type of information for Chicago is not available at this time and must be approximated. All stations are located two to three stories (10-15 meters) above ground level, and are usually located on top of schools and public buildings. (The addresses of the stations are presented in Appendix VI.) Chicago has three major airports, two of which provide detailed meteorological data, and the air pollution officials for the city of Chicago maintain up to 13 stations that have telemetered meteorological data. However, during this period it was found that the Chicago data were somewhat inconsistent and very little information was used. In Northwest Indiana there are no full time meteorological stations. However, there are a few stations that take gross measurements of wind speed and wind direction. There are but one or two stations that give more detailed chart tracings. The locations of the meteorological stations are presented in Figure 2.3 and are listed in Appendix VI. Having personally inspected almost all of the sampling stations, especially in the Northwest Indiana area, the author would conclude that most are wellplaced in order to gain the most accurate and descriptive results.

Locations of Meteorological Data TAM-I TAM-2 N +TAM-7'~TAM-3; LAKE MICHIGAN CHiCAGO D+M*W + \ TAM-5 TAM' TAM-B ~ WI MGAN CITY ARG x X *+_^ x liosAIninRY Illinois | Indiana x 10 km Figure 2.3: Key to locations of sources of meteorological data.

-322.2 PURPOSE OF THE INVESTIGATION The problem was approached at different levels. The first experiment was started with Professor Winchester and his students on Lake Michigan on the vessel operated by the Great Lakes Research Division of the University of Michigan, the Inland Seas. The Inland Seas sailed from Grand Haven, Michigan, on 21 May 1968 to Calumet Harbor, returned to Grand Haven, and again returned to the approximate center of the southern Lake Michigan basin, completing the cruise on 26 May 1968. At the time it was desirable to develop a way to determine the source strength of pollution going into the lake (see Appendix I). After many contacts, additional land-based samples taken on 21 May and 22 May were obtained from the local air pollution groups and were analyzed as a pilot study for lead, copper, cadmium, and bismuth. The method of collection was with standard 20 x 25 cm (8 x 10 inch) high volume filters taken by the local pollution officials for their routine suspended particulate analysis. There were no special preparation instructions given prior to the sampling; in fact, most of our samples were obtained after their sampling, which was for the sole purpose of obtaining suspended particulate data. After analyzing the May samples it appeared that the research was feasible and the analysis technique was sensitive enough, and it also became obvious that the data could be of extreme interest. After inspecting the scheduled sampling of Chicago, the Northwest Indiana Air Resource Management Group, and the Porter County network (under the

-33supervision of Dr. El-Naggar of Valparaiso University), only five days of simultaneous sampling during the summer of 1968 were available for analysis. The city of Chicago collects samples three days a week on Tuesday, Thursday, and Saturday; Northwest Indiana has a somewhat random schedule; and Valparaiso (or Porter County) has a different random schedule. (The 1968-69 Northwest Indiana schedule is presented in Appendix VI.) Because of the analysis technique, lead, copper, and cadmium were simultaneously analyzed, but bismuth was too scarce and was analyzed only for the pilot study. Sulfur dioxide data and suspended particulate values were obtained from the local control agencies and are presented as additional data for information and comparison. 2.3 ANALYSIS PROCEDURES 2.3.1 Sample Preparation and Handling All of the Northwest Indiana and Porter County districts offered the full 20 x 25 cm (8 x 10 inch) glass fiber filter paper which was already exposed, while Chicago samples consisted of a 2.5 cm (1 inch) strip from the center of the 2 2 20 x 25 cm filter paper. A 12 cm (2 in. ) section of each filter paper was cut into small strips and inserted into a 25 milliliter volumetric flask. Four milliliters of perchloric acid were added and then heated to 300~C. The carboncontaining material was dissolved and volatilized to carbon dioxide, leaving the free ions and glass fiber filter. Any vaporized ions were re-vaporized on the cool top of the flask.

-34The vials were equilibrated to the 25 milliliters and allowed to sit for a few days. No further sample preparations were necessary. (Several samples were prepared at once, but it is suggested that no too many samples be heated at one time due to the possibility of explosion from large amounts of perchloric acid. A hood was used.) At no time were metal objects allowed to come close to the fiber filters, but since the filters were originally used on a metal holder, there is no guarantee that some contamination was not present. However, the blanks were very low for the metals studied and little systematic contamination effect was observed in the final results. 2.3.2 Method of Analysis Lead, copper, cadmium, and bismuth were chosen because of their electrochemical properties and the availability of an electrochemical technique called Anodic Stripping Voltammetry (ASV). Because of a unique cell design we were able to gain a much greater sensitivity than was previously available (Matson, 1968, 1970). Further design modification had made this instrument available for semi-routine use. The process is similar to the hanging drop electrode used extensively in electrochemistry, but has the advantage of stripping metal ions quickly as compared to the hanging drop. This is achieved by use of a composite carbon electrode to which the mercury is plated. For the non-electrochemist, it should be pointed out that all of the metals studied in this work are

-35soluble in mercury; that is, during plating they form an amalgam with the mercury and then deplate easily. The limiting factor in the stripping or deplating is the distance the ions must travmel through the mercury to get back into the solution. With a hanging drop electrode the mercury layer is quite thick. In the composite carbon electrode the thickness of the droplets or layer of mercury is quite small, and the metals strip quickly, forming a separate and discrete peak for each metal. The physical characteristics of the unit are shown in Figures 2.4 and 2.5, with a sample resultant stripping curve presented in Figure 2.6. From this latter trace we can see that the order of elements are zinc, cadmium, indium, lead, copper, bismuth, and mercury. Of these, zinc, cadmium, lead, and copper are found in large enough quantities to be far above that of indium and bismuth as found in nature. Thus only four peaks are usually observed before that of mercury. The location of each peak relative to the voltage is variable according to the reagent used and the acidity and the characteristics of the cell. An additional advantage of this equipment is that several samples can be run simultaneously. In this case, four units were used with one minute plating time separation being the rule. Several analyses were conducted in order to ascertain the cell characteristics, the repeatability, the deterioration and the overall sensitivity for each metal. It may be simply stated that the sensitivity can be as low as one nanogram in situ; and the deterioration is from less than 1% to typically 3-4%

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40 30- CU 2 r \ /n\ l^ X 20 / ] 10 I0-1.25 -1.05 -0.85 -0.65 -0.45 -0.25 REFERENCE VOLTAGE Figure 2.6: Sample response curve for ASV in chloride (0.2 M).

-39per run between washings (Appendix IV). All of this can be monitored and corrections can be made. The overall accuracy can be better than 20% (Matson, 1970). However, monitoring runs should be implemented in case of cell or reagent contamination or electrical charges. This was done routinely in all of this work. A lengthy discussion of these matters can be seen in Appendix V. Due to problems with standards, this study does not claim more than factors of 2 accuracy in all values although many points are much better. 2.3.3 Data Reduction The standard procedure for each session of analysis was to run several spike runs with blank in order to ascertain the calibration values for each metal. The spike was typically 20 nanograms of cadmium, 100 nanograms of lead, and 100 nanograms of copper. After three to four uniform spike runs larger spikes were added to find the calibration curves over a large range of concentrations. These data are presented in Appendix IV.3. The cell was then washed and a new blank plus spike run was made. To this run was added, without washing, an aliquot of the sample. After this analysis the cell was washed and the blank plus spike run repeated, and so forth throughout the session. For the three elements, both peak heights and peak area under the curve were measured in order to compare and to find out which data reduction method was the most accurate. The area under the curve is the most physically significant, but the peak height is the easiest to

-40measure and because of cell characteristics can be used over a large part of the concentration spectrum for analysis and calibration (Appendix V). The concentration versus response curves were not always run, but enough were done to solidify the calibration curves. A sample curve is presented in Figure 2.7. The results of each session and each cell were separated and typed on computer tape. The original data tables are listed in Appendix IV.3. A computer program automatically sensed the code and determined whether the run was a spike run, a calibration run, or a sample run. The spike run was subtracted from the sample run or the repeat run and the volume was calculated as well as the value of the aliquot. The calibrations, also presented in Appendix IV.3, were fed into the computer separately and the concentrations were then calculated. The final output of the computer was in the format of run number, and the value of each of the three elements repeated for peak height calibration and the area under the curve calibrations as well as the averages of the two. When the two methods of calibration differed markedly we went back to the original curves and re-analyzed. It was found that most of the errors were due to problems in reading the planimeter that was used to measure peak areas. With a little additional observation and experimentation it was found that drawing the base line could also be expedited by using a horizontal line rather than trying to follow the charging curve. For each session a plot of the

-410 Rig. I x 2 A 3 3000 + 4 (x () Estimated x itl 1000 E x + E +'- 300 _ IL I I Q~~~I~ ~ — 30 300 1000 3000 10,000 Pb AMOUNT, ng Figure 2.7: Sample concentration vs. response curves, cells 1 to 4.

-42spike plus blank curves was made and the percentage of deterioration was noted. Then the results were corrected for this deterioration and written in an additional table. All data were rounded to two significant figures and retyped on computer cards for listing and calculation of ratios. These data are presented in Appendix IV, and the ratios are also presented in Appendix IV. Additional discussions of cell design, cell characteristics, carry-over and reproducibility are found in Appendix V.

3.0 RESULTS 3.1 REPRESENTATION OF DATA Tables 3.1 to 3.6 are tabulations of the concentrations of each element for the six days studied. Detailed meteorological data are in Appendix IV.1. For each of the six days there are 11 figures depicting: 1. wind speed and direction; 2. suspended particulate isopleths; 3. suspended particulate values at their respective stations; 4.-11. sulfur dioxide, cadmium, lead and copper presented as for suspended particulate. A brief description of each representation should be made before summarizing the results. Wind, as presented in Figure 3.2.1, represents the wind speed and direction by hour, with the wind direction being represented opposite to the usual meteorological convention. That is, the line represents the direction towards which the wind is blowing, as the arrows indicate. The reason for this choice is that we would like to clearly represent the direction in which a pollution source would be advected if one were present at the meteorological station. The length of the line is the sum total of all the wind speeds along that 10~ vector over the 24 hour period from midnight to midnight. The number at the end of the vector is the total number of -43

-44Table 3.1 Atmospheric Concentrations of Cadmium, ng/m3 STATION MAY 21/22 JUIE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 50 5 30 10 10 2 -- ** 20 20 10 20 3 10 50 30 3510o** ** 50 ** 3~ 4 30 ** 5 10 8 5 40 10 10 50 ** 7 6 10 8 20 10 10 10 7 -- 8 60 10 10 8 15 ** 5 10 8 9 50 7 10 20 10 20 i 3 6 11 10 40 6 - 12 70 10 * 15 30 50** 14 -. 15 15 -_ _ 16 7 9 17 10 17 10 ****** ** ** 18 **20 ** 10 ** 20 19 9 ** 40 20 10 6 80 20 5 20 21 - -- 50 40 ** 22 — 5 300 1** 23 3() 50 50* 24 -- -- 20 7 20 10 25 - -50 ** ** 26 5 7 10 ** 27 -_ -- 10 20 A ** 20 20 10 30 B 50 30 10 53 30 C 50 10 0 ** D M 20 ** 20 20 E 60 -- - -- 15 40 F 20 10 10 -- 10 5 G 50 10 **10 -- 15 H ** *20 8 50 40 I -_ - - - _ _ _ ** J 80 -10 -- 8 -- K 20 ** 8 10 10 10 L 50 15** 20 30 M 40 6 9* 20 ** N 10 8 20 9 10 50 10 10** 10 7 P 5 20 9 20 *30 Q 50 10 6 15 -- 6 R 20 -- 7 *10 -- T 10 10 9 ** - U 9 ** 10 ** 20 -- V 40 7 40 6 30 30 W 40 9 10 -- ** ** SHIP -- -- -- 20 Individual Data Points are Reliable to a Factor of 2. **-= <5

-45Table 3.2 Atmospheric Concentration of Lead, ng/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 2000 800 1000 100 1000 1000 2 -2000 3000 2000 3000 2000 3 3000 1000 3000 2000 2000 2000 4 5000 1000 2000 800 2000 2000 5 1000 900 2000 400 1000 1000 6 2000 900 4000 600 4000 2000 7 --- - 3000 700 3000 2000 8 1000 700 2000 1000 1000 1000 9 2000 500 600 2000 2000 500 10 2000 300 800 1000 700 600 11 2000 1000 2000 -------- 19 4000 700 2000 — - 13 6000 2000 3000 —- ---- ---- 14 ---- -..... - ------- -- 15 1000 500 2000 — - -__ 16 5000 800 -------- 17 1000 500 2000 900 2000 700 18 400 300 800 500 100 2000 19 500 400 400 ---- 100 3000 20 900 700 1000 1000 600 1000 21 — ---- 1000 500 600 —-- 22 -- 1500 400 1000 —23 --- -— 70 100 500 700 24 - -- - 1500 500 500 500 25 --- --- 500 300 200 ---- 26 1000 -- 1000 700 800 500 27 ---- -— 3-. — 500 400 800 A 7000 1000 5000 2000 3000 4000 B 4000 2000 2000 800 4000 4000 C 5000 500 2000 600 2000 3000 D 5000 2000. 300 2000 4000 3000 E 4000 - -o --- 1500 5000 F 6000 2000 3000 --- 3000 4000 G 4000 2000 4000 500 -- 3000 H 2000 1000 5000 700 3000 4000 I - -- - --- -- ] —-- 2000 J 6000 9 200 -— 2000 ---- K 5000 LOO 2000 500 2000 2000 L 3000 1500 2000 200 4000 2000 M 6000 1000 2000 400 2000 4000 N 5000 1000 3000 600 2000 2000 e 6000 1000 2000 500 2000 1000 P 5000 1000 4000 600 2000 5000 Q 4000 700 2000 700 - 2000 R 4000 -— 2000 500 2000 T 5000 1000 2000 800 ------- U 4000 1500 5000 1000 35000 -—. V 4000 1000 4000 1000 3000 2000 W 4000 1 8002000 0 00 00 SHgIP........ —.... 700. Individual Data Points are Reliable to a Factor of 2.

-46Table 3.3 Atmospheric Concentrations of Copper, ng/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 70 300 400 150 150 300 2 — 100 1000 150 200 150 3 300 200 2000 200 80 600 4 900 2000 200 80 600 400 5 1000 3000 600 60 500 200 6 2000 7000 (7000) 2000 2000 4000 7 ----- 1000 300 1000 600 8 5000 9000ooo 5000 2000 3000 9000 9 7000 5000 9000 7000 10000 10000 10 4000 5000 1500 2000 (9000) 10000 11 300 700 400 o - 12**5 300 500 - - 13 80 700 200 ---. 14 --- --- _-____ 15 200 200 150 - 16 100 200 — - ---- -- 17 150 200 150 200 30 70 18 500 200 300 200*** 100 19 400 700 400 --- 70 100 20 150 200 100 200 40 100 21 -- -- 100 70 70 22 --— 5 300 70 70 23 --- -— 90 *** 100 100 24 --- -500 60 100 70 25 --- --- 200 60 90 - 26 80 --- 300 200 400 200 27 ----- ** 300 300 200 A 70 0** 600 100 300 B 300 200 70 200 300 150 C 100 100 100 20* 100 D 150 70 30 100 200 200 E 400 -- -- -- 500 1000 F 200 ***80 --- 100 100 G 400 100 70 200 -- 200 H 500 20 80 20 100 ** I.. --- - --- --- 200 J 200 100 ** —- 200 K 200 ******200 100 100 L 200 100 70 *** 800 200 M 80*** 60 o 600 90 N 100 80 300 60 300 100 e 300 200 200 100 200 200 P 300 100 200 200 200 200 Q 900 30 100 200 --- 200 R 500 *** 200 --- 200 --- T 200 200 200 30*** 200 200 200 20 300 -- v 600 100 400 80 200 200 W 200 40 100 --- 200 200 SHIP -- --- 100 -- -- Individual Data Points are Reliable to a Factor of 2. ***= <20

-47Table 3.4 Atmospheric Concentrations of Bismuth, ng/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 ** 4 1. 5 2. 6 5. 7 -- 8 0.7 9 2. 10 1.5 11 0.4 12 0.6 13 0.4 14 15 0.3 16 ** 17 18 19 20 21 22 25 -- 24 25 26 * 27 A M B ** C A* D M E 0.8 F 1. G 0.1 H M I -- J ** K 0.6 L ** M M N ** e ** P 0.3 Q 0.4 R 0.4 T 0.2 U ** V ** W 0.8 SHIP - - Individual Data Points are Reliable to a Factor of 2. **= ~0.05

-48Table 3.5 Atmospheric Concentrations of Total Suspended Particulate, yg/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 115 170 117 32 198 148 2 218 344 64 161 92 3 81 151 256 159 148 167 4 126 143 128 54 152 145 5 140 169 278 66 156 242 6 142 201 382 125 256 233 7.- - 332 193 191 174 8 62 108 210 105 91 122 9 83 115 134 148 122 109 10 78 109 198 -- 100 96 11 76 153 228 -- 12 128 179 249 15 120 187 255 -- 14 -- -- 15 46 136 100 16 80 154 85 -- 17 66 109 117 142 -- 18 98 86 107 64 17 19 55 98 70 -- 46 20 78 96 88 126 62 21 -- 77 44 4065 22 - 104 55 49 65 25 - -- 66 27 39 57 24 - - 32 38 81 25 - 81 -- 4 185 26 6b -- U., 27 -— 49 84 69 A 88 174 141 71 138 107 B 113 212 116 105 239 214 C 114 55 50 49 132 139 D 125 261 19 60 243 188 E 144 -- - 305 952 F 153 206 169 -- 185 218 G 154 181 172 152 -- 145 H 50 176 256 86 182 186 I -- -- -— 181 J 166 205 259 -- 166 -- K 154 139 245 103 158 154 L 180 229 180 43 225 218 M 139 130 183 98 170 195 N 142 115 211 86 154 136 8 163 205 263 108 174 178 P 141 153 286 51 177 214 Q 195 161 408 109 -- 235 R 145 -- 241 110 130 -- T 92 152 81 67 132 U 75 172 121 74 146 - V 114 186 190 100 196 148 W 131 155 216 -- 161 185 All Data Furnished by the Local Agencies

-49Table 3.6 Atmospheric Concentrations of S02, ppb STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 20 1 2 5 17 21 62 69 5 4 5 15 24 -- 48 4 6 7 - -- 2 - 1 8 -- ** -. 9 9 10 11 2 -- 15 - 12 15 ** -- ** 15 16 17 18 19 - 1 - - -- 20 21 -- 9 2 1 1 14 22 - -- 1 ** ** 25 - 8 4 1 11 24. -- 1 2 -- 25 26 27 A 75 5 10 8 5 4 B 14 1 27 55 5 26 C 54 17 10 1 4 6 D 22 67 12 30 13 11 E F 10 59 9 13 9 54 G 52 45 * 6 3 16 H 27 94 51 9 55 5 I J 7 1 7 1 6 7 K 80 12 14 12 24 -- L 25 15 29 1 27 -- M 1 -- 6 1 15 52 N 1 - 25 12 4 39 e 1 -- 20 4 5 20 P 1 -- ** 1 2 5 Q 24 8 51 7 2 44 R 17 7 51 4 2 - T 1 2 12 12 28 16 U V W 4 9 15 24 22 20 **= o0.5 All Data Furnished by the Local Agencies

-50hours that the wind came through that vector; for example, a 3 would mean that the wind was blowing in the direction of the arrow for 3 out of the 24 hours. (These hours need not be consecutive.) Non-labeled vectors are one hour occurrences, and calm (C) is defined as under 3 mph. This compromise seems to be the most reasonable method for a graphical representation of general medium-range advection of pollution in this area. For reasons of clarity in the drafting of the data values at each sampling station, each element's data was uniformly scaled. Suspended particulate is given in pg/m3 (parts per billion), SO2 in pp billion, cadmium in ng/m (pp trillion), 3 lead in pg/m multiplied by 10 (pp hundred trillion), and 3 copper by ng/m divided by 10 (pp tens of trillion). For each parameter both isopleths and data points are presented in separate figures. In the following sections we will attempt to point out pertinent features of each day and each parameter in order. In addition to calling attention to the obvious facts we will comment on particular areas for later discussion under Section 4, "Interpretation." 3.2 21, 22 MAY 1968 Tuesday, 21 May, is represented generally by a northwest wind; that is, a wind coming from the northwest blowing to the southeast. We would then expect pollution from the Chicago area to be advected from the northwest to the southeast.

-51On Wednesday, 22 May, in the Northwest India a region, the general advection would be from the southwest to the northeast. The same wind directions occurred at East Chicago and Gary with slight differences at Michigan City, providing a good representation of a wind shift due to lake effects, and these effects can be observed throughout the six days studied. With these general wind directions in mind we can now inspect a transport of particulates. 3.2.1 21 May 1968, Chicago Suspended particulate analyzed by each local air pollution facility shows a broad maximum in the southeast and central areas, Figures 3.2.2 and 3.2.3, with a minimum in the west. The sulfur dioxide in the Chicago region, also taken by the local control agency, shows a large maximum in the northwest region slowly diminishing towards the southeast. There is a single point maximum in the south central region, suggesting an advection to the east-southeast. Cadmium, Figures 3.2.5 and 3.2.6, is represented by two maxima, one in central Chicago and the other in southeast Chicago. Lead, interestingly enough, shows the northwest maximum, as in the S02, slowly diminishing to the southeast. There is also a maximum in the central and east central regions with a definite minimum in the west central region. Copper has not been isoplethed in as great detail as the other elements, but shows a maximum in the north central Chicago area with a slight bulge to the southeast and a maximum in the southeastern section.

-52Bismuth was analyzed for these two days only since it was found to be in such low levels, it is not usually thought of as a toxic material, and it requires a four fold increase in analytical time. There is a slight maximum in the central 3 downtown ("Loop") area, but the value is only about 1 ng/m. It seems that there could be a case presented for general advection of specific trace metal pollutants from the northwest to the southwest. It is especially interesting to note the large source region northwest of Chicago advecting into Chicago for sulfur dioxide and lead. The cadmium maximum in central Chicago is very close to a maximum of sulfur dioxide. Copper and sulfur dioxide coincide in south Chicago, copper and cadmium in the north central area, lead and suspended particulate in central and north Chicago, and lead and sulfur dioxide in the northwest regions. 3.2.2 22 May 1968, Northwest Indiana For the 22nd of May in the Northwest Indiana area the suspended particulate is characterized by a heavier loading in the metropolitan Gary area, as well as in Whiting and north Hammond. It is to be remembered that the general wind direction for this day was from the southwest. There seems to be a relatively moderate amount of sulfur dioxide in the HammondWhiting area, and a small amount for the rest of the region. Cadmium presents an interesting pattern with a maximum in East Gary with isopleths to the east, and a slight maximum in northwest Hammond, but with a broad minimum in the east Chicago area. Lead seems to show a maximum in the central

-53business districts of Gary and Hammond. Probably the most significant occurrence is the large amounts of copper found in Northwest Indiana, with a copper maximum found at station 9 in East Chicago extending southwest to station 8. The maximum value at station 9 is 7 pg/m 3 and at station 8 is 5 pg/m 3 as shown in Figure 3.2.11. Bismuth seems to be more abundant in the Northwest Indiana area than in the Chicago area, but, again, the wind directions are different and a plume of bismuth seems to be present from southwest Hammond to northeast East Chicago and Whiting. This data seems to show that suspended particulate is present in the metropolitan areas and seems to be advected from south Chicago into Whiting and north Hammond and East Chicago. In summary, for these days sulfur dioxide data is scarce and inconclusive, cadmium seems to be present in the northwest Hammond area (possibly from south Chicago and a source in east Gary), copper may have a source in southwest East Chicago and northeast East Chicago advecting with the southwest wind, and bismuth seems to be advected from southwest Hammond to the northeast. Additional shipboard data are available for 20 May through 23 May and are presented in Appendix I.1. 3.3 6 JUNE 1968 Thursday, 6 June 1968, is characterized by south to southeast winds. At the O'Hare station the wind direction is

-54definitely southwest, while at Midway it is from the southwest to southeast, and at the East Chicago station there is a definite southwest wind. In Michigan City the wind is mostly out of the south with little variation because the meteorology station is located within 20 m of the lake, and the greater frictional retardation of the ground roughness is probably not seen as well as at the more inland stations. We can thus characterize this day by a southwest to south wind. The suspended particulate data bears out this wind direction by showing a maximum in east downtown Chicago and minima in the west. In the Northwest Indiana —Chicago area there is a plume of particulate extending from central Hammond through northeast East Chicago, with a broad maximum in Gary exhibiting an effect of the combination of an urban and industrial region. The sulfur dioxide value is very high in the north central Chicago region, with a maximum in the west of the plume and another maximum occurring in the east side of the corridor. The wind direction from O'Hare and Midway is more northwest than west and the sulfur dioxide seems to be advecting from the west-southwest to the east-northeast. This could be explained by the lack of information at station V which may show a bulge or a northwest advection which we could not draw without this information. The Northwest Indiana region shows a corridor of sulfur dioxide at a much lower value extending through Hammond to Whiting. Cadmium, again, is present in low values with a broad plume from southern Chicago, extending along the shoreline in East Chicago, with

-55a slight maximum in northeastern Chicago. A broad maximum seems to exist in northern Gary, in the industrial regions. Lead seems to follow the automobile traffic intensities with a shift to the northeast from central Chicago. In the Northwest Indiana area the maximum lead concentrations are somewhat concurrent with the urban traffic densities with advections to the north. Copper has not been contoured for Chicago due to the overpowering contrast in the Northwest Indiana area; however the data are accurate enough to warrant some contouring, if so desired. Copper is obviously available in very large amounts in Northwest Indiana. Station 8 with 9 pg/m of copper exhibits maximum values, and station 6 shows 7 3 Pg/m3. The isopleth patterns tend to bear out the wind directions and seem to indicate that a source is present in southwest East Chicago, or somewhere close to Hammond. Concurrent patterns occur, with suspended particulate showing a secondary maximum north of downtown Chicago, as well as with SO2, cadmium and lead. An additional overlapping exists in Gary with cadmium and lead, and the maxima also overlap well with lead in most areas. 3.4 20 JUNE 1968 After presenting two days of northwest wind in northwestern Indiana and one day of northwest wind in Chicago, Thursday, 20 June, represents a southeasternly wind that should show some differences. It should be pointed out, however, that the winds are relatively light and that there are

-56several periods of calm where aerosols might go just about anywhere, over a short distance. The suspended particulate loading seems to increase slightly because of the low wind speeds, especially in the south Chicago region. Most of the area is represented by broad maxima, with minima close to the lake due to the incursion of the cleaner lake air from the east and southeast. This is especially true at location D in Chicago which is close to the lake, and generally throughout the lake stations. The corridor from north East Chicago is a result of heavy concentrations of steel industries located close to the lake. (A point to be remembered is that the turbulence characteristics of the mixing layer are not the same over the lake as they are over land, and these effects can influence the ability of the mixing to bring a suspended particulate down from a high source region advecting over the land with a possibility of lifting occurring over the lake.) A maximum extending inland from downtown and a strong maximum in north Chicago are also present. Sulfur dioxide is similar to the suspended particulate in the southern Chicago and western Northwest Indiana regions, with an additional maximum occurring in the western edge of central Chicago and extending from the northeast. There does seem to be an unexplained large sulfur dioxide source either in Hammond or southern Chicago. Cadmium is slightly uniuue for this day in the Porter County area. We are not sure that these samples were nor uniformly contaminated, but this is not to say that they were. This was the only day that shows large amounts of

-57cadmium present. One would not expect that all samples would be high due to the analytical procedures since they were run in different cells. The only possibilities are that the data is real or that the samples for that day were brought close to some cadmium-emitting device or material. In Figure 3.4.7 the bracketed data represent real measurements, and the second number is an estimation based on uniform contamination. There are two cadmium maxima for this day, one in north central Chicago and the other in northern Hammond. The isopleths show a somewhat northwest advection. Lead also displays a maximum in the northwestern Chicago area emanating from the downtown area in the east central region. A broad maximum exists in the southwest region as well as maxima in the business areas of Hammond, Gary and in northern East Chicago. The copper picture becomes somewhat clearer in the Northwest Indiana region. Stations 6, 8 and 9 show a double maximum, with a minimum at station 7. This would imply a double source. The advection to the east or northeast is of only a moderate extent, and there seems to be some advection or sources in the west Gary area. Again, there seems to be a source of copper particulate in the northwest Chicago region, but details north of this area are not available. Suspended particulate heavily correlates with sulfur dioxide in south Chicago as well as with lead in Hammond —East Chicago plume. Cadmium does not seem to correlate well and copper only in East Chicago. In northwest Chicago, cadmium and sulfur dioxide have overlapping maxima, and lead and copper also have a

-58strong overlapping maximum but further north (Station A). This is the second time the lead has occurred in such large quantities but the first time that the copper was overlapping. The minimum at station D in east central Chicago is present in all parameters and at station 11 in East Chicago except for copper. 3.5 9 JULY 1968 Tuesday, 9 July 1968, was characterized by a strong south to southwesterly flow with a frontal passage approximately half way through the sample period. A strong north to northeasterly wind occurred in the second half of the sample day. Additional data were taken in the southern basin of Lake Michigan by the research ship Inland Seas (operated by the Great Lakes Research Division of the University of Michigan) by Dale Gillette (1970). These winds were strong and would imply a lower particulate loading and a greater amount of mechanical mixing and diffusion than previously seen. The deviation of the prefrontal passage wind direction at the Michigan City station is probably a lake effect, if one precludes instrument error. All the data show a decrease in concentrations. Suspended particulate loadings are low and present maxima in central Chicago and East Chicago. For this and the following two days there are no data available for the city of Gary. There were some administrative changes during the latter part of the summer of 1968, and no suspended particulate or Hi-Vol samples were taken. The sulfur dioxide

-59data show a maximum in northern Chicago along the lake and one in the western section of Chicago. An additional maximum source occurs in Hammond, but due to lack of data in East Chicago and Gary, it is difficult to say much about wind direction or sources. Cadmium is present in south Chicago along the lake, somewhat coincidentally with the sulfur dioxide data. Northern Porter County again shows a relatively high amount of cadmium, leading us to believe that there is a possibility that the previous data set might be real for cadmium. Lead is low and shows a plume between northern Chicago and the central downtown area on the lake. This isopleth does not coincide with wind direction, but it does coincide somewhat with traffic patterns, but again the levels are low. An additional maximum occurs in Hammond in the business area. Copper shows a double maximum, one at station 9, as on 20 June. These isopleths seem to coincide with the wind directions. To restate the overlapping of maxima and minima, we notice that all parameters have high values north of downtown Chicago, cadmium and copper in southwest Chicago, sulfur dioxide and cadmium in Hammond, and suspended particulate and cadmium in East Chicago, Indiana. 3.6 8 AUGUST 1968 Thursday, 8 August 1968, is a different day meteorologically as the winds are variable and light throughout. Only at Michigan City, Indiana, are the directions and velocities

-60more pronounced. There is a lake breeze situation operating, and it is evident by comparing the close lake stations with the more inland stations such as O'Hare and Midway. One would be hard pressed to predict the general directions of advections for this day. We could say that this day could be representative of a random wind direction situation. This conclusion may be incorrect as industrial emissions as well as local wind can change from day to day. The suspended particulate data seem to bear out this random distribution fairly well, as all areas have above average values, but there are no real sources except in the southern Chicago area. This source is probably a steel mill located at the point of maximum (E), also the maximum in East Chicago is located close to a heavily polluted region. For sulfur dioxide one could guess that there is a source in northeast Chicago, one at station H in west central Chicago, and one, possibly, at stations W and L. Cadmium is present in northern Chicago at moderate levels but does not seem to have any maximum for this day at other locations. Lead is high, but generally distributed, as expected, with a maximum northeast in Chicago and in northern East Chicago, with the isopleth extending through to the residential and business areas of Whiting and Hammond. Copper is present at two locations in Chicago but now in extremely large quantities. Again, station 7 is low and stations 6 and 8 are persistently moderately high.

-61The coincidences, or lack.thereof, become very informative for this day. Sulfur dioxide does not correlate at all with suspended particulate, but lead, copper and cadmium coincide well in Chicago, except for station E in south Chicago at the steel industry. Lead is reasonably synonymous with suspended particulate in all areas. Cadmium and sulfur dioxide relate well in Chicago except for the northeast station. 3.7 29 AUGUST 1968 The last day, 29 August 1968, is similar to 20 June, but exhibits some lake effects but not to the extent of the 8 August situation. The wind direction is generally from the east with a moderate amount of meandering through the western half of the direction, but mainly to the northwest. Suspended particulate is moderately heavy with a maximum at station E on the south shore of Chicago, close to a steel-making facility (station E is usually run only when winds advect from this area), extending to a maximum in northeastern Chicago, and with a broad maximum in southwest Chicago. Similarly, in the East Chicago —Whiting area there is a maximum coinciding with the heaviest particulate sources. Sulfur dioxide shows maxima in the business district of Chicago and in the southwest, with a minimum intervening between another maximum occurring in the south. No sulfur dioxide data are available from any of the major cities in Northwest Indiana. Cadmium is present in a broad maximum seeming to advect from the east section of Chicago, and again in the heavy suspended particulate region

-62in south Chicago. A slight maximum occurs in mid Lake County, south of Gary, and it is not at all clear as to its origin. Lead is quite high in northern Chicago with some minor maxima occurring in and to the west of the business area, forming a small corridor. In the business and industrial areas of Northwest Indiana, lead is slightly higher than at other locations. It is not clear how far copper advects, but we do see an increase at station 3 in Hammond, showing the extent of the eastern advection of copper aerosols due to the east-northeast wind. Again, station 7 is lower than the adjacent stations. Whiting also seems to show a little larger copper value than for the other winds, but the eastern advection is not as clear cut as would be desired. Thus it does seem that two sources are probably present. The unfortunate emission of data from Gary does not allow us to make more definite conclusions for this situation. The small maximum in southeast Chicago is due to the heavy dust loading at station E. Isopleths of suspended particulate and sulfur dioxide are not overlapping at all, except in the downtown Chicago district, but cadmium and lead correspond well in most of Chicago. Copper and cadmium are not well matched with sulfur dioxide on this day.

Tues. 21 May 1968 Wed. 22 May 1968 WIND N 6 + 5 L AKE MICHIGAN CHICAGO 2, \ 2 2 2 35 2 10kmIn Iiana Figure 3.2.1: Wind rose for 21 and 22 May 1968. J~~n ^ Vffi^^4 ^^^^ ~~~~~~~MICHiGANI CITY | *- * - I * X e lllinois |' Indiana'~'' I, 10 krm| Figure 3.2.1: Wind rose for 21 and 22 May 1968.

Tues. 21 May 1968 Wed. 22 May 1968 Suspended Particulote, g-m-3 100 + *- +P I N O00 100 <+ < 150 LAKE MICHIGAN 100 CHICAGO + \\~\ \ 1 1150 1 m1 00 ^ MICHGAN CRY F3:ea l s h22 y 150~~5 50 50 Indiana Illinois x 10 km Figure 3.2.2: Suspended particulate isopleths for 21 and 22 May 1968.

Tues-21 Moy 1968 Wed. 22 May 1968 9. fs Suspended Porticulate,1g-m-3 114 +88 114 125I 50 1 5034 +1 53 LAKE MICHIGAN CHICAGO 166 154 + + 139 142 1V4 ^^yj 163 * P?0~~~~ 163 I^^ -MCHOGAN OTY 141 321~ 195 143 1 T6'6~0 x.120 + I | 128 I -I I.66 ~G 6RY 46 98 I~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~I ~~I~~~llinois j#~ ~Indiana Illinois x 10 km Figure 3.2.3: Suspended particulate data points for 21 and 22 May 1968.

Tues. 21 May 1968 Wed.22 May 1968 705020 S02,ppb 70~~~~~1 60 N 50 40 20 10 30^^ ~LAKE MICHIGAN CHICAGO 2 go 10 2010 3A OTY 10~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ 10 0-c +~ c +,~ Illinois I Indiana K 10 km Figure 3.2.4: SO2 isopleths for 21 and 22 May 1968.

Tues.21 May 1968 Wed.22 May 1968 /-^ J V \ _ T S02, ppb + +75 14 54 + N 37 32 22 LAKE MICHIGAN CHICAGO 7 *+ 80 23,? i l ^i)^ ^^^^^^Mla<GAN O~~~~~~~CTY 24'17 + > 4!- bIOIGAN OCTY Indian Illinois Indiana x ti a~~l " I *- 10 km Figure 3.2.5: SO2 data points for 21 and 22 May 1968.

Tues. 21 May 1968 Wed.22 May 1968 10 Cd,ng-m-3 20 40 tO }9f r LAKE MICHIGAN 40 { CHICAGO 20 509 40 WHIGAN OTY 20~ 10GR * 0 x )O Il>inois f'1IndianI 10 km Figure 3.2.6: Cd isopleths for 21 and 22 May 1968.

Tues. 21 Moy 1968 Wed.22 May 1968 + nd 9 Cd,ng-m-3 30 30 + 40 nd + 50 * 5 20 LAKE MICHIGAN CHICAGO 80 20 30 + + |40 10 0 50 50 0~~~~~~~~~~~~~~~~~~~~~~~~~~~~~( MICH5AN CITY 10m GARY Is nd 9 Illinois' Indiana T i t i ~~~~~10 10 km Figure 3.2.7: Cd data points for 21 and 22 May 1968.

Tues. 21 May 1968 Wed. 22 May 1968 60 40 Pb, 9g-m m-3x 10 Io + s+I ~ + 20 ^0 ZLAKE MICHIGAN CHICAGO +a MCHIGAN CTY + /i \C ~20 Illinois | Indiana K JJJ~LLLJ I 10 km Figure 3.2.8: Pb isopleths for 21 and 22 May 1968.

Tues. 21 May 1968 Wed. 22 May 1968 ^-^rUJ5Pb,,g-m33xIO v+- +70 40 40 50 + 20 30 + 40 &* +6 LAKE MICHIGAN CHICAGO 60 50 + 0 50 60 c 50 MI'Fe^ CMHIGAN CTY 40~ 10 32 3 + ^^ *60 X 10 I l^ eI5 3 Illinois Indiana x LLLL"*~ I 10 km Figure 3.2.9: Pb data points for 21 and 22 May 1968.

Tues.21 May 1968 Wed. 22 May 1968 Cu, ng-m'3 0.1 00 251 2 5\ LAKE MICHIGAN CHICAGO 25 50 100 209_ ^ uly n^'~~~~0 WHOM5T CI^ laGATY 600 25 25 50' ^ ^^ F 1 x ) 50 Illinois' Indiana x 10 km Figure 3.2.10: Cu isopleths for 21 and 22 May 1968.

Tues.21 Moy 1968 Wed. 22 May 1968 Cu,ng-mr3x0.1 + +7 20 10 + 60 15 50 +40 +| * + 20AKE MICHIGAN CHICAGO 20 0 20 20 + + [,8 10 40 7~~~~~~~~~~~~ 30 90 P^30'tSO MOICGAN CITY <90 5p ^ o ^ -^ —^^ * n 8 iX *15 G^ i 50~~~~5 +~~~~~~~~~~~~~~~ 40 Illinois Indiana x 10 km Figure 3.2.11: Cu data points for 21 and 22 May 1968.

Tues,21 Moy 1968 Wed.22 Moy 1968 Bi, ng- m'3xlO + + 0+ o Z.E/CLAKE MICHIGAN J* +' ~~ LAKE^S^ ^^ MKHIGN CITY +4C O 1010 + + GARY... Illinois Indiana x Il L1, k. I 10 km Figure 3.2.12: Bi isopleths for 21 and 22 May 1968.

Tues,21 May 1968 Wed 22 May 1968 Bi,ng-m-3x 10 + +2 M L ND N ND +M + iC 10 LAKE MICHIGAN CHICAGO + ND 9 M * NDD^N ND ND WD^ND b MICHGAN CITY 3+q ~ 4~~~~~~~~~~~~~~~~~~~ + + *4 x 20 -6 01 GARY Illinois Indiana x 10 km Figure 3.2.13: Bi data points for 21 and 22 May 1968.

1. 4 9' / /5.Thurs. 6 June 1968 2 WIND + I, 4~~~~~ * + ~~~~6 \ 5 L AKE MICHIGAN wICAGO 2'^O9~~~~~~~~ }^^ ^ ^ KMwGAN CTY * I, | ^S^CA *R )I ~~~~~~~~~~~~~~~~~~~~~~~~~~~~0 Illinois Indiana 10 (0 mph l -1iii t i II - 10 km Figure 3.3.1: Wind rose for 6 June 1968.

Thurs.6 June 1968 Suspended Particulate, pg-m"3 + + 200 N 1 50 too 250 100 150so LAKE MICHIGAN ++ l5ot 200 150 150 jP 200 MOW" CI TY + ~~~~150 5 15 - + x 100" 100 Illinois Indiana x 10 km Figure 3.3.2: Suspended particulate isopleths for 6 June 1968.

Thurs.6 June 1968 /w<r f _pSuspended Particulate, g-m-3 +J +174 172 55 N Ie 186 176 261 + * +206 LAKE MICHIGAN CHICAGO 205 1 - 139 229 + + 130 g 170 20 143 nD 05 ^i^?.^^^ MOWHGAN CITY 53~ 1 1 5'1 +9.187 15 *109 G0 1.36 86..... *98 Indiana Illinois 96 (0 km Figure 3.3.3: Suspended particulate data points for 6 June 1968.

Thurs. 6 June 1968 S02,ppb N 20~~~~2 30 401 s 20s L AKE MICHIGAN f CHICAGO 30. 10 J^ * iW^^ ^^^ ~~~~~~MCHIGAN aTY Illinois j Indiana + x tx 10 10 Illinois Indiana LLLL iLLAJi I I 10 km Figure 3.3.4: SO2 isopleths for 6 June 1968.

Thurs. 6 June 1968 I,~~~~~~~~ SO, p A + +5 S02 17 67 *'* ~ ~ ~ ~ ~ CICG 121 1'''' i,i + ~~~~~~~~~~~45 + + LAKE MICHIGAN 0~~~~~~~~~~~~~~~~~~~ 0'~~~~~~ ~Fgr 3.3.5:SO aapit o 6 June 1968. 2 I1 r^JT-^-r^ Sg~p2 / Illinoi n d I AN c~~C + + ^^^VM T --- + L-^ o j.0 x 10 km Figure 3.3.5: So2 data points for 6 June 1968.

Thurs. 6 June 1968 10 Cd,ng-m-3 + + * 1 20 20 +b *\LAKE MICHIGAN CHICAGO ++ + I+ 10 10~~~~~ rCHIGAN aTY 10 (^T?? —^! ~ 20 10 + xx 10 1 Illinois' ndiana x Lir~ l II 10 km Figure 3.3.6: Cd isopleths for 6 June 1968.

Thurs.6 June 1968 + 1dnd Cdng-m3 30 6 +N 7 nd + 9 + +10 LAKE MICHIGAN 4: CHICAGO nd 9.+ nfd 1 6 8 tO 5 J~~2^' "p^ ^^-^^~ MI~CHIGAN CTY I204^!l 020 nd Illinois Indiana x 10 km Figure 3.3.7: Cd data points for 6 June 1968.

Thurs. 6 June 1968 Pb, f/g-m-3xlO ~~+ + I,"" 15 20 2.0 t.o 20 LAKE MI/CHIGAN I / +, CHICAGO i07 v'. - -J —'"o 5' Illinois | Indiana 10 km Figure 3.3.8: Pb isopleths for 6 June 1968. Figure 3.3.8: Pb isopleths for 6 June 1968.

Thurs.6 June 1968 + 10.5 Pb, g-mrA Io 0 20 + 200 LoXAKE MICHIGAN CHICAGO 9 I 9 00 10~~~~ MICHGAN CITY 10 F 3P t n6 e 7 + 20o GATY 4 Illinois (' Indiana 7 III-K [ll 111 10 km Figure 3.3.9: Pb data points for 6 June 1968.

Thurs,.6 June 1968 *0^ J Cung-m-3xO.I + *- N AO * LAKE MICHIGAN CHICAGO + + 2550 x 10~km 100 Figure 3.3.10: Cu isopleths for 6 June 1968.,200 400 25 50' IlnoisI Indiana 10 km Figure 3.3.10: Cu isopleths for 6 June 1968.

Thurs,6 June 1968 (^ 20 GCu,ng- r xO.' + o I0 _+ 10 + *L d LAKE MICHIGAN CHICAGO 10 4[+ nod ip nd 8 P-110' 4^~^ ^^ MICHIGAN CITY CC 1 00S C / X / +!'Oip- o-. 70 20 Is Indli, al 10 km Figure 3.3.11: Cu data points for 6 June 1968.

4^~~~~. ~Thurs. 20 June 1968 WIND C-6 +Y~ LAKE MICHIGAN - CHICAGO / 3, o~ ~ ~ ~ 4MCHGAN OTY 3~~~~~~~~~~~~~~~~~~~ 4 I~.c [ s^-^^ Illinois Indiana ~~~~~~~~~~~~~~~~ 0 10 L4-1 mph Inn. l ni l I ~ 10 km Figure 3.4.1: Wind rose for 20 June 1968.

Thurs. 20 June 1968 100 + ^^^^ 100 Suspended Particulote,pg-m-3 100 ~~~~~~N ^^1~~~~~~~~~~~~~~~~4A OTY^io 150 100 200. 150 LAKE MICHIGAN CHCAGO ~+ + ( +~ 0200 200 ^T^) ^ 250 ^/^ 1S 250 ^^^ MICHIGAN CITY 200- 0^^0 10^250^^^^ ^^r^^ * x ^ 200 200~ 2 AR 250~ ~XB~XO~VT. IL150 100 Figure.. Supne atclt spoInSdiana Illinois 10 km Figure 3.4.2: Suspended particulate isopleths for 20 June 1968.

Thurs. 20 June 1968 +r^-^ r^JSuspended Particulate,pg-m-m3 11 6 150 N I* 1? \ 90 235 19 + 172 + 169 LAKE MICHIGAN CHICAGO 259 a4AT f~f 245 |8d 183 211 64 ^256'.2^9 *255-1 —1 ~~~~~~~~~~~~~~~~~~00 117 263 128 Illinois I ndiana IVIDWWI CITY ++~~~~~~~~~81 X4 408 241 1;7 66 +2 56-29 255'****'****' 88 ~~~~~~10 ~km~~104 Figure 3.14.3: Suspended particulate data points for 20 June 1968. 10010 Indiana Illinois 81 10 kmm Figure 3.4.3: Suspended particulate data points for 20 June 1968.

Thurs. 20 June 1968 10 S02ppb +~~~~~ 20 I0 20 3'20 * LAKE MICHIGAN I0 CHICAGO 10 0 +~ + 2.0 Ilinois'Indiana 10km Figure 3..MCH: SO isopleths for 20 June 1968.aT 20~~~~~~ Illinois Indiana 10 km Figure 3.4.4: so 2 isopleths for 20 June 1968.

Thurs. 20 June 1968 + 410'.1 S02,ppb 27 0' +' N 2' * +5 LAKE MICHIGAN CHICAGO 7 14 29 25 8 Illinois Indiana 10 km Figure 3.4.5: SO2 data points for 20 June 1968.

Thurs. 20 June 1968 r A 10< ^~~ ~Cd,ng-m-3 ( *LAKE MICHIGAN CCAGO \. 10 2Q I10 km 10 Figure 3.4.6:' Cd isopleths for 20 June 1968. Illinois 10 km Figure 3.4.6: Cd isopleths for 20 June 1968.

Thurs. 20 JUNE 1968 + ^20! Cdcng-m-3 nd to + 40 N 20 20 nd I 0 LAKE MICHIGAN CHICAGO 10 J1';19 " ^S^ ^^^ MICHIGAN OTY L6 7 5^<^ —T^ ^ --- + " ^n+. nd n *C30)10 x "^ —'"^^1 H (30) 10 n~~~~~~~~~~~~~~~~ (20) nd Illinois Indiana (30)10 X. i (80) LLLlJiJJJs I.Irin 10 km Figure 3.4.7: Cd data points for 20 June 1968.

Thurs. 20 June 1968 40 43 Pb, g-m-3xl0O A 10 iy'r LAKE MICHIGAN CHICAGO + l~~~~~~~~~~~~~~~~o 1 0 30~i'd. ~;j.0 WMH5AN OTY ^' \ ~~~~* I 0 ~20~~ \ / 30 10~~~~~~~~~~~~~~~~~~~~~~~c Illinois j Indiana',^ x t10 10 km C Figure 3.4.8: Pb isopleths for 20 June 1968.

Thurs. 20 June 1968 Pb, lg-mm3xIO + +50 3() 20 + 40 N 30 CA 0 +0 LAKE MICHIGAN V CHICAGO 20 20 20 ^+ 2'0 \+ 18 34.100 20 MICHGAN CTY 6~~~~~~~~~~~~~~~~ d200^^ oT-T1^ + 6~~~ + - 30 7 x 220.20 GARY 6*10 I 1-J20 *8.15 IS Illinois 4 Indiana x.5. ^ ^ ^, ~~~~~10 10 km Figure 3.4.9: Pb data points for 20 June 1968.

Thurs, 20 June 1968 25 5.50 Cung-m-3 x O.I + N + 0 * + /LAKE MICHIGAN CHICAGO + + 25 25 i/ 50~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ 100 25 / / I~~~~ // ~ / 1 I'. /- I Illinois I / Indiana / I /~ 1 ~~~25 ^ -.- ~~-.-, - LALLLJ*~~ I. 10 km Figure 3.4.10: Cu isopleths for 20 June 1968.

Thurs. 20 June 1968 +^ 20 c~Cung-m-3xO.I + ~ +60 20 10 + 40 + 7 j7 f AKE MICHIGAN / CHICAGO nd 0.+ nd 7 6 30 30' P-j" ~~~~~~20' y~~o M0GAN CTY 102~~ 200~~50 1 +940 Illinois' Indiana 2~~+.2f~20 x I0,inois IIndiana 10 km Figure 3.4.11: Cu data points for 20 June 1968.

2 2 4Tues. 9 July 1968 WIND N C-I / /- ~LAKE M~/CHIGAN \c-\2/ 3 * Illinois nin 0 10 0 K 2~~~~~~~~~ 10 IkmQA 1 2 Figure 3.5.1: Wind rose for 9 July 1968. 2 2C 2il ~~~~-tl+ I I K+ d j!~~~~~~~~~~~~ Mlindis 7 r ndiana 0l 1 0111 111 1 121I Figure 3.5.1: Wind rose for 9 July 1968.

Tues. 9 July 1968 r^ + 0- Suspended Particulate,,f-m'-3 + * * ~~100 +\~~ *+ ^ *^ iv N 50 * 50 ^-if~y^ LAKE MICHIGAN - CHICAGO J5 j* Y50 050 + I 50 50 *~50 Illfinois'Ind'iana x k404K4fl OTY X ~~~~~~~~~~~~CD3 Date~~~~~~~~~~~~~~~~~~~~~~~~C * Illinois I Indiana 100 (0 km Figure 3.5.2: Suspended particulate isopleths for 9 July 1968.

Tues 9 July 1968 6? HJ^^Suspended Particulote, g-m3 71 + + 74 105 49 N 100 60 86 + 152 152 + LAKE MICHIGAN CHICAGO 103 4 98-108 86 6 n1? 32 54J? ^^ MICHIGAN CITY 51 C 48 66 <49 + 1 s 109 110 44 2 --- " - *+ X H + 4+ 139 D 55 143 32 Indiana Illinois x 126 10 km Figure 3.5.3: Suspended particulate data points for 9 July 1968.

Tues. 9 July 1968 + + r" 20 S02o,ppb + 30 N 30 + 20 | 30 L AKE MICHIGAN CHICAGO 0 10 + + 00 2030 40 50 MICHIGAN CITY 50 X 04 Illinois Indiana x 10 km Figure 3.5.4: SO2 isopleths for 9 July 1968.

Tues. 9 July 1968 SO2,ppb 35 4 N 36 +9 6 - * i LAKE MICHIGAN CHICAGO < 22.9' Illinois | Indiana 10 km Figure 3.5.5: SO2 data points for 9 July 1968. 12N + 9 Illinois Indiana 10 km Figure 3.5.5: So2 data points for 9 July 1968.

Tues. 9 July 1968 Cd,ng-m-3 10 20 20 + * + LAKE MICHIGAN CHICAGO + / 10 20 10 10 — H^ issin 1;q-0^^^^ /xh * O Date~~~~~~~~T 20~~~~~~~~~~~~~2 Illinois Indiana x 10 km Figure 3.5.6: Cd isopleths for 9 July 1968.

Tues. 9 July 1968 +4 20^ nd^~ ~Cd,ng-m-3 \+ ^""^ -21 nd I0 nd 1. 6 V.20 N 8,20 +1 LAKE MICHIGAN CHICAGO J * *+ 10 nd I20 ni MIGAN OTY -+ Ip -F~ I0 ndA^ p0^ ^^^ *nd Illinois I Indiana 10 km Figure 3.5.7: Cd data points for 9 July 1968.

Tues. 9 July, 1968 + 10 Pb, pg-m-3x10 )O~~~~~~~~~~~~~1 i N I to + LAKE MICHIGAN CICAGO * 5 5% \+ + 1\%+ 0 MOW/ CITY'I + 10 + 9~;aa Illinois Indiana x lo\ (1~~0 km I0 L Figure 3.5.8: Pb isopleths for 9 Jul 1968. 90 km I'c' Figure 3.5.8: Pb isopleths for 9 July 1968.

Tues. 9 July 1968 8 Pb, 4g-mM3 x lo ^+ ^s + 4-2010 8 6 7 10 N 0 20 + L AKE MICHIGAN CHICAGO *+ 2+ 4 6 5 Illinois Indiano 6 MCH~~~~iLI ~~~N OTY x 0) Illinois Indiana 3 X'. I.... t 1^ LL ~1LuJ I 10 km Figure 3.5.9: Pb data points for 9 July 1968.

Tues.9 July 1968 Cu,ng-m- xO.I n *'+ LAKE MICHIGAN CHICAGO' —] * oo 400 MissgIGAN C TY + D Gct Rr Illinois | G Indiana x 10 km Figure 3.5.10: Cu isopleths for 9 July 1968.

Tues. 9 July 1968 (^ ^P^ ^ 2Cu,ng-m3 xO0.1 +'10 2 + 20' * C LAKE MICHIGAN - / CHICAGO nd 6 0 15 _20 MICHGA N CITY./+~ ~~30 Illinois Indiana 6 X 20 6 X 1 1 1 20 *"Iinois I nieno 10 km Figure 3.5.11: Cu data points for 9 July 1968.

Thurs. 8 August 1968 WIND 4 N C-4 4 4 2~~~~~~~~~~~~~~~ + 2 3 ^^ 2^1^4 LAKE MICH/GAN " 3A / 33 Illinois 0 Indiana 0 10 K t-t~4 ~ ~ ~ c Illnos ndan mph 10 km Figure 3.6.1: Wind rose for 8 August 1968.

Thurs. 8 August 1968 150 Suspended Particulate, /Lg-m-3 l* ^"^4> o/^ r 200 50 300 250 I 2QO'IMMC~~~~~4GN f~TY 150 ~ ~ ~ ~ ~' * + 100 r~~10 % I H Missing Data lc39 ~ ~ AR Indiana Illinois /50 — 10 kmn Figure 3.6.2: Suspended particulate isopleths for 8 August 1968.

Thurs.8 August 1968 _ 1 n<rSuspended Particulate, /g-m-3 C+ ^+13 146 239 158 22 1 0 15 305 9 _498 Illinois | Indiana Figure 3.6.3: Suspended particulate data points for 8 August 1968. — ] e. ~61 19 39 8 + Missing 49 38 46 Indiana Illinois 43 62 j,,ita I,, I L 10 km Figure 3.6.3: Suspended particulate data points for 8 August 1968.

Thurs. 8 August 1968 MD r*^^ -^ 20 S2. ppb rO~~~~~t 10~~~~1 20 10 30'o * + 130 * LAKE MICHIGAN - CHWCAO 20 0 1O *20 20 2 9~~~~0 + WHIGAN CITY + Illinois I Indiana x 10km Figure 3.6.4: SO2 isopleths for 8 August 1968.

Thurs.8 August 1968 2qJT^_j- SO2ppb + 3 4 N 13 + 3 + +i 3 ^ Z.LAKE MICHIGAN CHICAGO 6 *^24 2 4~~~~~~~~~~~~~~~~~~~~~~~ 0 MKHM~~~~~~~~~CHGN MYY + + 5 4 9 3 2C~~~~~~~~~~~4%A + TY40 3~~~~~~~~~~ GARY! ~~nd Illinois Indiana x (i..1 ~ ~i I *~l 10 km Figure 3.6.5: SO2 data points for 8 August 1968.

Thurs. 8 August 1968 + + 10 Cdng-m-3 N 20 N~20 J~LAKE MICHIGAN CHCAGO IO *A/ 0 + + 10 10 \,~~~~~1 * [ |NGAT ^'O I %/ ~ / C~~~~.,J + ~ ~ ~ ^;/ Illinois I Indiana x 10 km Figure 3.6.6: Cd isopleths for 8 August 1968.

Thurs. 8 August 1968 + io 20 Cdng-m-3 30 20 30 + + 110 LAKE MICH/GAN CHICAGO 8J nd10' +C 20 0 2 F ~10 Vnd5+ 1 10~10 km Figure 3.6.7: Cd data points for 8 August 1968. n+,~d' >"'^I* I L-J dndr n 20 nd Illinois' Indiana nd X 10 km Figure 3.6.7: Cd data points for 8 August 1968.

Thurs. 8 Aug. 1968 Pb, p/g-m-3xlO +'~ "' q40 X. 40. LAKE M/CHIGAN CKOCAGO + + 20 20 20 + 20 MHGAN CrTY 2100 GOIR e H Indiono Illinois Indiana 10 km Figure 3.6.8: Pb isopleths for 8 August 1968.

Thurs. 8 Aug. 1968 +r^JT^J"^~ ~Pb, g-m-3 x 10 30 20 + 30 N 30 40 + LAKE MICHIGAN CHICAGO 20 + 20 40 + + 20 20 15 20 10z 20 MCHIGAN CTY 3 illinois I Indiana * ~ ~ ~ * 20~~~~~~~~ ~"^ ""' I + 6 6;5 + + Mi S~ng 10 20 3s GARY Illinois Indiana 2 tj 011ti-I 21 10 km Figure 3.6.9: Pb data points for 8 August 1968.

Thurs.8 Aug. 1968 Cung-m'3x0.I + + +~~~~~~~~~~~ [' LAKE MICHIGAN CHICAGO 25 25 25 50 100 25 25 25 25 50 00200?sil -' GI.RIGAN YTY. Ij ^I +~~~~~~~~ H Illinois Indiana x 10 km Figure 3.6.10: Cu isopleths for 8 August 1968.

Thurs. 8 Aug, 1968 + 3QF Cu.ng-m-3xO.I 30 30 *nd 20 1 20 0 + * +0 L AKE MICHIGAN CHICAGO 200 5 Po2 010 60 30 s0 10 20 60 5? MK0IGAN CITY J^' " r000 ^^ MCIOT.30 20P 20o^'r,o + + MisWing x j GRY nd 10 7 l~~~~~~~~~~~~~l Illinois Indiana 9 X 4 b" <'d L l 10 km Figure 3.6.11: Cu data points for 8 August 1968.

Thurs. 29 August 1968 3 WIND C-4 ~3~2 3~~~~~~~~~~~~~ 4~~~~~~~~~~ 2 H 2 4 C-S 2 LAKE MICHIGAN 9 1~~~~~~~~ 2 9~~~~~~~~~~~~~~~~~~c Illinois 0 Indiana 0 0 mph Figure 3.7.1: Wind rose for 29 August 1968.

Thurs.29 August 1968 - s 150 Suspended Particulote, g-m, 3 / 200 N 150 IO + 200 L AKE MICHIGAN CHICAGO 200 100 50 F u2 3iA t x II Illinois I Indiana G7o0 x 10 km Figure 3.7.2: Suspended particulate isopleths for 29 August 1968.

Thurs. 29 August 1968 Suspended Porticulote, Ag-m-3 +J) 4+ 143 214 139 * 148 186 ~188 + 143 I+ I8 LAKE MICHIGAN lei CHICAGO 8 134 218 195 136 953 — I_ _'r8^>^^2 ^^^^ ~KIO5W CITY J- 214 9 os^6'9 + 8 1^.S S17 X Dot Indiana Illinois lilt~~~~ 185 10 km Figure 3.7.3: Suspended particulate data points for 29 August 1968.

Thurs.29 August 1968 20 SO2, ppb + * 30 LAKE MICHI/GAN CHKAGO* 20 20 30 ^o^-p —>^\ 30 ^~\P,^^^^ MCHKSAN ITY + + ~~~~~~~~~~~~~~~x Illinois Indiana x Il r I * "1 I * 10 km Figure 3.7.4: SO2 isopleths for 29 August 1968.

Thurs. 29 August 1968 16~jL _j-y ~SO2, ppb +~ + 26 6 + 16 +34 LAKE MICHIGAN CHICkAGO 7 + + 32 39 Illinois | I ndiana + r" 10 km + + Indan Illinois ni o 10 km Figure 3.7-5: so2 data points for 29 August 1968.

Thurs,29 August 1968 20 (^q ^^+ Cd,ng-m-3 20 I0 o+ LAKE MICHIGAN/ CHICAGO 10 20 2 40 ~~~~~~Doto ~~X GA. RY Illinois Indiana x Figure 3.7.6: Cd isopleths for 29 August 1968.

Thurs. 29 August 1968 C^130 Cdng-m-3 30 nd + 30 N20 + 15 + LAKE MICHIGAN nd CHICAGO rd3 ~+ 10 X + + 30 M1O*BAN CITY *Missing' -I n nd nd0 Z-J 20 10 40 Illinois 0 Indiana x I I I ~~~~~20 iA1J'LaLJ'L'i I. 10 km Figure 3.7.7: Cd data points for 29 August 1968.

Thurs. 29 Aug. 1968 40 Pb, g-m-3x 10 40 NJ 40 400 L AKE MICHIGAN CHICAGO + + 40 40 20 1t ^ -o0^ MCHIGAN ITY v^ +^ s + MilsSfl^^ * K 20. ~Dqto^ - *1 GARY -20 I / Illinois I Indiana x 10 km Figure 3.7.8: Pb isopleths for 29 August 1968.

Thurs. 29 Aug. 1968 Pb, g-g m3 x 10 + 40 30 + 20 40 + 30) 3 LAKEZ MICHIGAN CHICAGO 20 o20 + + O20;0^ %5 10 rO20 0~~~1 S^^' ^^ ^^ MOCHGAN OTY.8 IJ20 2 20 Dcitct Illinois30 Indiana~~~~~~~~ ~00 Illinois' Indiana x 10 L'*"~*"W I. (0 km Figure 3.7.9: Pb data points for 29 August 1968.

Thurs, 29 Aug. 1968 25 25 Cu.ng-m-3xO. I + 7+ +r N + * + LAKE MICHIGAN CHICAGO 25.+ + 5 0 25 50 5010 500 6 000 MONGAN ITY + 2 2 5 Missilng ro 5 to c GARY Illinois I' ndiana x 10 km Figure 3.7.10: Cu isopleths for 29 August 1968.

Thurs.29 Aug,1968 + +30 ^j-^ ~Cung-m-3xO. I 15 J^ 10 + 20 C A J20 nd +9 10 c —|~X? 0 40.^ T * 1LAKE MICHIGANTY 0 2 10 ~o ~-1 1 00 100 + x 1200 0Missng 7 | I QRY I +~10 ~ ~ 100 420 Mto~~~~~~~~~~~~~~~~~~~~~~~~C 8 10 Illinois ndina x 10 10 km Figure 3. 11: Cu data points for 29 August 1968.

4.0 INTERPRETATION 4.1 SUMMATIONS AND AVERAGES OF THE DATA Due to the large number of data points and the diversity of emission sources and conditions, many potential conclusions are not obvious. In order to attempt a further interpretation of such a large amount of data, Tables 4.1 to 4.4 have been constructed. Table 4.1 represents a compilation of pertinent meteorological data from Midway Airport in Chicago, Illinois. The average concentrations and their respective average ratios are presented in Tables 4.2 and 4.3. An attempt is made to separate the regions by tabulating Chicago and Northwest Indiana separately, and then a summation is given for both areas. Concentrations of copper for East Chicago, Indiana, (stations 6-10) are presented separately in order to eliminate an over bias in the rest of the Indiana region. This is not necessary for the ratios since the copper values in the numerator result in a very low number in the ratio. Table 4.4 presents correlation coefficients of each pair of elements. Additional representations in the form of histograms and of ratios of the element pairs are in Appendix IV. 4.2 TRANSPORT AND DIFFUSION The meteorological data in Table 4.1 show that the sample days were similar. Wind direction was markedly different for 21 May and 29 August, but the range on those days tends -131

Table 4.1 Average Meteorological Characteristics Wind Range Speed Range Temperature Direction degrees m/s m/s Max. Min. Ave. Precip. Relative degrees OC ~C ~C mm Humidity May 21 290 560 5.5 C-7 15.9 8.5 11.1 Trace. May 22 i80 280 5.5 c-8 16.7 6.1 11.7 2 -- June 6 i80 40 5.5 2-8 3355.9 20.0 27.2 None 55 June 20 150 150 5.8 5-8 25.6 15.5 19.4 Trace 61 July 9 210 170 6.8 4-10 29.4 16.1 22.8 Trace 60 Aug. 8 200 560 35.9 2-16 51.1 22.2 26.7 0.5 77 Aug. 29 090 150 4.2 3-6 24.4 15.0 20.0 None 58

-133Table 4.2 Average Concentrations for Each Day in Chicago and Northwest Indiana Day, Cd Pb Cu* SP S02 Bi 1968 n/ ng g/m3 n g/ gm/m ppb ng/m3 21/22 May 2000 Ind. 21 200G 180 92 1 Ill. 29 4300 300 150 0.25 Both 25 3300 750 19 0.63 6 June 3500 Ind. 8 830 390 140 Ill. 9 1300 830 170 Both 9 1100 970 160 20 20 June 3900 Ind. 15 1700 260 170 Ill. 10 2700 250 200 Both 12 2200 1000 180 16 9 July 1600 Ind. 19 810 130 84 Ill. 9 810 99 83. Both 14 810 510 84 12 8 Aug. f4800 Ind. 5 100 L 120 100 Ill. 13 2600 250 180 Both 9 1900 1300 146 9 29 Aug. 4000 Ind. 12 1500 1 140 120 Ill. 16 3100 220 180x Both 14 2200 1200 156x 17 Totals: all data Mean 19 1900 1000 150 18 0. 6 Max. 80 7000 10000 950 80 3. Min. < 5 100 < 20 30 <0.5 \C. 05 (*, stations 1-10 and 11-22 listed separately; x, station E excluded)

-134Table 4.3 Average Values of Selected Ratios for Each Day in Chicago and Northwest Indiana Day, Cd/Pb Cd/Cu Cd/SP* Pb/SP* Cu/SP* Cu/Pb Cd/S02 1968 x0.5xl0 3 21/22 May Ind. 0.012 0.099 0.023 2.2 1.7 0.89 Ill. 0.007 o.14 0.023 3.5 0.25 0.080 Both (0.010) (0.12) (0.023) (2.9) (0.92) (0.44) (9.0) 6 June Ind. 0.018 0.031 0.0098 0.57 1.49 3.4 Ill. 0.011 o.16 0.0078 0.76 0.071 0.13 Both 0.014 0.10 0.0086 0.67 o.85 1.9 4.2 20 June Ind. 0.021 0.11 0.022 1.1 0.87 1.3 Ill. 0.0044 0.087 0.0071 1.6 0.11 0.060 Both 0.012 0.10 0.014 1.4 0.54.78 3.8 9 July Ind. 0.047 0.15 0.034 0.97 0.73 0.88 Ill. 0.018 0.15 0.019 1.0 0.13 0.15 Both 0.036 0.15 0.029 1.0 0.48 0.56 7.3 8 August Ind. 0.014 0.053 0.013 1.1 2.4 2.6 Ill. 0.007 o.o83 0.010 1.5 0.15 0.12 Both 0.009 0.070 O.011 1.3 1.3 1.5 3.8 29 August Ind. 0.012 0.095 0.012 1.0 2.5 5.4 Ill. 0.007 0.096 0.013 1.7 o.11 0.082 Both 0.009 0.095 0.015 1.4 1.2 1.6 3.2 Totals: all data Mean 0.015 O.11 0.016 1.4 0.87 1.11 5.5 (*, b)

-135Table 4.4 Correlation Coefficients All Data Cd Pb Cu SP S02 Cd -- Pb 0.36 -- Cu -0.09 -0.10 -- SP 0.02 0.40 0.05 -- S02 0.05 0.21 0.04 0.29 21/22 May Cd -- Pb 0.46 -- Cu -0.10 -0.52 -- SP 0.54 0.60 -0.20 -- S02 -0.04 0.21 -0.11 -0.09 6 June Cd -- Pb 0.58 -- Cu -0.18 -0.28 SP 0.29 0.75 -0.18 -- S02 -0.10 0.55 -0.05 0.26 20 June Cd -- Pb -0.16 -- Cu -0.11 0.09 -- Sp -0.48 0.50 0.5533 -- S02 -0.42 0.29 0.37 0.52 9 July Cd -- Pb 0.10 -- Cu -0.07 0.48 -- SP 0.30 0.43 0.37 -- S02 -0.64 0.49 0.06 0.57 8 August Cd -- Pb 0.4 -- Cu -0.25 -0.16 -- SP 0.55 0.79 -0.10 -- S02 0.55 0.59 o.00oo 0.32

-136Table 4.4 (continued) 29 August Cd Pb Cu SP S02 Cd -- Pb 0.60 Cu 0.03 -0.33 -- sP 0.40 0.47 -0.10 -- S02 -0.70 -0.18 -0.32 0.41

-137to negate their usefulness in diffusion calculations. June 6 is the only day with a reasonably small variation over the 24 hour samples, but its usefulness is also limited as far as a diffusion model in so far as the East Chicago plume is advected over the lake and much of the surface plume profile is lost. However, assuming that the source is close to station 8 and directly upwind and that station 6 and/or 9 is downwind on the plume axis we can estimate the source strength by the following arguments. If we assume that the stations are located along the center line of the plume (y = 0) then Turner (1969) gives us the following equation. X(x,O,0;H) - - exp Ifa a u z y z where Q (g/sec) = source strength; X (g/m3) = concentration at sample point; H (m) = effective stack height; u (m/sec) = average wind speed; a y, (m) = deviation of wind in the y, z directions. At station 8 let H = 20 m, x = 0.1 km, X =9 x 10-6 g/m and from Turner (1969), a = 12 m and a = 7.5 m. At station 6 y z -6 3 let H = 20 m, x = 0.6 km, X = 7 x 10 g/m, and from Turner (1969), a = 62 m and a = 38 m. Solving for Q at both y z locations:

-138Q8 = 0.45 g/sec, Q6 = 0.27 g/sec The agreement is satisfactory considering that no refinements of the estimation of H on a,a were made. Then, if we y z accept the value of Q = 0.4 g/sec, the output of the source would be 35 kg/day (13 tons/year) of copper-containing aerosols (at $2/pound the dollar cost would be $77/day or $28,000/year!). This calculation points out the necessity for forecasting the wind conditions for optimum information in order to estimate the source strength of point sources. The other source strengths are not so easily calculated by virtue of the area source nature. From the point of view of bulk transport of pollutants it is evident that a case can be made for a general transport by the gradient winds. The isopleths show concentrations along lines parallel to the wind direction and, in some cases, some semblances of a plume. Due to the complexity of the sources and the mesoscale wind effects it is difficult to completely convince oneself of this fact for every element for every day, but a general pattern usually becomes evident after close examination. An example of the complexity of this situation occurs 8 August with low wind speeds, variable direction, and a lake breeze effect during the late morning and early afternoon. A lake breeze can be shown to form a convergence zone that seems to concentrate pollutants in a very narrow band, and if this band passed slowly over a station, it would give a disproportionately high amount of suspended particulate and thus pollution

-139elements. The lake stations would have lesser amounts of aerosols and the stations further inland beyond the lake breeze front would have a normal proportion of the suspended particulate. One could probably argue that an attempt should be made to further model the concentration characteristics of the region for these particular days, but considering that only one station was available (East Chicago, Indiana) with any detailed wind information, it would be difficult to try to provide more detailed calculations. Thus, in order to further interpret these data,greater meteorological detail must be obtained with more first order meteorological stations and a greater density of samplers. The present station is adequate for gross measurements but does not provide sufficient data to do a complete diffusion analysis. 4.3 REMOVAL PROCESSES The primary removal processes are mixing and advection out of the source area, chemical reactions, fallout, and washout or rainout. Mixing and advection are not usually thought of as removal processes but are used here as mechanisms for decreasing concentrations in the sample areas. From Table 4.1 the average wind speed is about 5 m/sec or 18 km per hour; thus, most aerosols emitted into the air have an average residence time of less than one-half hour over the cities, precluding fallout. Mixing is faster due to solar insolation during the

-140day and is primarily mechanical at night. If we assume that airborne particles have an average fall rate of 1 m/min, then the particles would fall 30 meters in one-half hour, which is small compared to the horizontal advection and vertical mixing under normal conditions. We then would assume that a large part of the aerosols emitted in the metropolitan area are advected out of the immediate environment. Due to the proximity of Lake Michigan and the prevailing winds we should concern ourselves briefly with the possibilities of contamination of the lake and surrounding regions downwind from these sources. Winchester and Nifong (1969) have calculated from available data various estimates of trace metal transport both by rivers and by fallout of air pollution. The positive argument presented is that almost half of the prevailing winds are from the southwest sector which would advect most of the industrial effluents over the lake. Looking closely at the total picture of isopleths for each metal, we can give an educated guess as to the various size distributions and thereby the fallout rates of these materials. First of all, lead is known to be of the order of less than one micron mean diameter and usually is stated to be about 0.25 microns mean diameter (see Appendix II). Therefore, lead, once airborne and thoroughly mixed into the mixing layer, will not settle out very quickly, although initial fallout should occur very close to expressways and emission sources. The copper component, especially in East Chicago, Indiana, shows a definite

-141fallout close to the source with closely packed isopleths decreasing rapidly. Also, cadmium aerosol isopleths close, but not as quickly as the copper and not as slowly as the lead. It can be assumed that the cadmium fallout would lie somewhere between the lead and the copper. In the Ann Arbor area the aged Cd and Cu aerosols have a similar size distribution with a maximum at 1.0 p diameter. If we are allowed to make an inference from that data to this study area, we can predict that the Cd and Cu aerosols will behave similarly except in the anomalous regions in East Chicago, Indiana. Therefore, fallout would be slow except close to the sources where coagulation and agglomeration usually occur within the process system. Please see Appendix 1.5 for a recent dust fall measurement. Probably the most efficient method of removing these mixed aerosols from the atmosphere is convective rain and snow storms. Gunn (1960) has shown that electrified storms are extremely efficient at removing aerosols quickly. Thus, we predict that all of these trace elements are not falling into the lake by dry fallout in as large quantities as that due to precipitation once they are advected from their points of emission. Copper, close to East Chicago, Indiana, under southwest wind conditions, is falling into the lake but close to the shore. The primary area affected is probably no larger than twice the size of East Chicago itself, approximately 30 kilometers. Appendix 1.4 presents a few rain samples from the area and indeed removal seems to be taking place.

-1424.4 SUGGESTED SOURCES —COMPARISON WITH EXISTING DATA In Table 4.4 the correlation coefficients do not show the results expected. Only lead and suspended particulate are at all consistently positively correlated; the remaining parameters have varying coefficients from day to day. One would not necessarily expect lead and sulfur dioxide to correlate well, but copper and cadmium and possibly sulfur dioxide were expected to have resulted in some dependence due to their similar natures and possible sources. Frequency tables were generated by a multiple pass program eliminating data that contributed to less than 6% of the total on either side of the maximum category resulting in smoother distributions. Passes 1 and 5 are listed in Appendix IV. Some micro structure is apparent but the significance is questionable. Also in Appendix IV we have listed all possible ratios of element pairs. Table 4.3 is a selected summary of that data. The usefulness of these ratios is apparent by considering that even though the total values vary and other elements are randomly contributing to the total suspended particulate, the ratios would remain the same if no other sources were present. These ratios are also useful in predicting the sources and the compositions of the aerosols. As far as finding the sources of the elements, the persistent copper maxima in East Chicago, Indiana, are the only convincing small area (or point) sources. All other data seem to imply more area-wide sources except for a few occasions of suspended particulate at station E in south Chicago

-143and Gary. The lead seems to be persistent in following the traffic densities, as far as we know them, with broad maxima and little fine structure. Also, cadmium and Chicago copper have only broad distributions with many other small sources implied. Sulfur dioxide is higher in the Chicago region, probably due to the larger amounts of coal being used there as compared with Northwest Indiana. Figure 4.1 is a representation of the fossil fuel burning facilities in the Chicago area. Comparison with the isopleths shows a good agreement in location of sources (e.g., 21 May), but insufficient information is available for comparison to source strengths. A logical next step to be taken is to try to match the atmospheric data given here with known inventories. Source inventories of trace metals are very scarce for the Chicago and Northwest Indiana regions. Winchester and Nifong (1969) have compiled a conservative estimate of trace metal emissions in the study area. Table 4.5 is an excerpt of that inventory. Table 4.6 presents a comparison of ratios obtained from independent sources for comparison to the data presented in this work. In addition to the Winchester and Nifong estimates of source emissions, Kneip et al. (1970) have presented data for four stations in New York City for cadmium, copper, and lead (section 1.3.5),and McMullen et al. (1969) have compiled averages for 147 stations throughout the United States for copper and lead, and sulfate particulates (section 1.3.4). From the table it appears that the non-anomalous copper and the cadmium can be explained by the burning of fossil

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Table 4.5 Contributions of Fuels to Lead, Cadmium, and Copper to Chicago Area Suspended Particulatea Coal Coke Fuel Oil Gasoline Combustion estimate, megatons/yr 20 15 7 8 Particulate emission estimate, kilotons/yr 220 18 14 b Pb emission estimate, tons/yr 300 22 30 1,800 Cd emission estimate, tons/yr 11 1 - t Cu emission estimate, tons/yr 100 7 26 aAfter Winchester and Nifong (1969). All units are metric. bAssumed 2 g Pb/gallon and 25% of emissions airborne.

Table 4.6 Comparisons of Average Ratios from This Study to Independent Data Cu/Cd Pb/Cu Cd/SO Cd/S Cu/SO Cu/SO~ Cu/S Pb/SO Pb/S 2 2 4 2 This Study Chicago 8 10 -- -- 0.036 -- (0.018) 0.28 (0.14) All Stations: 9 0.9 0.0055 (0.0027) 0.1 -- (0.05) 0.2 (0.1) Winchester and Nifong (1969) Fuels Only: 11 18 -- 0.000017 -- -- 0.0002 -- 0.0034 All Sources: 270 0.7 -- 0.000017 - - 0.005 -- 0.0032 Kneip et al. (1970) New York 10 15 McMullen et al. (1969) U.S. Average: -- 4. la -- - - -- 0.016a (0.005) -- (0.022) aUrban and "proximate" values only. ( ) Estimated from SO or SO4 values.

-147fuels and that the data is consistent with that found in New York City by Kneip et al. (1970) and predicted by Winchester and Nifong (1969). There is a discrepancy between the predicted ratio in the Winchester and Nifong data from all sources including metallurgical for the Cu/Cd ratio. This difference may be partially due to the fact that our value is averaged over a fairly uniform grid over a large area, consisting of many low source regions, which may not have been representative of all metallurgical sources near the lake shore. Similarly, the Pb/Cu ratios agree within reason considering the non-anomalous sources. The values for this work are close to the values of McMullen et al. for the U.S. and lie between those of Winchester and Nifong's estimations for all sources and those of fuel sources. The agreement is close for both categories. If copper and cadmium are indeed emanating from coal ash or fuels, then there should be some agreement with the estimation of ratios from these elements and sulfur dioxide measurements. Since sulfur dioxide oxidizes into sulfates, the ratios should be taken with total sulfur, but as usual this data is not available but can be estimated. Sulfur usually exists in the atmosphere as S02 gas or as sulfate particulate (and some H2S04). The summation of each component should equal the total emission inventory of sulfur. By inspection of the Winchester and Nifong inventory values and those calculated from this study we can see that the element

-148to sulfur ratios fall below the estimated by a factor of 10 to 100 for all three elements. The interpolated Cd/S values are larger by a factor of 100, the Cu/S by a factor of 10, and Pb/S by a factor of 100 as compared to the Winchester and Nifong data. Comparison to the McMullen et al. interpolated results show a similar discrepancy of 1C for Cu/S and five times higher for Pb/S. Since most values of the ratios of S02/SO4 are unity we probably could not make up the difference by adding the missing components as it would not be factors of ten. Taking into account all the information in Table 4.6 we must invoke the possibility that the trace metal inputs estimated by Winchester and Nifong (1969) are too conservative or that our values are too high by a factor of around ten. (It seems unlikely that Winchester and Nifong have over-estimated the sulfur output in this area by ten-fold.) Four possible explanations for the discrepancy can be offered. 1. Since the emission inventory is a conservative one, and due to the small average size distributions of the elements (Appendix II), there exists the possibility that the Cd and Cu in the fly ash are differentially emitted in greater amounts than hitherto expected (Caffee and Gerstle, 1967). Since most collections are size dependent, this reasoning is a plausible explanation that leads us to be concerned about our projected emission and exposure rates. 2. There is a probability of a differential settling rate between the particulates Cd, Cu and Pb, and the S0O gas;

-149warm gases rise but most aerosols fall except under mixing conditions. When observing a plume one can sometimes see the fallout of aerosols from the plume with the steam and gases continuing in a normal diffusion manner, which leads us also to be reminded that the samples were all taken in the summer months with most of the sulfur emitted from power and manufacturing industries, which in all probability have high stacks. Thus the argument given previously about comparing the high volume emitters and their inventories with a wide-spread sampling grid, especially with the emitters high above the samplers, leads to difficulty. 3. The latter argument leans heavily on the notion that other sources of the trace elements exist but with low-sulfate contents. For example, most of the stations are located in populated areas where much home incineration and some trash burning is present. All of these emissions would contain trace materials but an unknown quantity of sulfur. The coincidence of maintaining the Cu/Cd ratios is not surprizing due to the fact that most of the material burned in these areas is of organic and, most probably, wood origins. 4. Finally there is a reasonable amount of reflotation of cinders, etc., in these areas, whereas the SO2 is converted to sulfate and does not return to SO2 to be refloated. Thus, a comparison of trace metals to SO2 is difficult due to the many unknown behavioral characteristics of the SO2 life cycle as compared to those of the aerosols.

-150In conclusion, the anomalous copper in East Chicago, Indiana, is due to a point source suspected but as yet unknown. Other copper particulates and those of cadmium are best explained by the burning of fossil fuels and incineration as pointed out by the close agreement in the ratios and their distribution characteristics. Lead is obviously emitted almost entirely by automobiles, and no other source is expected. A final comparison should be made. The National Air Sampling Network (NASN) runs more than 100 Hi-Vol stations in communities all over the United States. Approximately 17 trace elements are analyzed and reported. Since a NASN station was in operation at location 2 in Hammond, an opportunity exists for a comparison. Table 4.7 represents three classifications of NASN stations in the state of Indiana: Hammond, an industrial-urban site; Beverly Shores, a proximate station; and Parke County, a rural location. These results are compared with the results of the six day study and point out some inadequacies of using the NASN station in Hammond to represent the whole southern Lake Michigan region. Only cadmium, and possibly bismuth, are representative, and then probably because of their low values. In addition, the station is not placed according to population exposures since the most populated area in the Northwest Indiana region is around station 9 (U.S., HEW, 1966), where the prevailing winds carry the copper, with a large amount of lead already being emitted in that area.

Table 4.7 Comparison with NASN 1963 Data, ng/m3 Pb Cd Cu Bi NASN, ParkeCo., rural 24-57 1.8-5.2 17-80 <0.5 NASN, Beverly Shores, proximate 100-200 ND-10 30-50 <0.5 NASN, Hammond, urban 100-1,200 ND-55 30-180 <0.5 This study, all stations8 100-7,000 <5-80 <20-10,000 <0.05-3.0 This study, station 2, Hammonda 1,000-3,000 <5-20 100-1,000 --- aIndividual values reliable to a factor of 2.

-1524.5 ECOLOGICAL EFFECTS —TOXICOLOGY Before presenting a discussion of toxicological levels of these pollutants we should point out once more that there is little known about the synergistic effects of these various pollutants for 24 hour exposures over several years. The arguments presented are based on eight-hour industrial exposures for healthy males, as listed in Table 4.8. In order to estimate a 24 hour exposure limit we can point out that a 40 hour work week is one-fifth of the total week and that, as in radiation limits, an additional factor of one-tenth is invoked to account for continuous exposure. Thus the eighthour limits have been reduced by 50 for totally exposed receptors. No element is equal to or greater than the threshold limit values available, but lead and copper are approaching prohibitive quantities in some areas. This is especially evident considering the cumulative effects of lead and that these are not the highest values possible under extreme conditions that frequently do occur in this area. Although the observed concentrations are below the human receptor levels, there is another parameter that must be considered —plant ecology and transport to clean waters in streams and lakes. Since the streams in the area are contaminated by industrial discharges, we will neglect this discussion except to note that some clean streams may exist in the out county areas and could be influenced by pollution aerosols.

-153Table 4.8 Comparison to Toxic Levels Element TLV Highest Level 8 hr. 30 days Observed 24 hrs. 3 3a 3 Cd 100 P 5 g/mm3 0.08 Pg/m Pb 200 Pg/m3 10 vg/m3 7 Pg/m3 Cu 1,000 pg/m 50 Pg/m > 10 Pg/m3 Bi None -- 3 ng/m aEstimated, see text. bAmerican Industrial Hygiene Association (1969). Threshold limit values for healthy males of working age.

-154The only evidence of possible plant damage available to us at this time is indicated by a large copper maximum in * East Chicago, Indiana, and the more frequent occurrence of reported plant damage. If we accept the addition of copper by fallout to the soils to be over 30 micrograms per square meter (= 3 ppm) per year, we can predict that in a decade the topsoil will have approached the toxic limits found by Reuther and Smith (1955) of 160-180 ppm. This amount has already been achieved at station 9 by the results of measurements cited in Appendix I. Since the copper concentrates primarily in the tree roots, the toxic value can be allowed to go slightly higher since a large amount, but not all, of the roots are below the topsoil. We must also ask whether the copper is in a soluble or organic form quickly available to the plants. Table 1.6 shows that less than 10% of the copper fallout is water soluble. The question then arises of how long the copper has been deposited. Less than a century is sufficient to allow copper to enter into the larger percentage of the root systems, considering especially that the water supply usually comes from the topsoil. For example, a copper poisoned tree will exhibit blackened root tips and concentrations of up to 5000 ppm, but the leaves would contain a lower concentration of 32 ppm with young trees being especially susceptible to Mr. Dennis Karas, Director of the East Chicago Air Quality Control Division, has found moderate damage hitherto blamed on SO2.

-155copper poisoning. The problem, then, is not as straightforward as we would like, and lends itself immediately to the suggestion that the copper content of soils in this entire area should be measured with respect to solubility and insolubility fractions,and the real causes of already reported plant damage should be investigated. A partial bibliography has been prepared by Jerry Klein at Argonne National Laboratory, Illinois. 4.6 CONCLUSIONS AND SUGGESTIONS FOR FURTHER INVESTIGATIONS An obvious situation in need of immediate further investigation is the large copper maximum in the East Chicago area. Since there are several industries capable of producing copper in large amounts, we cannot say as yet which specific industry or corporation is responsible. From the data presented in this work we can design experiments with which to discover the exact location and the industry causing the copper aerosols, and thus hopefully lead to its abatement. This study has strongly shown the need for more areawide studies of this type not only in the southern Lake Michigan region but in all large metropolitan and industrial areas. Finding a large and potentially dangerous source such as the East Chicago copper plume is sufficient justification in itself. Additional information such as levels of receptor exposures and matching with source inventories are extremely useful. Anodic stripping voltammetry (ASV) is capable of sensing a few more elements, but recent developments in neutron activation analysis (NAA) and acquisition of new

-156equipment has made an additional 30 or so elements available for analysis at the University of Michigan. Experiments have been and are being continued along the same concepts. Other agencies should also seek to enter into area-wide sampling and research using these more sensitive methods. A simple way to investigate the problem of both dry fallout and precipitation is to analyze the dust fall taken at almost every station in this area, which is reported in the soluble fractions and the insoluble fractions that are available for analyses giving the input fraction. With a soil analysis we can obtain a good estimation of the amount of trace metals that are being washed from the topsoil into the streams and then into the lakes. A direct measurement of the streams could also be used and may be done more easily. More on site measurements should be taken before additional speculation is proposed. A final parameter that has been examined at the University of Michigan is size distribution of various trace elements. Our inability to satisfactorily calculate the percentage of fallout of these various trace elements by classical diffusion equations points out the need for more information on the size distribution with respect to each trace metal, as well as simple dust fall measurements. In addition, a great amount of information is gained by examining the ratios and distribution of various trace elements in order to attain their probable form. For example, if a ratio is constant over a distribution, and the distribution shape is

-157similar, it can probably be deduced that both, or all, such elements are from the same sources and are probably coagulated on the same aerosols. A 42 hour continuous sampling study was conducted at the University of Michigan and was presented at the annual American Meteorological Society meeting in 1969. This paper is presented in Appendix II. In this paper we suggest that airborne particulates can be shown to be advected over moderately large distances from urban industrial regions to more nonurban areas if sufficient accuracy and meteorological data are present. From the former discussions we can make several final observations pertinent to the criticisms of this type of area-wide survey. The first, and perhaps the more important observation, is that from Table 4.2 one can now state clearly the general exposures of receptors in this area to the six parameters studied. The levels are high in some regions, but not yet to the toxic levels. We would hasten to add that these levels in conjunction with additional element stress could make these concentrations prohibitive, especially considering the long term exposures incurred. A second important conclusion is that relative to copper the NASN station satisfies neither the maximum (source) concentrations nor the maximum population (receptor) exposure, and that the NASN lead values seem low for rural stations. From this conclusion we can immediately suggest that this type of area-wide survey be periodically undertaken to best

-158suggest the proper location of the NASN stations for observing the criteria desired. This study, in conjunction with Harrison et al. (1970), suggests that station 9 is probably the best receptor location and also is nearly the maximum industrial exposure according to prevailing winds. Due to the fact that this study was an initial attempt at a trace metal survey, with only 3-4 metals analyzed (Cd, Pb, Cu and Bi), and that the sampling days were predetermined, the maximum information was not obtained. Six days, weekdays at that, are more than sufficient to describe such an area. In the future, three forecast days will probably be sufficient: one with wind from X~ with little variation, the second with wind from X + 90~ (for source location), and a low wind day for maximum concentrations. This information, in conjunction with dust fall data, would greatly increase our knowledge of the source locations and fallout information. From the information presented here there is only one partial day with a rapid incursion of a "clean," new air mass, notably 9 July. Most of the other periods were similar; low ventilation and "old" air masses. Thus, forecasting is necessary if the cooperation of the local agencies is forthcoming. The attempts at calculations of source strengths were tenuous at best. At least a lower limit can be found from the dust fall data by multiplying the area of measurable fallout by the average non-background concentrations. Probably the better procedure is an inventory and stack sampling study in

-159conjunction with aerosol measurements, suggested by such areawide surveys as presented in section 4.4. Concerning sources for each element, only copper shows a definite and persistent source with concentrations of more than 100 times greater than those of rural areas. Subsequent studies by Harrison et al. (1970) have shown sources of other elements in the Northwest Indiana region obtained by neutron activation analysis. Lead shows the expected traffic dependency but cadmium and copper in other areas show no single source but have persistent non-stationary broad maxima in Chicago. Another important observation is that suspended particulate measurements are extremely deceptive. Suspended particulate is a broadly distributed parameter not showing, at all, the large concentration gradient seen in this work. Suspended particulate is relatively stable except during rapid incursions of clean Canadian air and possibly during heavy precipitation. Thus, the fine structure of specific pollutants cannot be implied in any way from total suspended particulate data. Boundaries of states, cities and counties are meaningless in pollution studies, and additional inter-agency cooperation is immediately necessary. The duplication of manpower and the scarcity of needed talent amoung these agencies, which seems necessary as long as boundaries and limits are set, seems to be a real waste of this manpower and talent.

-160An unexpected observation is that plumes of elements are lost very quickly into the background. This phenomenon was unexpected to the great degree in which it was observed. The pollen studies mentioned previously implied an advection by 850 mb winds of 20 micron particles of density one for a distance of over 300 km (section 1.6). This expectation of observing plumes into the proximate areas by ground-based stations was not at all realized due to high background levels and non-steady state meteorology. Proximate stations are affected by urban emission but cannot as yet be fully quantified. We are then led to the question, what are the background levels? The data shown here can put an upper limit of 3 3 < 20 ng/m on copper, of < 5 ng/m on cadmium, and < 0.05 ng/m3 on bismuth, but lead is more elusive since it is more widely distributed and is measurable at all stations under all conditions. The lowest value of lead observed was 100 ng/m3. Since the rural levels are so high, one is not able to trace the cities' contributions much further than the city limits. And, there are other trace metals equally as well distributed. Sensitivity is a limitation in the NASN studies. A once-a-month sample in questionable locations leads to a questionable result, considering that one station represents several hundred kilometers and some of the values reported above are barely above the sensitivity of the instruments used. But, the data in the urban areas do seem to show a

-161real persistence over the six days studied. Thus it seems that the random sampling is possibly sufficient if the sampler is properly placed. We would recommend more long-term, lowvolume sampling with more sensitive techniques for receptororiented monitoring. Finally, it would seem that a study of this type should be made in all suspected pollution regions at least once every decade as industrial activities may change significantly in even shorter times. The information is valuable to future interim studies both for abatement and scientific purposes. These initial results have been of use to other researchers in location and selection of sampler sites, as well as to the local abatement agencies in their abatement activities.

APPENDIX I SUPPLEMENTAL TRACE METAL DATA -163

APPENDIX I SUPPLEMENTAL TRACE METAL DATA I.1 RESEARCH SHIP INLAND SEAS —MAY 20-23, 1968 During the week of 20 May to 23 May 1968, the Great Lakes Research Division research ship, Inland Seas, made a voyage from Grand Haven, Michigan, to Calumet Harbor at the IndianaIllinois border at Chicago, returning the following day (21 May) to Grand Haven, and then voyaging from Grand Haven to the central part of the southern Lake Michigan basin for a 24 hour on-station examination of trace metals in aerosols and size distribution. Table I.1 represents the time intervals, coordinates, meteorological parameters and the concentrations of lead, cadmium, and copper during each of the intervals cited. The first coordinates given are the beginning coordinates, and the following coordinates in the column are the beginning coordinates of the next sample interval, and so forth. Intervals are adjacent within 30 minutes of each other except for the night samples in the port of Grand Haven. The interesting results of this study are that lead seems very high in the Calumet Harbor but is an average of 1.5 pg/m in the center lake station (the 24 hour station) for a surface wind sector of 270~. Cadmium seems to be higher than expected and may be due to contamination from the ship itself. The data does seem fairly consistent throughout all stations except in the Calumet region where the cadmium increases markedly. The -164

Table I.1 Inland Seas Data for 20-23 May 1968 Date Time Interval Termination Wind Wind Temp. Weather Cd Pb Cu Starting Start Min. Coordinates Direction Speed ~C ng/m ng/m3 ng/m5 Number CST Knots 20 0726 114 45.1x86.4 500 8 5.4 low 350 2,700 790 1 1006 33555 42.9x86.6 300 6 6.9 cloud 152 407 152 2 1558 74 41.9x87.5 070 3 9.7 cloud 52 8,100 190 5 1726 595 Calumet090- --- ----- 214 4,600 2500 4 21 0003 155 Calumet 270- -— 1 —— 57 16,600 560 5 0223 217 Calumet 280 C --- ----- 28 10,600 610 6 0651 241 Calumet 2505 9.53 ----- 66 660 180 7 1044 258 42.5x87.0 2506 9.2 ----- 48 4,200 350 8 1516 255 45.0x86.5 27 9 7.1 --— 9 850 440 9 22 0645 255 Gr. Haven 1706 8.3 ----- 102 1,240 520 10 1046 250 42.5x87.0 l80 7 10.0 Fog 41 2,900 120 11 1508 908 42.5x87.0 140-090 6.7 8.5 L. rain 18 1,100 160 12 25 0655 202 42.5x87.0 090 8.8 9.5 ----- 20 1,200 250 15

-166Wis. LAKE MICHIGAN Michigan GRAND HAVEN N.l ) Af 0 10 20miles 0 10 20 30 Km CHICAGO 3 i a Illinois Indiana Figure I.1: Trajectory of research vessel Inland Seas, 20-23 May 1968.

-167levels of cadmium on the lake other than run 2 are below 3 0.1 Pgm/m as would be expected from the six day study, but Calumet and Grand Haven seemed to be above this value. The on-station values for cadmium are 20-40 ng/m3. Copper also seems consistent except for the initial period in the Calumet Harbor when the wind shifted from the east, that is over East Chicago, Indiana, to Calumet, giving a single point anomalous high of 2.5 pgm/m3. Another anomaly that exists shows up in 3 run 8 where the low value for lead is 4.2 pgm/m following a 3 low value of 0. 7 pgm/m. Either run 7 is in error for lead or the research ship went through a plume of lead aerosols at stations 8 to 9. We would not say much more about this data in so much as this was a very preliminary attempt at grasping the values on a non-emission source area. All of these aerosols must have been advected from emission sources, be they either natural or human, or the vessel; thus, one can gain some idea of the background levels for the particulate air mass during the study days. It is interesting to note that the light rain did suppress the cadmium slightly, but not the other parameters. This decrease for cadmium is probably not significant due to the low signal. It also should be mentioned that the high volume samplers were not in shelters and sampled fallout as well as suspended aerosols, and the possibility of local contamination is always present. In conclusion, we can observe that the copper source in East Chicago is again validated by sample no. 4 and that lead values are increased for a sampling

-168station located close to the ground, that is to say that the Inland Seas sampling station in Calumet Harbor was probably not more than 5 meters above water level and the Calumet Harbor is below the average street level and close to expressways. Thus the samples for lead should be higher than the above street level samples from the Hi-Vol stations in the six day study. The final suggestion is that more studies of this kind, with additional controls, be made to ascertain the fallout into the lake. Hi-Vols in conjunction with dust falls would give a great amount of additional information that our research group is now seeking. 1.2 MARIETTA, OHIO, 1969 Table 1.2 presents the tabulation of a preliminary study in the mid Ohio Valley region of the Marietta, Ohio, region. There are large pollution sources in the area that are suspected for their rain suppression characteristics. It was desired to gain some insight into the trace metals in the aerosols. The three metals were analyzed by Anodic Stripping Voltammetry and showed no significant anomalies except that an additional background level is gained by observing the average values of each trace element presented. 3 Lead is usually less than 1.0 pgm/m and cadmium is less than 3 0.07 pgm/m except at one point which is probably a result of contamination.

-169Table 1.2 Hi-Vols Taken of Marietta, Ohio, Region, 1969 Interval Date Weather Wind Cd Pb Cu Station mph ng/m3 ng/m3 ng/m3 Jan. 08-08 18/19 L.rain 7 870 460 3 " 20 L.rain 31 830 150 " 23 ----- (330) 1100 190 26 Clear 66 2700 590 29 - - 14 500 230 31 ----- 69 860 240 Feb. 08-20 2 ----- 19 660 250 20-08 2/3 -- 14 760 110 12-12 16 ----- 38 600 180 2 March 5 ----- 21 810 90 "I 14 -— 43 500 120 II 21 ----- 6 760 70 if 28 - - 8 540 70 I April 5 ----- 128 460 130 Average 36 850 220

-1701.3 MEXICO CITY During a brief vacation in Mexico City, Mexico, in 1968, two samples were taken using a low volume sampler and a 1964 high volume sample was obtained from local authorities. These data are presented without reference to location as the exact location of the 1964 study is not yet known, and in the 1968 sample there was a building under construction close by and might have led to contamination of the sample. The night sample is probably the most representative (S2M8) and the 1964 sample is also very representative but of a different area within the city. If these values are correct, Mexico City should quickly institute a trace metal study to determine the source and the true levels of some of the toxic elements. We cannot validate this information so we will not comment much further except by corresponding with the local authorities and urging them to look into this matter more completely. I.4 RAINFALL During the logistics of the 1968 study three rain samples were taken. On the south side of Chicago near the lake, the second at the Gary-East Interchange on the Indiana Tollway approximately 200 yards from the expressway, and the third in a park adjacent to LaPorte, Indiana. Table I.4 is a listing of the concentrations of the three trace metals with respect to the concentration per 10 ml sample and the concentration in the total rain collected. Cadmium exhibits a high concentration in south Chicago diminishing through LaPorte. The outstanding result for lead is that the total amount per rain

-171Table 1.3 Mexico City Hi-Vol, 1964, and Low Vol, 1968 Date Sample Cd Pb Cu Code ng/m3 ng/m3 ng/m - - Hi-Vol 1964 24 hrs. 23 6800 1030 S1M4 Aug LowVol 2400 30, 400 11500 S1M8 1968 Intermittent2400 21,800 7700 28,000 Aug Night 2700 4,000 M S2M8 1968 LowVol

-172Table I.4 Rainfall, June 26, 1968 ng/10 ml ng/total rain Cd Pb Cu Cd Pb Cu south Chicago 1952 453 437 77300 18200 17500 Gary-East 430 245 387 30100 17200 27100 LaPorte 246 209 109 20900 17800 9300

-173is the same for each occurrence within 5%. Copper, however, shows a high concentration at the Gary-East Interchange. These results are as expected, except for lead. The copper high in Gary-East is probably due to the advection of copper into a storm in East Chicago, Indiana, washing out by impaction and uptake by raindrops. The consistency of lead per storm is extremely interesting and is being further investigated by myself and A. N. Dingle of the Department of Meteorology at the University of Michigan. I.5 FALLOUT It is not the purpose of this work to investigate the complete cycle of aerosols in this area but to examine the concept of area-wide sampling and to test the reliability of the NASN stations for trace metals. In order to try to give some idea of the fallout, a suite of five samples of dust fall was analyzed for stations 6-10 in East Chicago, Indiana. These data are tabulated in Table 1.5 and plotted in Figures 1.3 and 1.4. In addition, soil samples and grass roots were analyzed close to station 9. The local abatement personnel have related that the month of August, 1969, presented here was an exceptionally low dust fall month and can be assumed to be close to the lower limit. The data were obtained by perchloric acid digestion and analyzed by anodic stripping voltammetry (ASV). Using this data we can calculate deposition rates of 2 2 50 ng/m -min and 30 ng/m -min for copper and lead respectively. If we use our average concentrations we can approximate

2 Table 1.5 Dust Fall for August 1969, mg/m2-month STATION 6 7 8 9 10 soil(9) grass roots(9) Pb Insoluble 5.2 29. 14. 16. 5.6 Soluble 0.94 0.36 0.34 0.26 0.68 Total 6.1 29. 14. 16. 6.3 0.7mg/gm 0.4mg/gm 2.6 7.2 7.6 6.8 3.5 Cu Insoluble 0.76 4.1 3.7 2.0 0.31 Soluble 0.24 0.20 0.21 0.10 0.16 Total 1.0 4.3 3.9 2.1 0.47 O.16mg/gm 0.58mg/gm fo ~0.43 1.1 2.1 0.89 0.26

-175N W E 25 / S Average Speed: 7.6 MPH Midway Airport August 1969 U.S.Weather Bureau Figure 1.2: Wind rose for August 1969.

-176DUST FALL Total Lead mg/ma -month August 1969 010~10 Solbl20 16.3 10 29 O.4 Total Figure 1~~~~~~~. / Figure 1.o3: Lead fraction of total dust fall.

-177DUST FALL Total Copper mg/m2 -month x 10 August 1969 O Insoluble X C f o ta d 21 16!O 39 / T Soluble I~ Total Figure 1.4: Copper fraction of total dust fall.

-178a lower limit value of the fall velocity of 0.2 m/min and 0.3 m/min for copper and lead. Since the dust fall was said to be low for this period the results are not too far from the generally accepted average of 1.0 m/min. Thus the particles seem to be in the submicron to micron range. Future work by Nifong (1970) will further elucidate the size distributions in this area.

Relatively Heavy Urban Traffic Densities + 4~~~ 1+ LAKE MICHIGAN CHICAGO ++ CA. RY Illinois Indiana x LLLLLLL~~~ I.* 10 km Figure 1.5: Estimation of traffic densities.

APPENDIX II TIME VARIATIONS OF LEAD, COPPER, AND CADMIUM CONCENTRATIONS IN AEROSOLS IN ANN ARBOR, MICHIGAN American Meteorological Society 49th Annual Convention, January 20-23, 1969 -181

APPENDIX II TIME VARIATIONS OF LEAD, COPPER, AND CADMIUM CONCENTRATIONS IN AEROSOLS IN ANN ARBOR, MICHIGAN* Paul R. Harrison, Wayne R. Matson, and John W. Winchester Department of Meteorology and Oceanography The University of Michigan, Ann Arbor, Michigan 48104 II.1 ABSTRACT The atmosphere in Ann Arbor (50 km west of Detroit) was sampled for aerosols for two-hour periods over a 42-hour interval Friday to Sunday, April 26-28, 1968, using a modified seven-stage Andersen cascade impactor and a glass backup filter. The eight particle size fractions from each sampling were analyzed separately for lead, copper, and cadmium by means of anodic stripping voltammetry (ASV) with the composite mercury graphite electrode. Average particle size distributions were similar for the three elements over 0.1 < r < 10 p, the radius range covered by the impactor stages which sort particles into factor of 2 radius intervals. Pb, however, showed a significantly greater proportion of its total concentration in particles caught by the filter (r < 0.1 p) than did Cu or Cd. Detailed differences in size distribution from sample to sample for Cu and Cd were similar and differed from those for Preprint of paper presented at the 49th Annual Meeting of the American Meteorological Society, January 20-23, 1969, New York, session on atmospheric chemistry, John W. Winchester and Julian Shedlovsky, co-chairmen. -182

-183Pb. Substantial parallel time variations in total concentra3 tions were seen in the ranges 6000 > Pb > 600 ng/m 3, 3 3 1000 > Cu > 100 ng/m, and 300 > Cd > 100 ng/m. Two prominent maxima were observed at 0200-2400 EST, April 27, and suggested a wind shift from north to east. The results imply that some of the Cu and Cd, and much of the Pb at the maximum times came from the Detroit sector by easterly winds and that a two-hour sampling period is adequate for correlating changes in the environment with mesoscale meteorological parameters. 11.2 INTRODUCTION The analysis of urban atmospheres for lead and other trace metals has been carried out for many years, but because of the small quantities involved the majority of the work has been done on total concentrations of the elements studied. Ludwig and Robinson (1968), Lee, Patterson and Wagman (1967), and Wagman, Lee and Axt (1967) have obtained information on the size distribution of a few trace elements and sulfates. All of these samples, however, were obtained for periods of at least six hours, and most often for 24 hours or more. A short sampling time is important in order to correlate the time variation of aerosol concentrations and size distribution with mesoscale meteorological phenomena. Also, definition of the extent of variation of the quantity of an element is of interest from the standpoint of problems involving nonlinear effects with concentration, such as the exposure and uptake in an urban population, removal and chemical reactions of aerosol particles, or changes in the size distribution.

-18411.3 SAMPLE COLLECTION AND ANALYSIS On Friday afternoon, April 26, 1968, a modified sevenstage Andersen cascade impactor with an inline backup glass filter was attached to a Gelman Air Sampling Kit placed on a platform on the roof of the East Engineering Building at the University of Michigan in Ann Arbor. The area is characterized by gently rolling terrain with little local manufacturing or power generating industry. Located 50 km east of Ann Arbor, the metropolitan area of Detroit shown in Figure 2 II.1 covers an area of approximately 200 km2. It has a population of 2,000,000 persons, is heavily industrialized, and has a large amount of automotive traffic. The sampling was carried out at two-hour intervals and terminated on Sunday afternoon, April 28. Ambient meteorological data were obtained from instruments located in the immediate proximity of the sampler. The samples were obtained on 4 mil thick polyethylene discs which had been precleaned by ultrasonic agitation in double distilled water, dried, and placed over the stainless steel Andersen impactor plates. One half of each polyethylene disc was placed in a quartz cell with 10 ml of 0.1 M NaCl which had been pre-purified over a mercury pool electrode and the sample removed from the disc by ultrasonic agitation. The sample was then analyzed on a multiple plating anodic stripping apparatus using a composite mercury graphite electrode. The cell, electrode, and apparatus have been previously described by Matson et al. (1965) and Matson and Roe (1967).

-1850LOkm / LAKE I / DETROIT, ST.CLAIR ANN AROR ONTARIO, CANADA MICHIGAN LAKE ERIE OHIO _..I Figure II. 1: Location of sampling area in relation to Detroit.

-186Successive ultrasonic agitations of the polyethylene disc with fresh solutions showed a removal efficiency of 9097%. Runs on both halves of a polyethylene disc were within +5% of their average at the sample size of 200 ng. The major errors in the data come at high concentrations from the measurement of volume passed through the impactor with the Gelman Air Sampling Kit (+10%) and at low values from the subtraction of the variable and system carry-over blanks from the procedure (e.g., Pb 144, Cd 38, Cu 42 ng/stage). II. 4 METEOROLOGY The 24 hours preceding the beginning of the sampling period was under the influence of a low pressure system passing to the southeast through southern Ohio and Pennsylvania, west of the Appalachians. Light rain and high humidities with fog prevailed until the afternoon of Friday, April 26. At the beginning of the sampling period, the rain and fog had moved to the east and only light cirrostratus clouds remained. By morning of Saturday, April 27, a mesoscale high pressure area had moved into western Michigan and remained over the Michigan area throughout the sampling period. The tropospheric winds similarly decreased and remained moderate and out of the northwest. The air mass was of Continental Polar source region, and most of the residual aerosols would have been swept out of the air by the rain and fog leaving mostly recent and local material. The meteorological data and time intervals are listed in Table II.1 As seen in Figure 11.2 the temperature reflects the absence of clouds and has a smooth diurnal trace.

-187Table II.1 Meteorological Data Sample Time T Solar Cloud Temp. Dew Rel. Wind Wind Number EST Min. Ins.Ly. Cover T, C Pt. Hum. Speed v Dir. ^ Td,~C I m/s 1 1900 111 25 2 6.7 +0.6 65 2 1246 36 2 2206 107 0 0 6.1 +0.6 61 3 2 330 30 3 2405 104 0 0 5.0 -0.6 69 3 1 75 15 4 0159 110 0 0 4.4 -0.6 69 1 0 3 0 5 0400 110 10 0 2.8 -1.1 74 2 1 330 0 6 0602 118 160 0 3.9 +0.6 79 1 1 300 60 7 0825 85 430 0 8.3 +1.1 61 2 1 280 60 8 1002 108 515 1 11.7 _3.3 33 5 3 290 30 9 1201 110 625 1 13.3 -3.9 30 5 4 310 30 10 1400 109 550 2 14.4 -'3.9 27 4 5 360 30 11 1600 109 280 1 14.4 -3.3 29 4 3 360 30 12 1759 117 60 0 13.3 -3.3 32 5 4 80 50 13 1959 110 0 0 7.8 -3.3 44 3 2 90 90 14 2157 113 0 0 6.1 -3.3 50 2 1 85 20 15 2357 113 0 0 5.6 -3.3 51 3 1 70 15 16 0156 112 0 0 5.0 -3.9 52 3 1 90 2? 17 0355 115 0 0 4.4 -3.9 52 4 2 112 72 18 0600 110 110 0 6.7 -1.1 56 3 1 134 60 19 0759 113 400 0 10.6 -3.3 38 4 3 134 120 20 1001 136 550 0 13.3 -3.3 31 4 3 134 120 21 1223 121 570 0 14.4 -2.2 31 4 3 150 180

-18826.7 I I I 80 21.1- \ 70 15.6- RC - 60 1 C0 10.0 50 T -4.4 40 Td -1.1 30 -6.71 I I I I I I I i, i I I I m I a 20 22. 02 06 10 14 18 22 02 06 10 14 SAMPLE TIME, EST, 26-28 APRIL 1968 Figure II.2: T, RH, Td versus sample time. 5 180 -m/s S -.... SECTOR... 360 - N 0 6 H 327- W 22 02 06 10 14 18 22 02 06 10 14 SAMPLE TIME, EST, 26-28 APRIL 1968 Figure II.3: Wind speed and direction versus sample time.

-189The dew point decreased slowly during the first day and remained constant during the second except for the slight perturbation each morning after the sunrise as the ground moisture was mixed to higher elevations by heating. This phenomenon is typical in areas dominated by an anticyclone. Since relative humidity is a function of the temperature and dew point, it also follows a diurnal variation inversely proportional to the temperature. The winds were light and varied slowly through the two days. In Figure 11.3 the average direction is depicted by the horizontal lines whose length represents the average wind speed in meters per second. The vertical line represents the beginning of the sample time and the variation in the direction of the wind. Again, the situation is typified by low velocities and variations in the nocturnal hours and higher velocities and variability during the hours of solar insolation. The combination of the direction and the degree of variability determine the direction of our source region, and the speed determines the distance. Under these conditions we would expect no contribution due to large scale advection into the area. All variations should be due to diurnal meteorological changes and/or local changes in the source regions. II.5 RESULTS AND DISCUSSION Figures II.4 and 11.5 and Tables II.2, 11.3 and II.4 show the results for the variation of lead, copper, and cadmium during the period of sampling. Figure II.4 and

-1900 0 0 300- 00 0000 30 0 100 o o E O CdPb BlBlnk 300 A o A 100 3CE ro, c PbO Cu A Cd A 30 E Cd la - I I I I I I I I" 22 02 06 10 14 1822 02 061014 SAMPLE TIME, EST, 26-28 APRIL 1968 Figure 11.4: Total concentrations of Pb, Cd and Cu vs. time.

-191-, i I I I " 0 1000 Pb 100 o- — ~ - cc) Cd" 1.0 H G F E D C B PARTICLE SIZE -' Figure 11.5: Average particle size distributions of Pb, Cd, and Cu.

-192Table 11.2: Average of 21 Runs Minus Blank Stages 3 ng/m Stage Cd Pb Cu H 1.3 1230 15 G 28 159 59 F 9.1 122 27 E 7.0 126 52 D 2.7 92 18 C 2.4 100 9.3 B 8.6 95 15 A 1.3 74 4.8

-193Table 11.3 Gross Sum of All Stages for Each Run 3 ng/m Run Cd Pb Cu 1 189 1030 347 2 93 2440 226 3 141 1830 270 4 358 4070 368 5 374 3410 539 6 292 3320 332 7 371 3400 152 8 142 1150 214 9 64 1120 140 10 100 864 57 11 35 850 28 12 110 1090 276 13 183 3760 418 14 281 5770 385 15 246 3920 575 16 101 4070 227 17 197 2410 312 18 73 2030 207 19 89 1530 288 20 20 1010 47 21 92 1480 1160

-194Table II.4 Lead on Individual Stages 3 ng/m Run Stage A B C D E F G H 1 108 50 67 141 100 50 25 154 2 78 139 104 50 173 160 82 1260 3 o50 80 - 50 62 62, 50 76 1040 4 93 198 214 173 299 223 236 2240 5 105 109 168 143 168 219 227 1880 6 98 122 204 153 (145) 141 243 1850 7 180 218 174 109 104 71 180 1860 8 z5 0 z 5 0 50 z 0 5 50 50 0 618 9 -c50 -50, 50 <50 <50 <50 <50 598 10'50 -50 S 0 550 50 50 50 50 690 11 -50 <50'-50.a 50 -5 50 -50 <50 578 12 50 50 -50 z50 50 (c50) -50 146 602 13 160 135 160 177 139 164 160 2280 14 181 164 284 189 460 310 566 3250 15 86 131 172 115 394 205 420 2020 16 157 220 240 228 256 261 290 2030 17 73 133 121 (125) 133 254 314 888 18 76 126 80 172 84 84 105 940 19 86 201 57 86 L50 57 82 542 20 65 < 50 <50 z50 -50o 50 4 50 449 21 450 0 <500 rO50 103 80 103 734

-195Table 11.3 represent the gross total concentrations without subtraction of blank for all stages of the individual samples. Figure 11.5 and Table 11.2 show the average concentration on each stage for the 21 runs with the blanks subtracted. Table 11.4 shows the individual impactor stage values for lead. Because of the high blank to signal ratio of many of the runs for copper and cadmium, the tables for their individual stage values have not been included. The data indicate that there are wide variations within a 24 hour sample period. The variation of each of the elements studied is over a factor of ten within any 24 hour time period one chooses from the 42 hours represented. When initiating this experiment we expected to see some variations due to diurnal meteorological changes, but the large concentration differences in Figure 11.4 seem to be best explained by non-diurnal wind variations. Maxima occurred near 0400 and again near 2200 on Saturday, April 27. The minima are approximately at 1600 Saturday and 1000 Sunday. Since the variations seem to result in maxima and minima that are not diurnal in their occurrence and since the diurnal meteorological parameters were classic and almost identical for the two days, it could be possible that the major factor in these variations is wind speed and direction. By inspection of the wind direction plotted in Figure 11.3 and the total concentrations plotted in Figure II.4 one can see a definite coincidence with the occurrence of the wind direction coming from the Detroit sector as shown by the dashed lines. There is an expected phase lag of two to four hours.

-196One might also argue correctly that the concentration variations are caused by changes in the mixing depth and diffusion characteristics. It has been shown by Moses (1969) that under certain mixing conditions the variation in concentration can be over a factor of 1000. However, the conditions present at the time were not so extreme as to suggest that the large concentration differences found for each metal observed could be explained by simple changes in the mixing and diffusion regimes since lead must come from high concentrations of automobiles, i.e., the east sector. A much more extensive study would have been required to ascertain to what extent the changes in diffusion factor would control the concentration variations. As this experiment was a feasibility study the additional data was not gathered. The total concentrations seem to follow each other closely except in the later runs where cadmium departs toward lower values. Another interesting departure comes at the first minimum at 1200 on Saturday where copper and cadmium continue to decline below the average blank while lead levels 3 off to the value of about 500 ng/m. This implies that the lead is now coming from local sources or from the natural background during this minimum. One can argue that the variations are of local origin, but since lead is primarily from automobiles, and copper and cadmium are from other sources, either dependent or independent, it follows that the lead maximum comes from an area of large concentrations of autos, and there is no reason to suspect that the other elements

-197do not advect from the same region. It is also interesting to note from Table II.4 that in the samples taken during the minimum concentration, from 1000-1800 April 27 (samples 8 and 12), there is a much greater percentage of material in the smaller G and H stages than in samples 13-16 taken during the maximum concentration. This could be interpreted as a result of the aerosols from the northwest sector being older or more like continental background than those from the east. The average size distribution data is summarized in Figure 11.5 and Table 11.2. No attempt was made in this study to calibrate the Andersen impactor for the exact size of lead, copper or cadmium particles captured by the plates. About 60% of the lead particles is below a 50% cutoff diameter of about 0.2 p. This is in reasonable agreement with Robinson and Ludwig (1967) and substantiates the hypothesis that the lead is a product from a high temperature combustion source such as tetraethyl lead from automobile engines. The copper and cadmium tend to follow each other and show a slight preference for the middle range of particle size. II.6 CONCLUSIONS From an examination of the structure of the curves in Figures II.3 and 11.4 it appears that a two hour sampling period is needed but adequate for experiments concerned with the diurnal and mesoscale meteorological effects on the concentration and size distribution of aerosols. From the wide variation in concentrations over a relatively short period of

-198time it is apparent also that a great deal of caution must be used in interpreting the concentration of a trace element from a long period sample. II.7 ACKNOWLEDGMENTS The help of D. A. Gillette, R. H. Loucks, and K. Johnson on this project is gratefully acknowledged. The work was performed under Public Health Service Grant AP 00585 and NIH Air Pollution Traineeships. II.8 LITERATURE CITED 1. Lee, R. E., Patterson, R. K. and Wagman, Jack, "Particle Size Distribution of Metal Components in Urban Air," Proc. Am. Chem. Soc. (April, 1967). 2. Ludwig, F. L. and Robinson, Elmer, "Variation in the Size Distributions of Sulfur Containing Compounds in Urban Aerosols," Atmospheric Environment, 2, 13-23 (1968). 3. Matson, W. R., Roe, D. K. and Carritt, D. E., "A Composite Mercury Graphite Electrode for Anodic Stripping Voltammetry," Anal. Chem., 37, 1598 (1965). 4. Matson, W. R. and Roe, D. K., "Trace Metal Analysis of Natural Media by Anodic Stripping Voltammetry," Analysis Instrumentation, Vol. IV, 19-22 (1967), Plenum Pub. Co. 5. Moses, H., "Urban Air Pollution Models," to be published. 6. Robinson, E. and Ludwig, F. L., "Particle Size Distribution of Urban Lead Aerosols," APCA Journal, 17, 10 (October, 1967). 7. Wagman, J., Lee, R. E. Jr. and Axt, C. J., "Influence of Atmospheric Variables on the Concentration and Particle Size Distribution of Sulfate in Urban Air," Atmospheric Env., 1, 479-489 (1967).

APPENDIX III AREA-WIDE DISTRIBUTION OF LEAD, COPPER, AND CADMIUM IN AIR PARTICULATES FROM CHICAGO AND NORTHWEST INDIANA APCA Paper No. 70-118, June 1970 -19 9

AREA-WIDE DISTRIBUTION OF LEAD, COPPER, AND CADMIUM IN AIR PARTICULATES FROM CHICAGO AND NORTHWEST INDIANA by Paul R. Harrison John W. Winchesterb To be presented at the Annual Meeting of the Air Pollution Control Association, St. Louis, Missouri, June 15-19, 1970. Department of Meteorology & Oceanography University of Michigan Ann Arbor, Michigan 48104 aNow at: Dept. of Environmental Control, 320 N. Clark St., Chicago, Illinois 60610. Now at: Dept. of Oceanography, Florida State University, Tallahassee, Florida 32306. -200

AREA-WIDE DISTRIBUTION OF LEAD, COPPER, AND CADMIUM IN AIR PARTICULATES FROM CHICAGO AND NORTHWEST INDIANA Paul R. Harrison, John W. Winchester Department of Meteorology & Oceanography University of Michigan Ann Arbor, Michigan 48104 ABSTRACT Published air pollution emissions inventories for the urbanized and industrialized area along the southwestern shore of Lake Michigan include few chemical analyses of particulates, and estimates of the elemental composition of airborne solids may be made only indirectly and compared with NASN analyses from a few locations. As a first attempt to examine the area-wide distribution of specific chemical elements in this region, lead, copper, cadmium, and bismuth were determined in 24-hour average samples collected on glass fiber filters at 50 stations throughout the region. Samples from most of the 50 stations were obtained from local air pollution control organizations for 6 different days from May to August 1968 and were analyzed electrochemically by highly sensitive anodic stripping volammetry (ASV). Throughout the area the small variation of lead, generally a few micrograms per cubic meter of air, did not exceed that expected from the distribution of automobiles, the major source. Cadmium was generally 200 times lower without marked local variations and was close to the expected concentration if coal combustion is the major source. Copper was generally 20 times lower than lead throughout Chicago as expected if coal combustion is the major source of copper. However, certain stations in the northwest Indiana area showed reproducible anomalies where copper was 100 times greater than in Chicago and several times greater than lead at the same stations. The source of this anomalous copper has not been determined. -201

-202I. Introduction Until recently area-wide air pollution surveys of suspended particulate have commonly been made without determination of elemental composition, primarily because of increased cost of chemical analysis over that of simply measuring weight of total particulate collected on a filter. However, as the present work has found, geographic variability in the atmospheric concentrations of certain elements composing the particulate may exceed that of total suspended particulate in an urban or industrial area, and detailed chemical data may be necessary to evaluate public health hazards or to locate sources and estimate their source strengths. We have carried out chemical analyses by anodic stripping voltammetry (ASV) of particulate sampled on glass fiber filters by several local control agencies in the Chicago-Nothwest Indiana region for 6 24-hour periods during 1968: May 21-22, June 6 and 20, July 9, August 8 and 29. Data for Pb, Cd, and Cu are presented as well as data for Bi on the first day (May 21 for Chicago and May 22 for Indiana). One of the most extensive area-wide surveys was carried out in Nashville, Tennessee, (Zeidberg et al., 1961) utilizing 119 sampling stations distributed in and around the city. The parameters measured included spot tapes, total particulate, and sulfur dioxide, but no trace element analyses were reported. One of tbh first trace metal studies was by Tabor and Warner (1958) where 17 metals in 28 cities were determined, although none of the sampling sites were adjacent to each other and few were simultaneous. More recently Lee and Jervis (1968) and Brar, Nelson et al. (1970) have determined by neutron activation analysis several trace metals in atmospheric particulate from Toronto, Canada, and Chicago, Illinois, respectively. The latter study reported concentrations of 21 metals in 22 samples taken simultaneously over a 24-hour period in April, 1968. Significant variations in concentrations were found, presumably reflecting variability in the distribution

-203of industrial sources over the city. No data for Northwest Indiana were reported, and the relevance of meteorological conditions to the concentration patterns could not be determined from this one-day study. Kneip et al. (1970) have just published a trace metal study of New York with results consistent with ours in the present investigation. II. Experimental In the present work we present data for Pb, Cd, Cu, and Bi in aerosol particles from the Chicago and Northwest Indiana regions. This was a cooperative effort mainly with the City of Chicago and the Northwest Indiana Air Resource Management Group, consisting of Hammond, East Chicago, Whiting, Gary, Michigan City, and Lake County, with Porter County and Valparaiso University also participating. From these groups we obtained data for S02 and suspended particulate which we quote here as well as the samples which we analyzed in our laboratory for trace metals. Figure 1 shows the station designations in the area under study. The six sampling days selected, all Tuesdays or Thursdays, give the greatest degree of simultaneity possible over the several jurisdictions involved. All samples were collected on standard 20 x 25 cm (8 x 10 in) glass fiber filter paper, used routinely for suspended particulate analysis. After each filter paper was weighed it was folded and placed in envelopes by the local agencies and stored in a filing cabinet until taken to our laboratory at the University of Michigan. Our procedure consisted of the following steps: A 13 cm (2 in ) sample was cut as 2 equal-sized squares from the folded filter paper, and then slightly shredded and inserted into a standard 25 ml narrow neck volumetric flask. The organics were dissolved by digesting in 4 ml of perchloric acid heated to 300~C for approximately 1/2 hour. The samples were then diluted to 25 ml with water

-204and allowed to sit for one to two days before analysis. Equivalent portions of blank filters obtained with the samples were treated in the same manner, although we found no evidence of significant contamination by the glass fiber for the elements measured. The ASV technique, an electrochemical method akin to polarography, consists of electrodeposition of the trace elements from solution onto an electrode and then stripping by reversing the potential in a gradual sweep. The current caused by each element in turn re-entering the solution is recorded by a moving chart recorder, and the total charge collected, a measure of the element, is calculated by measurement of height or area of the current-voltage peaks characteristic for each element. Matson (1968) has given a description of the electrode used consisting of a thin Hg film coating a paraffin-impregnated graphite rod, and the construction of the electrochemical cell and associated electronics. In general, the technique is sensitive to nanogram amounts of metals which form amalgams and is well suited to air pollution investigations. An aliquot of each 25 ml sample solution, representing about 0.3m3 of air, was added to a vial of 10 ml pre-treated solution and subjected to ASV analysis. In order to facilitate mass production of analyses a routine for handling samples, blanks, and standards in a cumulative fashion was devised and is described in detail by Harrison (1970). To alleviate carryover from one sample to another each electrode system and vial were washed thoroughly and then an aliquot of blank plus a standard spike was added and run. The subsequent stripping was the sample itself with the former response subtracted from the sample run, thus eliminating contamination in the vial and by carryover from the previous analysis. Analytical control was achieved by running different cells at different times for the same filter paper and by using aliquots from various regions in the filter paper in replicate determinations. Due to the response characteristics of the apparatus the errors are variable according to the response to blank ratio. Since the ASV

-205technique is being given its first large scale test in an air pollution survey application by this work, we regard the relative concentration variations over the network to be of greater significance, and absolute concentrations for individual samples may be in error by as much as a factor of 2. III. Results Tables I through VI represent the results for the six days of lead, cadmium, copper, and bismuth by our work and of sulfur dioxide and suspended particulate data supplied to us by the local control agencies. Concentrations are given as ng/m of air sampled, the dashed lines ( —) signify no sample was taken, the asterisks (*) signifiy weak signals near blank level, and M indicates data missing for various reasons. All data have been plotted on maps and are given by Harrison (1970). Since a great deal of similarity is found among the six days of the study, in spite of differences in winds, we have selected only one of the days for plotting here. Thursday, June 6 is the day with the least variable wind direction, and Figure 2 shows the wind roses for four meteorological stations as lines in the direction toward which the wind was blowing for the number of hours indicated with lengths proportional to wind speed. C (calm) implies <1.5 m/sec winds. Lead in Figure 3 shows a mean concentration of 1-2 Pg/m and follows the average traffic density with no obvious strong local sources. Cadmium in Figure 4 has a mean value near 10 ng/m and does not vary markedly with location although the variability is somewhat greater than for lead. Copper, in Figure 5 shows a mean value near 100 ng/m3 over Chicago but has an anomalous "hot spot" in East Chicago, Indiana, where concentrations approach 100 times greater values. In Figure 6 isopleths of the region show the systematic decrease in concentration with increasing distance from an apparently localized source region. Total suspended particulate, Figure 7, does not reveal a maximum in this region but, like lead, seems to have a broad

-206distribution with no obvious localized source. Figure 8 presents SO2 concentrations with a pattern apparently unrelated to the particulate data. All six days investigated show essentially the same location of a pronounced copper maximum and qualitatively similar behavior for the other variables illustrated in Figures 3-7. Bismuth data, obtained only for May 21-22, show a low mean value near 1 ng/m. IV. Discussion It is seen from the data that a large amount of scatter is present even in the broadly distributed suspended particulate and lead values. Table VII summarizes the weighted average wind direction, the total range of wind direction variability, mean speed and variability, temperature, rainfall, and relative humidity for the six sampling days. Table VIII gives the averages of the parameters broken into two groups of Chicago and Northwest Indiana, with Indiana copper values for stations 1-11 and 12-27 listed separately because of the large anomaly in East Chicago. Meteorological effects do not appear to be important in this study in affecting the observed patterns of concentration variation. However, except for July 9, all days were influenced by old air masses and variable wind directions. A lake breeze was observed on August 29 but the 24 hour time gate does not permit an examination of this effect on trace metals. Thus, meteorology is still an unknown effect except for a bulk transport mechanism of pollutants. The complexity of the study area is further seen in Table IX giving the average values of ratios for each day separately for the Chicago and Indiana areas. The values of the ratios do not show large differences between the Indiana and the Illinois regions except for the large copper anomalies in Indiana. The mean Cu/Pb ratio and mean % Cu/S.P. are weighted strongly to Cu anomaly stations and show the large difference between Indiana and Chicago. Cd/Pb, % Cd/S.P., and % Pb/S.P. do not show this difference as no large anomalies of Cd, Pb, or S.P. are found. The mean of the Cd/Cu ratios is weighted strongly to the low Cu stations

-207in Indiana and shows a similarity to the Chicago mean as expected. Thus, the mean Cd/Cu ratio for all data is 0.11 and for the Chicago region is 0.12 for all 6 days. Correlation coefficients for all pairs and data points have been calculated (Harrison, 1970) but owing to relatively large random errors for individual analyses are not as informative as the averages. Elemental abundance patterns in an area-wide survey are useful in locating sources and may aid in making estimates of source strengths. We suggest from this study that Pb, Cd, and Cu over most of the Chicago and Northwest Indiana region come from area sources, but, in addition, Cu has a strong source or sources near stations 8 or 9 in Indiana. The source is persistent since the anomaly is seen on all six days of the survey, and tightness of the isopleths in Figure 6 and other days implies a rather short atmospheric residence time and travel distance, seemingly unaffected by meteorological differences among the six days. Which urban or industrial activity is the actual source of this copper component may be determined by further investigation. We may ask whether conventional area sources of air pollution are adequate to account for Pb, Cd, and Cu outside the anomalous region. Winchester and Nifong (1969) attempted to inventory some 30 individual trace elements of the Chicago-Northwest Indiana region from published information about fuel combustion and the steel and cement industries. Although only approximate, these estimates may provide a basis for comparison of our results. Table X shows a summary of the data used to make these estimates, considering fuels to be the only important area for Pb, Cd, and Cu sources. These data lead us to expect ratios of elements coming from area fuel sources to be Cd/Cu-0.1, Cd/Pb r-0.006, Cu/Pbr 0.06. Comparison of Table IX shows approximate agreement of the observed means with these ratios, and it appears to be unnecessary at this time to invoke any other sources to account for these elements outside the Cu anomaly region. However, we consider it highly desirable to refine this comparison by use of improved data on the composition of particulate emissions when they should

-208become available. Finally table XI is a comparison of our 6 day study with the National Air Sampling Network (NASN, 1966) stations in the area for 1963. Since our station 2 at or near the NASN station was available 5 of the 6 sampling days, we single this out especially for comparison. Cadmium falls within the variability presented by the NASN data, as does bismuth. Lead and copper are both higher than the NASN data, a disagreement which we cannot explain adequately at this time. Kneip et al. (1970) also find lead values in New York higher than NASN values and suggest that NASN determinations are erroneously low. We should point out that the NASN station is not located in the region of the anomalous copper and therefore leads to lower concentrations of Cu than we have found on the average in Northwest Indiana. In this study we have seen that area-wide studies can reveal (1) the general level of exposure of various pollutants, (2) previously unknown contaminants and sources, and (3) better locations for the placement of routine monitoring stations. Further studies of this type should be conducted under forecast meteorological conditions to gain knowledge of the mesoscale effects. The preliminary data suggest that the plumes diffuse rapidly from such areas and are lost in the proximate or non urban background levels. ACKNOWLEDGEMENTS. Cooperation of air pollution control agencies in Chicago and Northwest Indiana in providing samples for analysis and the Thesis Parts Program at Argonne National Laboratory are gratefully acknowledged. This work was supported in part by the U.S. Public Health Service through grant AP-00585 and through an Air Pollution Traineeship award to one of us (P.R.H.).

-209REFERENCES 1. Zeidberg, Louis D., Schueneman, I. J., Humphrey, Paul A., "Air pollution and health: General description of a study in Nashville, Tennessee," JAPCA, 11:6, 289-297 (1961). 2. Tabor, E. C., Warner, W. V., AMA Archives of Industrial Health, 17, 141-145 (1958). 3. Lee, J., Jervis, R. E., "Detection of pollutants in airborne particulates by activation analysis," American Nuclear Soc. Trans, 11, 50-51 (1968). 4. Brar, S. S., Nelson, D. M., Kanabrocki, E. L., Moore, C. E., Burnham, C. D., Hutton, D. M., "Thermal neutron activation analysis of particulate matter in surface air of the Chicago metropolitan area.-One minute irradiations,," Environmental Science and Technology, 4, 50-54 (1970). 5. Matson, W. R., Trace Metals, Equilibrium and Kinetics of Trace Metal Complexes in Natural Media, Ph.D. Thesis, Department of Chemistry, Massachusetts Inst. of Tech. (1968). 6. Harrison, Paul R., Ph.D. Thesis, University of Michigan (1970). 7. Winchester, John W., Nifong, Gordon D., "Water pollution in Lake Michigan by trace elements from pollution aerosol fallout," paper WATR-34 presented at American Chemical Society (April 1969). 8. National Air Sampling Networks, "Air quality data," 1966 edition, U.S. Public Health Service. 9. Kneip, T. J., Eisenbud, M., Stre hlow, C. D., Freudenthal, P. C., "Airborne particulates in New York City," JAPCA, 20:3, 144-149 (1970).

Figure 1 Air Sampling Locations G K MICHIGAN + K V e( P- ~ ~~ CI~^ ^ ^ CIA TY + +p~+ CHICI~~LKEMIHIA. 1& *~~~ #Wfl~ar alY + ~ ~ P' s 27''O ~~~~~~~~x H~ -0 1+ *~~16 *21 012 13 x2 - 28 IT la~~~I 24 Ilinois is Indiana x ~5 29 1O~ km 20~ 10 kin

Figure 2 11 4 |/ 5 rpThurs. 6 June 1968 WIND + 4 4 2 4 ~h~CAGO2 LAKE MICHIGAN 2O*CACO Illinois Indiana mph x 0 10 10 km

Figure 3 Thurs.6 June 1968 +~ + 5' Pb b - r i3x I 3 f+ 9p IC 2O 20 0 ~LAKE MICHIGAN 1 0 10 -- k.g Illinois Indiana 10 km

Figure 4 Thurs.6 June 1968 + 4dnd Cd ng-mr3 30 6 7 0 nd + 9 +1 LAKE MICHIGAN CHICAGO nd 9.+ ndjn 6 8 I0 MIHKeAN CITY 20 +"~ " I 100 i~" m nd r~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~d ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ A x nd Illinois indiana x 10 km

Figure 5 Thurs.6 June 1968 2~~~~~~~~+ nd 20 Cu,ngg m xO.I 20Cufg 10 + N 10 + P d L'p ITAKE MICHIGAN CHICAGO o0 4.- nd +~'p nd 8 L —|' 16 30?OO 0^ ^ ~ n^' S'Oiy^ ^ MKCHIGAN CITY 4 -500 Iro ~o Po 30+ 70 x 20 Gq~GRY 20 70 Illinois Indiana x 20 10 km

Figure 6 Thurs.6 June 1968 Cu,ng-m-3x O. I + *' +AKE MICHIGAN CH CAGO P- * I0flaP0 MONtGAN OTY k| I I / ^501 Illinois. Indiana x * 10 km

Figure 7 Thurs. 6 June 1968.,74nr,aSuspended Particulate pFg-m-3 ^+ +174 172 ~ 212 ~55 N 186 176 61 + 181 + 6 LAKE MICHIGAN t CHICAGO 205 * \ *+ 9139 229 + + 130 115 1r0m — 05 13 MON6AN CITY 96.109 k 136 86 Illinois Indiana 96 I0 ktn

Figure 8 Thurs. 6 June 1968 SO02ppb ~+. + 67 O 4s +39 /LAKE MICHIGANI mK >^ ^^^MCWWITY 9.2 12 1 + 4' Ilinois I Indiana x 10 km

-218Table I. Atmospheric Concentration of Lead, ng/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 2000 800 1000 100 1000 1000 2 -- 2000 3000 2000 3000 2000 3 3000 1000 3000 2000 2000 2000 4 5000 1000 2000 800 2000 2000 5 1000 900 2000 400 1000 1000 6 2000 900 4000 600 4000 2000 7 - -- - 000 700 5000 2000 8 1000 700 2000 1000 1000 1000 9 2000 500 600 2000 2000 500 10 20 00 800 1000 700 600 11 2000 1000 2000 ---- 12 4000 700 2000 ------- 15 6000 2000 3000 —-- - --- 14 --- - --- -- - 15 1000 500 2000 ---- ----- 16 3000 800 ------ ---- 17 1000 500 2000 900 2000 700 18 400 300 800 500 100 2000 19 300 400 400 -- 100 5000 20 900 700 1000 1000 600 1000 2 —---- 1000 500 600 - 22 ---- -— 1500 400 1000 23... —- 700 100 500 700 24 ---- — 1500 500 300 500 25 —.- -- 500 500 200 - 26 1000 --- 1000 700 800 500 27 ---- 5 —- _ — 300 400 800 A 7000 1000 5000 2000 3000 4000 B 4000 2000 2000 800 4000 4000 C 5000 300 2000 600 2000 3000 D 3000 2000 300 2000 4000 3000 E 4000 - - -_ -- 1500 5000 F 6000 2000 3000 ---- 5000 4000 G 4000 2000 4000 1500 —- 3000 I 2000 1000 3000 700 3000 4000 I.... - --- -- ---- - 2000 J 6000 900 2000 ---- 2000 --- K 5000 1000 2000 500 200 2000 L 3000 1500 2000 200 4000 2000 M 6000 1000 2000 400 2000 4000 N 5000 1000 3000 600 2000 2000 e 6000 i030 2000 500 2000 1000 P 5000 1000 4000 600 2000 5000 Q 4000 700 2000 700 --- 2000 R 4000 -- 2000 300 2000 - T 3000 1000 2000 800 ---- U 4000 1500 5000 1000 3000 ---- V 4000 1000 4000 1000 3000 2000 w 4000 800 2000 ---- 2000 5000 SHIP --—. 700... Individual Data Points are Reliable to a Factor of 2.

-219Table II. Atmospheric Concentrations of Cadmium, ng/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 50 5 50 10 ** 10 2 -- ** 20 20 10 20 3 10 ** **50 ** 30 4 0 ** ** 5 10 8 5 40 10 10 50 ** 7 6 10 8 20 10 10 10 7 -- -- 8 60 10 10 8 15 ** 5 10 8 ** 9 30 7 10 20 * 10 20 ** 3 6** 11 10 40 6 -- - 12 70 10 13 0 30 ** --?. 14 -- -- -- _- 15 15 ** ** - 16 7 9 -- 17 10) 17 10 ** ** ** ** ** 18 ** 20 ** ** 20 19 9 40 19 9 ** ** -- ** 40 20 10 6 80 20 5 20 21 -- -- 50 40 22 -- -- 30 10 ** - 25 -- -- 30 30 24 -- -- 20 7 20 10 25 -- -- 30** **'(- 5 — ** 7 10 27 --- -- ** 10 20 A ** ** 20 20 10 30 B 30 30 10 30 50 C 30 6 10 ** 20 D M 20 ** 20 ** 20 E 60 -- -- -- 15 40 F 20 10 10 -- 10 5 G 50 10 ** 10 -- 15 H ** ** 20 8 50 40 I -- - - -- - - -- ** J 80 10 -- 8 -- K 20 ** 8 10 10 10 L 30 15**20 0 M 40 6 9 20 ** N 10 8 20 9 10 * e 50 10 10 ** 10 7 P 5 20 9 20 ** 30 Q 30 10 6 15 -- 6 R 20 -- 7 * 10 -- T 10 10 9 U 9 ** 10 ** 20 -- V 40 7 40 6 3 0 30 w 40 9 10 -- ** ** SHIP.- -20 Individual Data Points are Reliable to a Factor of 2. **.= 5<

-220Table III. Atmospheric Concentrations of Copper, ng/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JUL 9 AUG. 8 AUG. 29 1 70 300 400 150 150 500 2 --- 100 1000 150 200 150 3 300 200 2000 200 80 600 4 900 2000 200 80 600 400 5 1000 3000 600 60 500 200 6 2000 7000 (7000) 2000 2000 4000 7 --- -— 10o00 1000 600 8 5000 9ooo 5000 2000 3000 9000 9 7000 5000 9000 7000 10000 10000 10 4000 5000 1500 2000 (9000) 10000 11 300 700 400 12 ** 300 500 -- 13 80 700 200 - - - 14 ---. --- _ —- --- - 15 200 200 150 -- 16 100 200 --- --- 17 150 200 150 200 30 70 18 300 200 300 200* 100 19 400 700 400 --- 70 100 20 150 200 100 200 40 100 21 --- - 100 70 70 - 22 --- _ 5000 70 23 -— 90 ***100 100 24 - -- 500 60 100 70 25 ---- 200 60 90 - 26 80 --- 300 200 400 200 27 ----- **00* 00 200 A 70 ***600 100 100 300 B 300 200 70 200 300 150 C 100 100 100 20** 100 D 150 70 30 100 200 200 E 400 --- ---- 500 1000 F 200 80 — 100 100 G 400 100 70 200 --- 200 H 500 20 80 20 100 * I --- -- - -- --- 200 J 200 100 --- 200 --- K 200 *****200 100 100 L 200 100 70 800 200 M 80 60 ***600 90 N 100 80 00 60 00 100 e 500 200 200 100 200 200 P 300 100 200 200 200 200 Q 900 0 100 200 --- 200 R 500 ***200 -— 200 --- T 200 200 200 30 * U 200 200 200 20 300 --- V 600 100 400 80 200 200 W 200 40 100 — 200 200 SHIP ------ - -- 100 --- -- Individual Data Points are Reliable to a Factor of 2. ***= <20

-221Table IV. Atmospheric Concentrations of Bismuth, ng/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 J** 2 3 3. 4 1. 5 2. 6 3. 7 8 0.7 9 2. 10 1.5 11 0.4 12 0.6 13 0.4 14 -- 15 0.3 16 17 18 19 20 21 22 23 24 25 -- 26 * 27 A M B ** C D M E 0.8 F 1. G 0.1 H M I -- J ** K 0.6 L ** M M N ** e ** P 0.3 Q 0.4 R 0.4 T 0.2 U ** V x** w 0.8 SHIP -- Individual Data Points are Reliable to a Factor of 2. *= 0.05

-222Table V. Atmospheric Concentrations of Total Suspended Particulate, yg/m3 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 115 170 117 52 198 148 2 -- 218 344 64 161 92 3 81 131 256 139 148 167 4 126 143 128 54 152 145 5 140 169 278 66 156 242 6 142 201 382 125 256 233 7 -- -- 32 193 191 174 8 62 108 210 105 91 122 9 83 115 134 148 122 109 10 78 109 198 -- 100 96 11 76 153 228 -- -- 12 128 179 249 13 120 187 255 14 -- 15 46 136 100 - 16 80 154 85 -- -- 17 66 109117 142 18 98 86 107 64 17 19 55 98 70 46 20 78 96 88 126 62 -- 21 -- -77 44 40 65 22 -- 104 55 49 65 23... 66 27 39 57 24 —- -- 32 38 81 25 -- -- 81 -- 43 185 26 68 — 64 63 79 45 27 -- -- -- 49 84 69 A 88 174 141 71 138 107 B 113 212 116 105 239 214 C 114 55 150 49 132 139 D 125 261 19 60 243 188 E 144 — -- -05 952 F 153 206 169 -- 185 218 G 134 181 172 152 143 H 50 176 26 6 182 186 181 I -- -- -- -- 181 J 166 205 259 - 166 -- K 154 139 245 103 158 134 L 180 229 180 43 225 218 M 139 130 183 98 170 195 N 142 115 211 86 154 136 e 163 205 263 108 174 178 p 141 153 286 51 177 214 Q 195 161 408 109 235 K 145 -- 241 110 130 T 92 152 81 67 132 U 75 172 121 74 146 -- V 114 186 190 100 196 148 W 131 155 216 - 161 185 All Data Furnished by the Local Agencies

-223Table VI. Atmospheric Concentrations of 802, ppb STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 20 1 2 3 17 21 62 69 3 -- 4 5 13 24 -- 48 4 6 7 -- -- 2 -- 1 8 -- ** -- - 9 9 10 11 2 -- 15 12 135 -- ** -- _ 13 15 16 17 18 19 - - 1 -- ** -- 20 21 -- 9 2 1 1 14 22 -- -- 1 ** 3 ** 23 -- 8 4 1 4 11 24 - -- -- 1 2 -- 25 26 27 A 75 5 10 8 3 4 B 14 1 27 35 3 26 C 54 17 10 1 4 6 D 22 67 12 30 13 11 E F 10 39 9 13 9 34 G 32 45 ** 6 3 16 H 27 94 31 9 55 3 I J 7 1 7 1 67 K 80 12 14 12 24 L 23 15 29 1 27 M 1 -- 6 1 15 32 N 1 -- 25 12 4 39 e 1 -- 20 4 3 20 P 1 -- ** 1 2 5 Q 24 8 51 7 2 44 R 17 7 51 4 2 -- T1 1 2 1.2 12 28 16 U V W 4 9 13 24 22 20 **-= 0.5 All Data Furnished by the Local Agencies

Table VII AVERAGE METEOROLOGICAL CHARACTERISTICS. Wind Range Speed Range Temperature Direction degrees m/s m/s Max. Min. Ave. Precip. Relative de grees 0C ~C ~C mm Humidity May 21 290 560 5.5 C-7 15.9 8.5 11.1 Trace. May 22 180 280 5.5 C-8 16.7 6.1 11.7 2 June 6 180 40 5.3 2-8 3355.9 20.0 27.2 None 55 June 20 150 150 5.8 5-8 25.6 15.5 19.4 Trace 61 July 9 210 170 6.8 4-10 29.4 16.1 22.8 Trace 60 Aug. 8 200 560 5.9 2-16 51.1 22.2 26.7 0.5 77 Aug. 29 090 150 4.2 5-6 24.4 15.0 20.0 None 58

-225Table VIII AVERAGE CONCEITRATIONS FOR EACH DAY IN CHICAGO AND N.W. INDIANA. Day, Cd Pb Cu* SP S02 Bi 1968 ng/m3 ng/m3 ng/m35 gm/m3 ppb ng/m3 21/22 May 2000 Ind. 21 2000 1 180 92 11 Ill. 29 4300 300 130 0.25 Both 25 3300 750 19 06 6 June 3500 Ind. 8 850 390 140 Ill. 9 1300 830 170 Both 9 1100 970 160 20 20 June r 3900 Ind. 13 1700 260 170 11l. 10 2700 230 200 Both 12 2200 1000 180 16 9 July 1600 Ind. 19 810 130 84 Ill. 9 810 99 83 5 Both 14 810 510 84 12 8 Aug. 4800 Ind. 5 1300 L 120 100 Ill. 13 2600 250 180 Both 9 1900 1300 146 9 29 Aug. 4000 Ind. 12 1300 l 140 120 Ill. 16 3100 220 180x Both 14 2200 1200 156x 17 Totals: all data Mean 19 1900 1000 150 18 0.63 Max. 80 7000 10000 950 80 3. Min. <5 100 < 20 30 < 0.5 05 (*, stations 1-10 and 11-22 listed separately; x, station E excluded)

-226Table IX AVERAGE VALUES OF SELECTED RATIOS FOR EACH DAY IN CHICAGO AND NORTHWEST INDIANA. Day, Cd/Pb Cd/Cu Cd/SP* Pb/SP* Cu/SP* Cu/Pb Cd/S02 1968 21/22 May Ind. 0.012 0.099 0.023 2.2 1.7 0.89 Ill. 0.007 0.14 0.023 3.5 0.25 0.080 Both (0.010) (0.12) (0.023) (2.9) (0.92) (0.44) (9.0) 6 June Ind. 0.018 0.031 0.0098 0.57 1.49 3.4 Ill.. 011 0.16 0.0078 0.76 0.071 0.13 Both 0.014 0.10. 0086 o.67 0.85 1.9 4.2 20 June Ind. 0.021 0.11 0.022 1.1 0.87 1.3 Ill. 0.0044 0.087 0.0071 1.6 0.11 0.060 Both 0.012 0.10 0.014 1.4 0.54.78 3.8 9 July Ind. 0.047 0.15 0.034 0.97 0.73 0.88 11l. 0.018 0.15 0.019 1.0 0.13 0.15 Both 0.036 0.15 0.029 1.0 0.48 0.56 7.3 8 August Ind. 0.014 0.053 0.013 1.1 2.4 2.6 Ill. 0.007 0.083 0.010 1.5 0.15 0.12 Both 0.009 0.070 0.011 1.3 1.3 1.5 3.8 29 August Ind.'0.012 0.095 0.012 1.0 2.o 5. 4 Ill. 0.007 0.096 0.013 1.7 0.11 0.082 Both 0.009 0.095 0.013 1.4 1.2 1.6 3.2 Totals: all data Mean 0.015 0.11 0.016 1.4 0.87 1.11 5.5 (*, %)

Table X CONTRIBUTIONS OF FUELS TO LEAD, CADMIUM, AND COPPER TO CHICAGO AREA SUSPENDED PARTICULATEa Coal Coke Fuel Oil Gasoline Combustion estimate, megatons/yr 20 15 7 8 Particulate emission estimate, kilotons/yr 220 18 14 b Pb emission estimate, tons/yr 300 22 30 1,800 Cd emission estimate, tons/yr 11 1 - - Cu emission estimate, tons/yr 100 7 26 -- aAfter Winchester and Nifong (1969). All units are metric. Assumed 2 g Pb/gallon and 25% of emissions airborne.

Table XI COMPARISON WITH NASN 1963 DATA, ng/m3 Pb Cd Cu Bi NASN, ParkeCo., rural 24-57 1.8-5.2 17-80 <0.5 NASN, Beverly Shores, proximate 100-200 ND-10 30-50 <0.5 NASN, Hammond, urban 100-1,200 ND-55 30-180 <0.5 This study, all stationsa 100-7,000 <5-80 <20-10,000 <0.05-3.0 This study, station 2, Hammonda 1,000-3,000 <5-20 100-1,000 --- aIndividual values reliable to a factor of 2.

APPENDIX IV DATA TABULATIONS AND RATIOS -229

-231IV.1 METEOROLOGICAL DATA

-232IV.1.1 East Chicago, Indiana

Table IV.1.1 Meteorological Data for East Chicago, Indiana, 1968 * xxyy; xx=tens of, yy=mph CST 21 May 22 May 6 June 20 June 9 July 8 Aug 29 Aug xxyy* A~ A0 A0 A~ A~ A A 1 30 — 20 2304 20 1806 30 1203 30 2210 60 9002 90 1204 60 2 30 — -- 2303 20 1806 30 2002 120 2311 60 1202 90 1204 30 3 29 — -- 2204 20 1806 30 2203 30 2310 60 1403 60 1304 30 4 29 — 20 2204 60 1805 30 2200 -- 2308 60 2103 120 1505 60 5 30 — 50 2204 40 1806 30 2200 -- 2307 60 2103 90 1606 30 6 30 — 60 2304 30 2007 30 2404 30 2408 60 2103 60 1605 30 7 2900 50 2404 30 2107 60 2400 120 2507 60 2004 60 1606 30 8 28 — 30 2505 90 2107 60 1203 90 2310 60 2005 60 1707 60 9 30 — 50 2105 70 2308 60 1206 60 2409 90 2205 60 1806 60 10 30 — 180 2206 60 2308 90 1105 90 2507 90 2206 60 1805 90 11 2909 90 2209 60 2309 90 1206 90 2706 90 2307 90 1605 120 Lake 12 3111 60 2109 90 2409 120 1106 90 2708 90 2507 90 0907 90Breeze 13 04 07 60 1909 120 2309 120 0906 90 3010 90F 2707 90 0908 90 14 0506 90 2110 90 2310 120 0907 60 3612 60 3314 90 0807 90 15 0603 120 1910 60 2310 120 1008 60 0515 60 0608 90 0807 90 16 0705 120 2010 60 2208 90 1007 60 0310 60 1307 60 0807 90 17 0605 90 1907 60 2009 90 1008 60 0510 60 1206 90 0706 90 18 ---- -- 1711 60 2011 60 1009 60 0409 60 i806 90 0908 60 19 ---- -- 2008 120 2010 60 1008 60 0409 60 1804 90 0908 60 20 ---- -- 2307 30 2009 30 1109 60 o4o9 90 18o6 60 0907 60 21 ---- 2403 60 2009 30 1207 60 0412 90 1607 60 0906 60 22 ---- -- 3602 120 2107 30 1407 60 0412 60 1805 30 1006 60 23 ---- -- 4703 30 2208 60 1507 60 0311 60 1704 30 1204 30 24 ---- -- 4704 30 2207 30 1808 60 3410 60 1504 30 1205 30

-234IV.1.2 Midway Airport, Chicago

-235Table IV.1.2 Wind Data - Midway Airport, Chicago, Illinois, 1968 CST 21 May 22 May 6 June 20 June 9 July 8 Aug 29 Aug xxyy* o 3103 1708 1810 2110 0806 0805 1 3104 2104 1708 1912 2110 0806 1403 2 3205 2105 1808 2010 2012 0706 2304 3 3204 2003 1808 2010 2010 1204 2403 4 3203 0000 1805 2010 2110 1605 2503 5 0000 2004 1808 1914 2110 1803 1304 6 2703 2006 1807 2012 2111 1805 1304 7 2704 2105 1910 2014 2011 2007 1707 8 2606 2105 2009 2117 2509 2206 1708 9 2810 1911 1811 2415 2207 2007 1809 10 2910 1911 2112 1906 2507 1908 1306 11 5014 1910 2108 1809 2207 2007 0907 12 3312 2012 2008 2212 2409 2510 0911 13 3111 1812 1915 1716 3512 3013 1211 14 3013 1911 191 1918 0416 0610 1212 15 3611 1810 2112 2014 0114 1608 0812 16 0608 1715 1912 1813 0313 1511 0710 17 0911 1511 1810 1716 0513 1708 0910 18 1307 1712 1910 1814 0514 2306 0910 19 1505 1708 1812 1614 0612 2205 0911 20 1305 1705 1810 1713 0414 1208 0908 21 1003 0000 1908 j812 0215 2105 0508 22 1305 0805 1906 1914 0117 2005 0705 23 1804 1005 2008 2012 0315 1806 0705 24 1904 1005 2106 2012 0213 1603 0505 * Key: xxyy; xx=tens of, yy=mph

-236IV.1.3 O'Hare Airport, Chicago

-237Table IV.1.3 Wind Data - O'Hare Airport, Chicago, Illinois, 1968 CST 21 May 22 May 6 June 20 June 9 July 8Aug 29 Aug xxyy* 0 3005 2103 1806 1 3104 2403 1705 2503 1910 0000 3304 2 3105 2103 1804 0000 2008 2104 0000 3 2906 2103 1805 2004 2010 2504 0000 4 3005 2303 1805 2703 1908 0000 0000 5 3003 1803 1805 0000 2205 0000 0000 6 2704 2204 1905 0000 2106 2804 2903 7 3005 2308 1908 0503 2105 0000 1301' 8 2706 2005 2107 0000 2206 2003 1705 9 2908 2008 1808 1204 2205 2805 1205 10 2710 2109 2009 0903 2204 2606 1605 11 3011 1809 2205 1803 2405 2806 1006 12 3411 1809 1909 0000 0208 3105 1109 13 3311 1712 1811 0910 0414 2804 1209 14 3410 2012 2208 0809 0212 3304 1210 15 0810 1609 1810 1010 0412 2703 0707 16 0309 1809 1909 1211 0218 0506 0507 17 0608 1408 1707 1110 0410 1206 0807 18 0204 1611 1808 1010 0408 1504 0405 19 1405 1710 1805 1208 0410 1603 0805 20 0408 2105 1804 1208 0510 5004 0607 21 1705 1503 1807 1308 0409 0407 1103 22 1905 1105 2104 1307 0311 0409 1104 23 2504 0707 2205 1408 0307 3610 0704 24 2304 2351 2207 1610 0203 0109 3104 * Key: xxyy; xx=tens of ~, yy=mph

-238IV.1.4 Michigan City, Indiana

TABLE IV.1,4 METEOROLOGICAL DATA-MICHIGAN CITY, INDIANA.,1968 *xxyy; xx=tens of 0, yy=mph CST 21 May 22 May 6 June 20 June 9 July 8 Aug 29 Aug xxyy* A AO AO AO AO A A0 1 0410 20 1605 30 16o4 50 17 — 75 1914 60 1006 75 1206 50 2 0481 20 1605 15 1704 30 16 — 50 1815 60 1506 75 1410 50 3 0508 20 1806 15 1806 15 15 — 50 i612 60 1607 45 1508 50 4 0207 30 1806 50 1806 50 15 — 30 1513 60 1709 45 1508 30 5 5608 50 1806 50 806 50 15 — 50 1514 60 1909 45 1508 50 6 560o5 30 1807 30 l806 50 08 — 75 1611 60 1809 45 1508 50 7 5402 20 1804 45 1806 45 05 — 60 1411 60o 1810 45 1508 350 8 5601 60 2103 45 1906 45 05 — 45 1410 60 1809 60 1509 45 9 3600 60 2102 45 2006 45 05 — 30 1410 60 1809 60 1410 60 10 35500 20 2801 60 2404 60 56 — 50 1410 60 1909 75 1411 60 11 5600 60 2802 60 2902 60 o 608 50 0609 30 1909 75 lo0 (150o) 12 56oo00 60 2107 75 2901 75 5608 50 0610 15 2709 75 1109 120 153 3601 60 2008 60 2802 75 3610 30 0o07 50 5009 45 1408 120 14 3400 45 2007 60 335502 60 0308 45 0 o10 45 5425 45 1608 75 15 35502 45 2006 60 3401 45 0411 45 0410 45 5520 45 0110 45 16 3606 45 2008 45 3400 45 0412 60 0412 45 1009 45 0412 45 17 3603 45 2008 45 2201 60 0510 60o 04li 45 1508 45 o413 45 18 oo102 60 2006 45 1905 45 o609 60 0412 60 1607 45 0515 45 19 54oo00 60 2505 15 1805 45 0706 60 05153 60 1607 45 9711 60 20 3400 2504 15 1803 45 o080o5 75 04015 45 1707 60 0706 75 21 3600 50 2406 30 i8o4 45 1210 60 o4l4 45 1704 60 1009 45 22 1703 30 2704 15 1804 45 1412 45 0418 45 2506 45 1010 45 25 1703 30 0000 1804 45 1411 50 0520 60 2404 30 1109 50 24 1502 30 2500 30 1804 45 1510 50 0520 60 2208 45 1508 15

TABLE IV.1.4 continued OD 8-8 5 S02=. 0011 0 0.0 3 13 1.0 2 8.7 H.V.=39.5 0 0 0.0 3 19.4 2 1 1.5 SPOT=.1180 7 9 1.6 7 21 1.5 0 0 0.0 SH 8-29 5 S02=.0032 0 0 0.0 2 1 6.2 5 21 3.1 H.V.=65.0 0 0 0.0 0 0 0.0 9 22 3.6 SPOT=.3269 0 0 0.0 1 0 2.0 7 7 4.0 CH 8-29 5 S02=.0038 0 0 0.0 9 18 2.4 4 20.6 H.V.=57.0 0 0 0.0 3 23 0.0 1 0 4.0 SPOT=. 1831 o 0.0 0 0 o.o 7 6 4.5 1

-241

-242IV.1.5 Porter County, Indiana

TABLE IV.1,5 PORTER COUNTY WIND DATA, 1968 *Key: x,y,z; x=No. of hrs in quadrant, y=sum of hrs between occurrences, z=av.wind speed Groups I, II, III; I=NW, II=N, III=NE W Variable E SW S SE Week Wind Data Station Date Day Contaminants I II III x y z x y z x y z SH 6-20 5 S02=- 0 0 0.0 0 0 0.0 4 9 3.6 H.V.=103.8 0 0 0.0 6 8 3.0 5 16 3.2 SPOT=.1680 1 0.2 1 0.2 7 21 2.5 OD 6-20 5 S02=.0088 1 0.2 13 19 1.7 2 1.8 H.V.=76.8 2 1 0.0 1 0 1.0 2 13 1.0 SPOT=.5298 0 0 0.0 1 0 0.0 0 0 0.0 SH 7-9 3 S02=.0009 0 0 0.0 2 2 9.5 2 2 6.7 H.V.=54.6 0 0 0.0 5 6 5.7 1 0 6.0 SPOT=.0893 7 9 6.3 7 15 6.1 0 0 0.0 OD 7-9 3 S02=.0023 00. 9 11 2.1 1 0 2.5 H.v.=43.9 9 8 3.2 1 0 1.0 1 0 2.0 SPOT=.1301 3 2 2.6 0 0.0 0 0 0.0

IV1.6 Surface Synoptic Weather Maps IV.1.6 Surface Synoptic Weather Maps

TUESDAY, MAY 219 1968 4Q, 15' 30' 25' 120' 115' 110, 105, 100, 95, 9 85' go, 75' 70' 65' 60- 55, -i::'YP i.:''s~~'. iI OP ri~~iii~iiiiiii8:::':i~~i::::"r:::::10 \ N........... F~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~iiiii~r XX 5~~~~~~~~~cr s ~:::~:,l!iiiCaiiirliiiiiiF 85 beiiain~$.~~5 XiiiiiirI F~~ i~ i ~i~ii~~~:~bi sa................ 0 z'~~'~'~'' a -)............ii~~ii~~i::~:~i ~iiiliiii-i~liii~iiiiliiliiiiiiiii ~ i::i::~~::::::: H~:d-: iiiiiiliiiiiiiiiiiiiiiiiil~ ii::~iiiii~iiiiiiiiii~i:'$iiii;~ B~~ Q fiii~i~i~iiiii~iiiili~i~:,iii.~9~: 40' "it -0oX~U3~S~'i l Yr rd COn 3 I6 ~ nipee 35' ~~~~5~~~~~~^31~~~~~~~~~~~o~~~~~, e' 3Z~ ~ ~ ~ ~ ~~~~~~~11;A' Dh ~ iiiliiii~ii~ gul\ QL -67 06o 5 to Al 9:,"~~~~~~~~~~ 7&, 4.1#rI ~yrs\ 1 \6\~~~~~~~~~~~~~3 I~ii-iiiiiijjiiiiiiiiiii 9gl's~~8 L ~~ ~ JA4`01 1 t Spr gs City A(. C7 Pp a95.Flo IV - k~ ~r~.~: —ii-iiiiiiiiiiii~Itlzji 37~t~rfo ~ s~';,csvl~e: Sp'ingtie\~ A-2 Is q 5,!'5, oa3:so-~~~~~~~~~~~~~~~~~~~~~~,, 4~~~~~~~~~~~~~~~ pg~~~~~.0*6'0,....... 611 ~ 4~~ vf 4 1 05,~~~~~~~~~~~~~~~~~~~1 Niiil 6G 063 1 \ 4L 91Oi.~ Cl 52~iJ:: i~d"o;a;Iv "~~g~~p~~;tiJ~~~r — ~, Pueblaj 36 u5\ L'~~~~~~~~s ~~iiiil~~iiiiiriiiiiiiiii!~iiii~~~~~iiililiiil ~ ~ ~ %% 5 I -r a09~2 46\6~~~~~~ ~~L~~f) ~ ~ ~ ~ 14.,d ~~~~19'1'10+3. se tl -lo\ okz Is~~~~~~~~~ 23~~'~~L+I~~~C;- ZS~~~~~1~~0~~9 43' \ v cJe City abD~i7) rgy~~~Ye v)~62. 25'~ biii~~~iiiliii~~~~~iiiiiiiliiiii~~~~~~:riiiii:~~~~~ril ~~~'i 6!J~ ~'",~''"':''':::'i~X~::::.:::: ~`a2-+b= 41~j T J ~p,~~bl a~'a5. I~rCh~\h.\.h0. W -IT.CA L LES AT \IAR r52I(IU., I-AT!n~ ~- /h~ 25)~5~ ~CQ~B~_I\.. SURAC WATERMA - AND STATION WEATHER 20-63F ~ I AT 7:00 A.M.. E.S.T.~ ~ ~ ~ ~ ~ ~ ~ ~ ~~~~~~~~~~~~~~6 88J 120' 115' 110,105' 100, 8- Y Figure IV. 1 6. 1'#Synoptic analysis for May 21., 19600 (ES'SA).s""~;

WEDNESDAY, MAY 22, 1968 140 15. 130' 125' 120' 115' 1 a ti 00 51.~: ~: 10, 105' 100, 90,'01ol- 0e 75'o 70, 65'' /, 1012 1 1016 J~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~/ I &" 10'8h'Oo 28 Yhj~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ / ~ ~ ~ ~ ~ 1 ~~~~pp ". /p~0''/(u i-]I~~~~~~~~~~~~~~~7 27 1 1 0,v-~ i. I 00 Ply 39 "La 2 E.W-VIN iimil 1.~ ~ ~ ~~~: %0... 37: ~ L2!() +.- F.,o\.0.o; 37 ~~~~~~~~~ ~~~~~030.41~L' Mneo"' Oh~~~~~~~~~~~p~~~~~~~~ ~~~t - 6 N 3,;'tap' ID i's,09 1 AG 1~ /' spig.01?d -1+3 of 4 3 7~ ir%-3Mds ~~c~~p ro;3S~~~~-~~- sno4IId.CV3 B Ljl~~~~~~~~ ~~?~~~19~~~8~~;5 IxrrC-5 k~~~~~~~~~b ~~~ City r-~ r~~~~~it S5 4 nqAPlo 9 03 6P50\ cU' I~ Is i~~j* ~ ~ ~ ~ 6~~a ~ ~~Grand b?~~~~~~lsLZ~~~di~~r.-J~ ~~,`b!3,,~~~~~"i"BG 7 k~~~~~s; bs4,.g E12\ 48~~q l 46? 0.4 r.1 00466\: S 68 Ro~~~~~~~~~~..11 Ta.)Ja~ 2 ~~3 +S/ t ~1J~~~~~~~~~~~Asm~~~~hl ~~~~."OO~~~~~-L~two S ii: r 6 —- r ~~~~~~~~~~~~~~~~~~8cn\\'~~~~ — \,Able, E4 05 Z T, VI1 6 El P a 9 r uO" o t y4L ~nm9 28 49 _,,,~~~7'24\. Abilene 6rS., A10016 1. loo...... I —- o1000e~arle AT 7: 00 A.M.. E. S. 1. A~7 09 ~ I outon bbj~ 120- 115- 110, 105' 100, 9 w' FigreIV1..2"Snoti Aalsisfo M-v22 0"0 ESA)

THURSDAY, JUNE 6, 1968. — 40 135, 130' 125' 120' 115'. 110 105' 100' 90 a 75' 70' 65' 60' 55 I:{ *J Wallis ------- - ---— ~~~- -~ - ~0. 5o6! ~ -..-~ ~~~~~~~~~~~~%. Ft lis 4 46 k-~ 4B 144. ~ Este.','",o mmnot ~ iiiii L 4ak ~ ~ ~ ~ ~ 4 S" Uplatte 113, 0 68FJ La~ia~p~l~b I ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~h......... C....'~~~~~~~~~~~~~~~~~3 City~~~~~~~~~~~~~~~~~~~~ct or~Q Ie, I:~': V,',,1 30 Nee,~'Si~~~~~~~~~~~~~;x, ~ ~ ~ ~, - I Ab!i e ~tg p"'"" I-i",:':0?,.:' -Ir A.10 r iO Chftitah,'a i~~~~~~~~~~~~~~~~~'~~").,,7~rll qB ~ r oo 0 0oo lo. 5r ~''.L t~,scY ~~~~~~~~~~~~~~~~~~~~~~~~G;O \ p\ \N " ~' SURFACE WEATHER MAP....... AND STATION WEATHER,-: AT 7:00 A.M., E.S.T. ~o.1 \ XD 20'''~"':Figure I[V.'I. 6.-3' S~ynoptic analysis for JTu~e 6,:].68: (E.SSA).

THURSDAY, JUNE 20, 1968 130' 125~ 120~ 115- 110" 105' 100~ 95' 90~ 85- s0o 75~ 70' ~5 6O. 5 1012 11008 1004 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~1016:::r +hpo..is 4S me, o+e, v'. cv..~~ ~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~.....:~~~~?:;~~?:::::::ait:::i::::::::::~:::x~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ii~~~~~~~~~i~~~~~~~iiiiiiiiii r~:i!~:.itii~iifii..~..:..~~~l: % I o ltl o ~eptinnem 41 4b'iliiiiiiiir~ ~ ~~~. ~ I d Q ar. — liiiiiii~i~.~~iQ~'~i II~rS~sJ.,.... --— (~....:, o,...... +3r 40-f -~~~i~~~i9~~~~i~~~.~~~~~:iiii ~ ~ ~ ~ ~ ~'~:'""'"~:':':'i i:: aCd~~s. L'".... S.. ~' 48~~~~~~~~~~~~~~~~~~~~~~~~.z -, *35._ ),,-, ~i:\:~,' ~~5 1\ ~ fL ~'"'"'~:~" ~~~~~.':::~ _.:,,o~o, ~,,'......., - A C._.o AS, alrln~~~~~~~~~~~~Vl 9 C 94~~~~~~~~ ~~~C 51 Choy...... r-tocrtellol os4,4 09b70?:. SURACEWEAHE MAP _'~"~ i'i' \ " y'L'\o~N~. ck ~ ~ 5 o - 46~rbi -fly,"K - — w a~_~~~i~ ~o. us. n o.,o~. zoo.....:~~~~~~~~~~~~~Gm.%PP 1 ~~~+zzr cS~~~i~'~~~ qG 41,i(i iCsv - "' "`";i;-~""~~~~~~~~~m ~ 0j)-h C4., _ Fiur I. 1..:Snpi nly s s frJn3016 ES) B S/r 64 r~~~~~~~~~~~~~i~~~ L~~~. 4 8 Dr I~~~~~411 f 3~~9~~i~ii~~i ~~:::: ~~cs,, 6 C~r Crmd ~~ 70 0~~~ C" -I (48 a I *8~~~", siia I C"'viv it~~~~~~~~~~~~~i 36 14~~~inidrd -~1016 3~~)$4!o G3 64\ Cr~~~~~~~~r~~9~~f jC S~~~~j4~~~\Qb 1/ - G 4 f',4-4A IhoriOOFrtmih1 d 72oiri J Zf~~~~~~~~~~~~~~~~~~~~~81 I 64F~rer7 T. I -1 C.66 73 4SvCl~~~~~~~~r l Ro~~~~~wtoll I 58 14L ~~~~~~'~~c;;~;;hfA M P~~~~~~~~~~~~~~6 AND TATON WATHR o AT 7:0 A.., E..T. 120' 115 110 10, low A Fiue V..4:Snptcaalss rJue20 9i084(ES)

i~0,.japo.~..` 9o~.:UESDAY, JULY 9, 1968....... 130 125'.. c,, 10, W 90, 85 so. ~0, 5' G0, 5' Ft A#e ~ X.,5 \:::: I do. 6 I I iis r S'i~~~~~~~~~F~~~d~~,,lSZ~~~~~~rrn Sm.4: ~'~~~~~~~....:~'' ~-E> 1 Sal" S' ~' " - - -- ~, Lv"hm.~~~ ~/0,1,,,, Hb:..: -40tell., %2,L9 to,;%~I ~ ~ ~ ~ - 9~~,~9~~f~ ~ ~I~~:O~~' ~ ~ 3~~~r\ 5819~~~3 9 ~ ~ ~ ~ q s C ity I 42Btsn ~~~~~~~rr ck 4~ ~ ~ s ti ~:~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~h..'~/ 3;..~h,~~~~~~~~~~~~~Z Lois j ~ (SS~~~~~~~h113~~~~~~~~~SI,,~~~~,,-l,~ Ba p., ~ T.- ~',,,,.. i~:~: ~ - ~~~ ~ ~~~~~~, Zt;4-!SS;. -... v,~o:6. F~z, c,, ~ D4 c, y.. V, -;, 9 ~ ~ ~ ~ ~ ~ ~~~~~ 60 tSC —~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ai 52 ~ ~ ~ ~ ~ ~ ~ ~ ~~1,-q0 Sg)~~,~ 5~~ar ~ FB'Zd~~ ~ C ity 7R0 b lh IS /8:iA4~,._ I~ tG'T lb ~/ 6 — -to 81 T~c~pipr~~:1 +or~~~,,~e "'~C SI I;kVjoth- -yr!8 5 ~~~96 Grand~~~~~~~~~6 o )9~~~~~~~~~~~~~~~~ i'~G' ton o ~ u as (~t c' ~ ~o - t ~ 107 ~ ~ ~ ~ it t Sz-fl"'. Al~ 39~~;~3 SURFACE ~AYHE MA ~'!'?,......... d 71 415 6 ~~~~~~~~~~~~~S.,o LOW SON W i i' k~ ii v.*,, 7.oo,,..,.,.,.:: Figur V1-EC...TUATTTDE6.5' S yoptcanlysis Pot3 J uy 9 96 ES) c~~Yumr 81 r G~#04 SCL FNUTCLMLS TVROS AfUE 50.00 0. 00.0o So AND STATION WEATHER 20. -R C\O~ I —-~~~~~~~~~~~+W;~~ —------- 120' 15' 110 105, 00, gt?X; pp~~~igr V 5 yopi nly sfo uy9. 93I(SA

h ir........._,-,.::::::.~..,..~~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~....... Z'~.e: ~:::i...........:............................ 5 -,o - _.. f,,...........:,[~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~....'~""""'~':':~~~~~~~~~~~~~.:.......,..........::..~.,.""''' (D~~~~~~~~~~~~~~~~~~~~~~~~~~~~~A H ci-~ ~~~~~m ~~~~~~~~~~6~ ~ 6 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~. 9'~~~ft; L i ~~~~~~~Wc ~ ~ ~ i 6 C 0~\0~4 Co O -la) 6)>,~ i~~ll ff, 14;j!P- 9 - ~cn I Co o,~- 6 -A o1 I~~~~~61 6 r3~: - cZ - 07 9\.~ 0 L 6 C 6 "1._~ L,, cL~~~~~6 L o Ir 6,x 6,c~~~~~~~~6 6 ci- 6,, 3J1 o Ln O?I - i -Ln ~~~~~ec ip~~~~~ii! "~~~~~~6;J'o r ~ ~ ~ ~ Po -S ~~~~~~~~~~~~~n~~~~~~~~~~U It;E, I,$- r V - -g'a 20 A~~~~~~aiVI ei~~~~~~83 6 4~ - -4s \ ts / 2Cz~~c u( nV co~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~" AJOV, S~ ~ ~~i~o ~ k CO~~~~~~~~~~~~C 8e C\~~~~~~~~~~C 61-i-~~~~~~~~~~~~~~~~ ~~~~~~ a ~ ~ ~ - si~~~~~~~iii~~~~~~~~~ll~~~0:::~~~~~~~~~~~~~~~~~~~~~0

-251 Go ~ ~'- —' ~L ~,:~i'ii~:~,~..........:i!~ii~""':::?~ ~~~~~~~~~~~~~~~~~~~~~~~~~............ F- ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ N 0~~~~~~~~~~~~~~ a.. >7>..H I@ - tA *7 ~~~~~' w ~:~,~~ 5..' ~ {:,' /......... ~'~.a,~.,E... co -'~.. —. = = =========================================~~~~~~~~~............................... l / >- / " t llWE S lZ: ~~~~ ~~~~~~~L. 4;;;0~~~~~~~~~~~~~~~~~~~~~~~~~~ >Z~~~~~~~~~~~~~~~~A ~~~~~~~~~ - ~ ~ ~ ~ ~ ~.....I (0...... —; ^,H............A.H N T >tf it t>' 6i _4; _ e~~ ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~aw f / <. O g |.~~~~~~~~~~~~~~~~~~.............. 8}gk (~! > taZ AAX' V [ 6~% ~~~~~~~~~~~~~~~~~~~~~~'0 g 5 $ X' t u.o| | >~~~~~~~~~~~Ol t 4'~ t > wJ n ov 1 t /tAS00 WX/ <. HJoe O

-253IV.2 RATIOS OF ELEMENT PAIRS, SUPPORTING COMPUTER PROGRAMS, AND DATA LOCATION TABLE

-254IV.2.1 Ratios of Element Pairs Cd/Pb-Cu-SP-SO2 Pb/Cd-Cu-SP-S02 Cu/Cd-Pb-SP-S02 SP/Cd-Pb-Cu-SO2 SO2/Cd-Pb-Cu-SP 2

-255RATIOS Cd/Pbj 1968 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 0.0253 0.0C62 0.0273 C.1240******** C.0109 2 0.0041*********' 0.0057 0.C150 0.0048 0.0132 3 ***************************** O.C274********** 0.0121 4 O.OlC4******************** 0.0060 0.005C 0.0047 5 0.0279 0.0108 0.0056 0.1351********* 0.005E 6 0.0065 0.0087 0.0043 C.0214 0,0027 0.0065 7 *******.************ O.C03C C,C879 0.0044 C.0056 -8 o0^.-0107#*** —******- 0.0028 0.0118 0.0062********** 9 __ 0.0150 0.0135 C.C207 c.C086******************** 10 O.0089** C46******** 00038 C **** *********** 11 0.0063 0.0355 O C035 ***4************************* i2 0. 0179. 0Q 62*********************** ************** 13 0.0054 0.0176*****************4********************** 14 ********************************* ****** ******************** 15 0.011 5l******************** 4***************************** 16 0.0025 0.0 10**************4 ************************ 17 C. 01 00*************************************************** 18 ***4****** 0.0515********** C.C283********** C.0119 19 0. 02************************************** 0.0130 20 0.0155 0.0C83 C. C7C, C.0162 0.0077 0.0208 21 ************,******* 0.0273 C.C7SC******************** 22 ******+****4******** 0.0193 C026******************** 23 ****** ************* 0.0414 C.2CCC******************** 24 **** —-******* **4**** 0113 C.0149 C.0500 C.0192 25 ****c************ 0. 0 674 ****** ******************- ***** 26 0.0038 *****-************* 0.0097 O.C 84********** 27 *******t*******t*****4 ******* ********* 0.0250 C.0212 A! <****r*************** 0.0037 C.0117 0.0032 0.0066 _' 0a o0 2 0.0148a*****4** * LC 158 O.*CC7 C.CC81. C 0.O00 (6 -'0214 ).o 254*****t**** ().0096*** ****** 0 *****44** * O. O0 e3**r***** C.0137********** 0.0074 E..; 0-40 -*****4***** ******* * ***** C.010C 0.0091 F 0.0034 000C48 C.0037********** 0.0035 0.0012 -G 0.0104 r.004 7********-*( C C0 93********* 0.0047 H ************** * **** 0.0061 C.C1CR C.Oc81 C.CC8C! 01?':'.........^.- O0-006********* 0.0035********** K.3;: -* *:*' *- -***, * 0 OC 440 0.0240 C.0061 o C.CCS8 L 0().fl0 7 0.010~******************** 0.0050 0.0112 m1 * 0.0066 0n.0043 C.C05C ********* 0.007t** ******* N O.CC3C 0.0067 0.0047 C.0148 0.0064********** 0... -0 O n.0087 0O. COC2 C. C.C4E******* ***!(* 0.0065 C.0054 P 0.001 0 o0.0175 0.,0024 C. C417********** 0.0107....0..... 0. -CO'O77.0. l0215 C.0026 -.0214***.****** C.C37 R 0.0067********** 0.0032********** 0.0076********** T'! 050.0045 0 0086 0.0045****************************** UJ' C.00224********** O. 0031s**4***** 0.0066********** V 0.0112 0.0C58 0.0084 O.006C C.O10- 0.0140 W i 0.0078 0.0111 0.0052***************************** SHIP * *** t***** 4******* ************* 00338******************

-256RATIOS 1Cd/Cu 168 STATICN MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 25 1 0.6575 0.0172 0.0789 C.0800********** 0.0480 -- 2 0.0433********* -0.0155 -0.1600 - 0.0684- 0.1786 3 ****************************** O.C8C******* *** a 0.0116 - 4.03 19***************** 0.0617 O.O01d90 0. 0200 5 0.0325 0.0034 0.0175 C.8065********** 0.0368 6 0.0059 0.0011 0.0O09 0a0050 0.0057 0.0031 7 ******************** 0.0083 C.2231 0.0124 C.0156 - -8 - 0-.- 9***-* ** -* - 0.0009 - 0.0062 0-.0024**** ***** 9 0.0040 0.0C15 C. C13 C.0026******************** 10 0.0036********** 0.0020 O.CC24******************** 11 0.0414 0.0534 0. C54****************************** -f2 ** - *- - -- T4 —— ** * ******* ** * ** ** ******* 13 0.3846 0.0417* ******** ****44********************** 14 *********************************************************** 15 0.0682**4***************** ********************* * 16 -.0636 C 0.0500 *********** ***** *** *** ********* 17 c *0*800************************************************** 18 ********** —. 4,0708***** ** C. 08i12********* C. 1357 19 0. *0209**************************** **** ****** 0.2917 20 0.0867 0-.0273 C. 5571 C.1235 0.1429 C.1923 21 ****************** 0. 3000 C.5217******************** 22 *************** ***. 1000 C. 1692******************* 23 ****4***4******4*** 0. 30855*******+**+********************* 24 *****-***-***-*-... 0347 0. 167 C. 16CC 0. 1333 25 ******** * * *********. 1722****************************** -.-;25 ** ** **-****+*** O0.038q O.C326********** 27 **a* ********$************************** 0.0302 C.0773 A $$$***********8* * 0.-0317 0.1615 0.1100 0.1000 B 0.C969 0l18z4,4*******~ C.0480 0.1037 C.2267 C C.2000 0.050. ***************************** n **D******* 0.2174*?****tX** C.2000********* 0.0952 F.,- 1- 0.1436********'*** ********* 4*** 4 0027 8 C.0429 F 0.1235,~********* O 146f3***c***** Co100C 0.0357 --- l)3.1-270 O. 0750Q********** C. C 75********* 0.0833 H ***'*************** * 0.2597 C.3610 C. 26C**********. f.. *,,;. -, * *. f**.,,,,,. *..,.., **-.***,,,. ~,' J,*340****** ***********************t* 0.C421**********.- --- t c...ni-00***********-**i **''**** C.0500 0.- 1400 0- 0.~786 L i. 1391 P.l17***l***************** 0.0220 0.1125 "M --- 0.475-0*l******** 0.14s52********* 0.0293********** N CoI100O 0.1067 0.0615 0.1385 Q.0424********* 0n 0.1625 C.06?7 C. C 625'** -***** 0.o687 C.C389 P 0(.0152 0.2188 0.0562 C.1389*********.__ C1304 0. 0. CC290 0.4828 C0.C545 0,0938********** C.0261 R 0.0462********** 0.0368********** 0.05.20********** T - o0.0684 0.0545. 0529 4** ******* ***************4 U 0.0500********** 0.0417********** 0,0559********** * —..-... 0.0750 n0.0714 C 00900 C.080c C. 1C8Q 0.1750 W i0.1750 0.2195 0O.857** 4 ***** **t ************3*** SHIP *********** ********** * ** C* * *********************

-257RATIOS Cid/S.P., * 1968 STATION MAY 21/22 JUNE 6 JUIE 20 JULY 9 AUG. 8 AUG. 29 1 0.0417 0.0029 0.0256 C.C375********** 0.0081 2 0.0160********** 0.0049 0,0375 0.0081 0.0272 3 **********:**** ************** C.0374********** 0.0174 4 0.0230******************* 0.0093 0.00C72 00055 5 0.0279 0.0059 0.0036 0.0758********** 0.0029 6 00.0092 0.0C40 0.0042 0.0096 0,0047 0.0056 7 ******************** 0.0024 C.C3C1 0.0063 C.CC57 8 0,.0242********** 0.0024 0.0124 0.0088********** 9 0.0325 0.0C61 O.CC9C C.0128******************* 10. 0205********** 0.0015****************************** 11 0,.0158 0.0255 0.C026****************************** 13 0.0250 0. *0160*************4 ************4*********** 15 0. 3326************************************************** 16 0.0087 5O***************** 4************************ 17 O. 0182 ************************************************** 20 0.016-.7..006-2...886 C. 16.7 0.00 ********** 21 *******************^* 3.0390 0,C8************ *********** 22 *************,279 * ************** 2.3 - * **** ****- ***'0439 C, 1C37*********** *..********** 24 4 * **j4 44****9 **r ** 0.0219 0.0421 ^ ro.0123 25 ****a**** *4********** 0. C 383*,*****,****************4******* 26...0074. 1. 0*.177 ********** 27 4*.t*** *4* ***^****4**4************* 0.0119 C00246 A!'*****4***o*******7**.Ct42 0.02%96 0.0080 0.0271 B 0.0274 0.0146*s******** C.C114 0.0117 C.C15q C 0.0246 O.0109 q.0087**-*******..........0 *..4..........:,00*77**-*** C.0367.********* 0.0106 E-,)3 9 *4 * * ** 0. 0 ^ 0'.^^^9^ C.0C44 F 0.0137 __3.OC449 (7;.07 * 4 07 007C59 C.0023 G 0..03! I C.0T50.*4*^** ** C.CCC<2********* C.0105 H **'***<******** 0o.0085 C.CC93 0.0143 C.C188 J 0.':)4'5******4*** 0. n 042 *********. NO48I********** K" ~.' -.. 3******033 C.C117 0.0089i C.?.C82 L L0.0178 0. 066******************** 0.0080 0.0124 M 0.0273 0.OC4h O.CC4$9 ********* 0.0 C1CO********* N. CC99 0.007() 0.0076 C.0105 O. 0091 ********* - - 0.0319 0 -. -'C4 C. CC3'38e********** 0.0063 C.0C39 P 0.0035 0.0137 9.0031 C.C49C********** 0.0140 0 ~ 6.Cl38,O.Ce7 0.0015 0.38401******** C.0026 R 0. 0168********** 0.0029********** O. 100********** T 0.0141 0.0079 0,0111 *****************************~tj 0 0120***X;****** 0.0083********** 0.0130**********.V - - 0.03 95 0.00,38 0.0189 0. 0060- C.0-138 0.0236 W 0.0267 0.0058 0*. 0056***************************** SHIP******

-258RATIOS Cd/SO2' 1968 STATIGN MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 **********4**********4************.****4****************** 2' *************t4****** ******4-** ****** ******************** 3 ********************+******** C. 7536***********4***4*** - *** — ******4***i**************************** ****************** 5 3.0000 0.4167********* *** 1oO4******************* 7 0000************************************** 7 ******************* 4000******.0000****** 8 - 0. 886 9444********* 9 ******4*4*************************4************************** 10 ***************** ********44**********4************* 11 6.* 00O4*4*44*4444* 0.4*0004*4*4*4*4*4* ~4**4*4r*~~*~*~** 11 6* O*********** C***O*************************** 13 ******************* *5*0 ************ * *********** 13 *********+* * ********* 7* **,**** ****** ******** 1 64 * * ** * * * * * * * ** * 16 w 4 *******4*** i4* T9W(w*-*4*F 4 ** 4-444*4**4* *4 4* 44 Wf 4*44*4 * 125 *********$+*******************************44****4*4* 21 * —-'-i -'*-';- **'*.*4 *** 15.0000 36. C1 ~ ******** 22 **29******.******** 29.C02*2** 5.**** 4**4 *****.2 O. * F.......-*.*.. *.t-*..'-, - * *-T *-*- *- * *..*. *.*.* ___ a._-000.3******* * ***.1'***** 21 *****+********* o 1*.50000 36-COCC.***:******1.** 8182*** F2 * 2*. IOCO 0,2564 333329*0000********* 1*.2222 0.14***71*-* 23 ******1**.*6.******* 7.25C0 2P.CCCO*** **************** 24 7.CO***CO 8. OCCC****4***** 25 *********************0. **.4** *4***4*444* 26 0.2941***4******4**1.l4***** 1.7500 1.5554********* A 2 4.0COO0********** 2.0000 2.6250 3.6667 7.2500 B?.2.43 3l.OCO***** **- C.342s9* 9.3333 1.3C77 ~C,3*-i' 518-3i it732 1. - 3f "" T 00* *****4 * -55? r44 -*4*4* F *.*4, *44 *<** 4'*********<***;*{* * 5. **C~**********.00 F___.2.1.( 2-64 1.'6.3333.**.*i*** 1.22?2 0.1471 R.-_ — 4187 ** 4. O 344 4*** 2.3333****. 5**** C.9375 H 4 e** * ****4* ** **8 0.6452 O.8889 0.7429 11.6667 J 13.8.'71*00 * 6U.********* 151 ***44** ********* ***1.33 ******** " K - o0.2500 n o * * ** * * - * 0.57 r14 W -tO- O0 -53*-****** L 1.3913 1*.**O****************** C***7*********** M —- 3 -,, 0 0Yf)i:******, ***. nn*******1i'**** N 1^..7 CO****5** 0,64000 C.75 CO 3.5000 ********* ~ 0 50 **** c) - ^^^*** 0.-5000********* 3-.6667 C.3500 P -5.1r0o***************4<* 25.CCO********_ 6.OOOC 0 1.1250 1.7500 (0.1176 2.142?9****4***** 0.1364 R 1,41184******** 0.1373**4****4* 6.5000**4****** T 13.TOOO O 6.0000 0 7500******************* Uj;**4**+^** ***4*t*+*4*4***4*4***4*4*****# *4*4***4 *444*4* W 8. 7500( 1.00C0 C. 9Z2t*4 4-4 I ^^^***** ^ SHIP ***i***********44*****444** ***********4**** ********

-259RATIOS Pb/Cd 1968 _ STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 39.5833 160.0000 36.6667 8.3333*3********* 91.6667 2 246.1538********** 176.4706 66.6667 207.6923 76.0000 3 ***************************** 36.5385********** 82.7586 4 96.5517* ****************** 166.0000 200.000 212.5000 5 35.8974 93.0000 18C.0000 7.4000.********* 171.4286 6 153.8461 115.0000 231.2500 46.6667 366.6665 153.8461 _ 7 * t************** ** * 337.5000 11.3793 225.0CCC 18C.0000 8 93.*3333********* 360.000C 6e.154 162.5000********* 9 66.6667 74.2857 48.3333 11 57895******************** 10 112 l 5000)********* 260.0000 216.6667 ********** ********* 11 158.3333 28.2051 283. 3333****************************** 13 1 86.6667 56.6667*************** ************************ 14 ********************************************************** 15 86.6S667 (**+** ******** ********** ***** ****i*******+$ 4t***+** 16 400.0000 911111 ****** 4 *** ** *4 *** *********** 17 100.**OO*************************************************** 18 ********** lgo 41 1 8'********* 3. 84 6********** 84 2105 19 35**,5555************a********************** ***** 77.1429 2-0 64.615-..4 12C.000 — 14.1 — 026 61. 9048 13-f000 4 8. OO 21 *******4****4******* 36.6667 1 3.3333********** ********* 22 ******** ************ 51. 724 1 8.* 1 ****3***s******* ***** 23 *****44: * ******** 24. 137. *C CC**************9** 2-4 88*2****3*5**-****** - 353 67.1429 2. CCCC 52.0000n 25 *;********* ******** 14. le P387**** 44********4t i*******4 i4** ** 26 26070.0 0 0** M** *4**t* **** 102.8571 54.2857********** 27 *:***** *****************4** ********** 40.0CCO 47IC5FF A *******e******T**** 270.0000 85. 7143 309.0908 151.7241 B 122.5806 67.7419*********_ 63.3333 150.0000 123.5294 C 167. 571 46.6667 184.61544*** **4** 104 34784********* D *********' 120.0O00*****4***** 72.7273********** 135.0000 E.71,426*-;fl *;**+****4* 4************* OC.00C 109.5238 F 295.2380 21C..001 n 266f.6665*****4*** 28 1.8181 80C.CCCC G 95.7447 2111 1 1****** ** 107. 1429t********* 213.3333 H ******* ******** 165.0000 92.500(0 123.0769 125.7143 J ~8 1.5789^q********* 28. 1818f********** 2?7. 5000o********** K 255. -0000 ******** 250. 0000 41.6667 164.2857 172.7273 L 103.1250 10no.OOO **8*8**o*88*****,**4 200.0000 88.8889 M 152. 316 233.3333?2C. C OCO********** 129.41 18********* N 33 5. 7141 150.030) 2 12. 5000 67.7778 157.1429***-******* 0 - 115. 3846 1.09.0909 2 1C0. 10000******* 154.5454 185.7143 P 1O0.00CC 57.1420 411.1111 24 CCCC********** 9a33333 0 120.6296 46.4286 383. 3333 46.6667********** 266.6665 R 15C.C00***0****** 314.2856********** 130.7692********** T 223.0769 116.6667 222. ******************************** it 411.1111,********* 320.0000* ****4***t 152.6316********** V - 88.8889 171.4286 119. 4444 166.6667 100.0030 71.4286 W 128.5714 90.0000 191. 66674* ************************* SHIP ************************** * 2.0 ***** ***,*********

-260RATIOS Pb/Cu 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JLLY 9 AUG. 8 AUG. 29 1 26.0274 2.7586 2.8947 C.6667 9.2857 4.4000 2 10.6667 16.3636 2.7273 10.6667 14.2105 13.5714 3 4********* 4.1667 1.4286 2.9231 2.8049 C.96CC 4..3.0769 0.6667 8.8000 10.2469 3.7931 4.2500 5 1. 1667 0.3207 3.1579 5.9677 2.4074 6.3158 6 0.9091 0.1243 0.2056 0.2333 2.0952 0.4762 7 *,4***************** 2.8125 2.5385 2.7835 2.8125 P ] — -- -.692 - 59 0. 3333 C-. 52'38 O. 3824. 01196 9 0.2647 0.1106 0.0630 C.2973 0.1333 C.C473 10 0.4000 0.0491 0.520C C.5200 C.0259 0.050C 11 6.5517 1.5068 4.3590***4 ************************* 2-...... - — T* —' ~ 76: 4- 44**..-.6 — 4 —.4 4- 4 4 -*-' 13 71.7949 2.3611 17.0588***************************** 15 5.9091 2. 0000 14, 6 667****************************** - 6 --- 225.4545 4. 5556***** 4*** ***:************ *** **** ** 17 8.0000 2.1818 14.6667 4.8421 65.5172 9.4366 -8 b...6......;6-67 — 1-37'0 2.3437 2.8750********* 11.4286 19 0.7442 0.6212 0. q474 ***4****** 1.9718 22.500C 20 5. 60-C 3.2727 7. 8571 7. 76471 18.57'14 9.2308 21 **** *4 ****4******** 1 1.0000 6.9565 8.5333********** 22 ******************* 5. 1724 6.4615 15.1615********* 23 *****************+** 7.4468********* 4.9000 5.8333 24.********* *******:* - 3.0612 7.8E.3 3 3.2 CGCC 6.9333 25 ************J******* 2.5556 5.3125 2.09 304******** 26 16.2500********* 3.5556 4.C0C' 1.7674 2.0000 27 C***4**4**4******4***** 4***** C.8182 1.2121 3.6364 A 101.4493 ******* o8.5714 13.8462 34.0n00 15.1724 B t1. 750 12.3529 33.3333 3..3C4C00 15.5556 2P.OOCO C 33.5714 2,-3333 17.1429 - 6.5C0********** 28.3333 D 22.6667 33.8028 1C.C000 14.5455 18.5000 12.8571 E' 1..2564**** ***4'-',* *********-* -**- *2.777"8 4. 6-39 F 36.4-706******** 39.0?244********* 28. 1818 2E.'14 G 12.1622 15.8 33 52'1739 9.3750********** 17.7778 H -3.170 50.0000 42.8571 35.23P1 32 *CC* ********* I *<* * 4 * *** **** t ***'** ** 4! 4****** 44*** **** ***** 10.0 9 c1 J 24~8000 7*2500******E******I****** * 12.1053******** * K 25.5 )OC-***** *** 4***'4i* 2.CE33 2-.OCCC 13. 5714 L 4a.3478 _1,.7143 28.7RF79******J**4 4.3902 10.00(l M 72. 53000*** ***** 2. C323********** 3. 7931 50.5618 N 33.5714 16.0000 13.0769. S3846 6.6667 15.3846 0 n 0- - 13. 75C 7.5000 13.1250.9231 —'.1. -2-5C.-2222 P 15.1515 12.50CO 23.125C 3.3333 7.3913 12.1739 0 3.7634 22.413 2).9091 4.-3750********** 6. C56 R h.9231** ****** 11,5789****4***** 6.8000********** T 15.2632 6.3636 11.7647 3C.76 2******************* U 20.5555 R.3333 13.3333 44.0000 8.5294********** V. 6.6667 12.2449 1.:) 7500 13.3333 LC.O'. 00 12.5000 W 22.5000 19.7561 16.4286***4***** 11.0000 1 3.333 SHIP i ***,-', -''-*-:, --—,,-, 7.4000*4*-*-"**: ***

-261RATIOS Pb/S.P., J 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JULY 9 AUG. 8 AUG. 29 1 1.6522 C.47C6 C.9402 C.3125 0.6566 0.7432 2 3.9506 0.8257 0.8721 2.5000 1.6770 2.0652 3 ********** 0.7634 1.1719 1.3669 1.5541 1.4371 4 2.2222 0.9790 1.7187 1.5370 1.4474 1.1724 5 1.0000 0.5503 0.6475 C.5606 0.8333 C.4959 6 1.4085 0.4577 0.9686 0.4480 1.7187 0.8584 7 _ *****t****43** ** C. 133 C.3420 1.4136 1.0345 8 2-2581 0.61 0.8571 1.0476 1.4286 C.9016 9 2.1687 0.4522 0.4328 1.4865 1.3115 C.4862 in 2.3077 0.2385 0.3939c.** ******* 0.7000 0.5729 11 2.5000 0.7190 0,7456**************<*************** 37....3...9...i_- - 3-49 C. _C639*********** ************** **13 4.6667 0.9091 1. * l33*****3************************ 15 2.8261 0.3529 2.6 oo****************************** 16 3.5000 0. 5325 ****2 ******2 5** ** *********** ****** 17 1.8182 C.4404 1.8803 0.6479*** 4*****4***** *** - 0.4 592 3.. ~3832-7 C. 7CC9; C.7 18~8 C.5882********** 19 0,5818 0,.4184 ), 5143,**4* *** 0. 3043**********. -......... 7. --..500 1'2500o 1.o317 1.04C84 ********* 21'I****~C******4. 4**** 1.4286 1.CSr I. 600C********:** 22 ************** ******* 1. 4423 03.736 2. C4t] G8****** *** 23 **4**. 6 C.5185 1.2564 1.2281 24.. I 4*** 4 **4* 8 - **4-* 1.468,7 C. 84 2 1 C.6420 25 ****^** ************ 0,. 57967q 4***4* 1,4 186*R***l**** 26 1. 1.**C 1. C 5a.000 1. 1 42 9 0.9620 1.0222 27 (**** 4** s** *** ** C*** ****** C.5510 0.4762 1.15c4 A 7.9545 0r.8046 3.8298 2.5352 2.4638 4.1121 B 3.362 C. 9SO6. C828 C. 7238 1.7573 1.9626 C 4. 12....2 - 5'. IC') 1 1.'"16000 " "1.285 -7 1..8 182 2.4460 D 2. 12~~' C0.9195 1.3684 2.6667 1.52226 1.436_2 E.2'77-7'***H-*,',*4",,*,*,-,. C.-4918 0.4832 F 4.; )2 3 I C 19 4 1.89.35 I*** **** 1.6 757 1. 8349 G 3.335 6 2 1. )4 i 2. C930 C.9868******* ** 2.2378 _H 3 altfji~3.400)0'.6a8 1 1. 4043 r.86C5 1. 7 r?_ C69 i 84$- **4*******~*****):~.~,5l —~~, ****** 1.326C J 3.734q 0.4244 O. q266********* I. 3855,******** K 3. 311 0.I.68 35.81 63 C.4 854 1.4 5 57 1.417; L 1.933 3363 3 655: 1.0556 0.6116 1.6000 1. 1009 M 4.1727 1,.C79 C.C836 (.3878 1.294.1 2.3077 __ 3. 3099 1. 0 4 3 5 1. 61 I I 4 C.7C93 1. 4 2 8 6 1. 4 7 06..-.0. 3.6810 0.5e~5-4 0. 7985 C.4722 0.7370 C3 P 3. 546 1 0.7 4 3 1._2 937 1.17_65 C.9605 1.3084 0 1.7949 n.4A? -.7 0.5637 C.64224********* C.6eC5 R 2.5175,******** 0.9129 C.2818 1.3077,********* T 3.15?2 0.9211 2?.4691,., * **** *********-* ( J 4.9333.8721 2.6446 1.4865 l.98e 3****** -*= V 3.'508.8 ~0.6452 2.2632 1.COOC 1.3776 1,6892 W 3.34351 0.5226 1. C4e***** * 1. 366 5 1. 95135 SHIP *********** *********************** ******** ********'******

-262RATIOS Pb/SO2 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JULY 9 AUG. 8 AUG. 29 1 ************************,******** ******** ******************* 2 ********** ****** +************* **************************< 3 *,******** 47.6190 48.3871 27.5362 766.6665********** 4 **,******* ******************,,**** ***,**** ***,,*************** 5 107.6923 38.7500********** 7.7083 325.COCO********** ************************* ******************* *4.4444********** 7 ********0*********** 130<. CCCC*************2**0**.************ 8 ***************************************** 1 44 4 5 ************************************************************ 1n **** ********* **************-*********************************** 11 50.003 0************ **. ************************ 12''.. ** **** ***-*-** * * * ** ** **** * * *'* *** * Va*** ** *_13 ******************** ************************************** *14 _ _ *_* ****** -i** * ***** ***** +** * * *** * * ** * * * T 15 ***********************************+************************* 16 *******-+*********** *!T****************5:*********~********** 17 ****** *****************.00n**1**.****** **********.- -^- - ^^.^.^^^-^^^^^^^-^^4 21.I**,***4***+***: ** 5** 5.000 4 ECCCC C. C 64C 0000********* 22 ****+s+****$***4** 1500* 0000********** 333. 333********** 23.********+****t***** 175.0000 140.CCCO 122.5000 63.6164 24 **~*************************** 47C.OCCO 16C.OCCC********** 26 76.4706********** 120.000 18C.OCCOO 8 4****** *** 27 ** ******^c****:****4(< ********: ^*^**b*0****44***4^*0****4****** -A 3.33333 280.0000 540.0000 225.00002 1133.3333 1100.0000 B 271.4285 210C.CC00 85.1852 21.7143 140000 00 161.5385 C 87 —-'. 7370-' 16.-4706 240.0000 63C.COCC 600.0000 566.6665D 154. 5454 35.82C9 21.6667 53.3333 284.6152 245.4545 F 620.0000 53.8461 355.5554***)~****** 344.4443| 117.647C G 140o625C 42.2?,22********** 250.COCO********** 200.0000 H 62.9630 1 2.7660 106.4516 82.2222 91.4286 1466.6665 I ****44**C******************4****** * * *** *4 4****** *** ********** J 885.7141 870.0000 342. 569********* 383.3333********** K 63.75%O 79.1667 142.8571 41.6667 95.8333********** L 143.4783 10G.0000 65.5172 22C.OC00 133.3333********** M — 58r00. C000*.****** 300.0000 38C.CCCO 146.6667 140.6250 N 4700.COO****S****** 136.0000 5C. 333 3 550.0000 51.2820 0... -. C_ 000-C * * *** **** * 1. 0 -5- 0000 1 27.5 000 566.6665 E65. 0000 P 5000.300********************* ^ 60C.CC(C 850.0000 56C.0000..0 -..14".8333. R 1 2500 45.0980 IrC.rOO-C0-6O******** * 36.3636 R 211.7647*********: 43.1373 77.5COO 850.00n0********** -T 2900.0000 700.0000 166.6667 6667****************** V * ************************ **** * *************4******* W 1125.COOC o9.0000 176.9231 ******t** 100.0300 140.OCCC SH I P * * 8* ******** *** *t** *** **** **** * 4 * ** 4 ****4*** -

-263RATIOS Cu/Cd 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JLLV 9 AUG. 8 AUG. 29 - 1 1.5208 58.0000 12.6667 12.50CO********** 20.8333 2 23.0769********** 64.7059 6.2500 146154 5.6000? ~*******-*******~************* 12.5000********** 8f.2069 4 31.3793******************** 16.2000 52.7273 50.0000 5 30.7692 290.0000 57.0000 1.24C0****:***** 27.1429 6 169.2308 925.0000 1125.0000 200.0000 175.0000 323.0769 7,*****4**4*********4 120.000C 4.4828 80.8333 64.0000 8 346.6665****4***** 1080.0000 161.5385 425.0000********** 9 251.851 671.4285 766.6665 389.4736******************** 10 281.25004******** 500.0C 41 e.65******************** 11.?4.1667 18.7179 65.0000****************************** 12- ~ *.0 * +" -23.6364************** ************************ 13 2.6000 4*000************************************* 16 14. 7666714*3, 0****************a************************a4 16 15.7143 0.O*OO * *****iT4*************-**** ******* ****** 17 12?5000*********4****+***t****** ***+******F*+***8**4* 18.:' * 14-,.. ".T.7-6* * *****t** 12.30 o7********** 7.i3684 19 47.77783**4****.******************4************ 34286 20 1.5385 - 36.6 67 107949 8.0952 7.0OCO 5.2000 21 *3*******4 **** **4*** 3.333 1gl67****************4*** 22 ***** ****** ******4*** lO. 0000.90*91 ** ** *:4** T ****** 23 ***** 4iC*********** 3. 2414***** *** * ****************4**4** 2. 2 8 8 2 E.5 7 1 4 6.2 3O 7. 000 26 16.-o: o 0: *4 * **** * 444**" 2. 714 3 3.7 i4 3 *****',*** 27 ***t** ******* ****** * *$ ***** ****** 3.o0000 12. 412 -A ~ ***********4***:. sooo 6. I9O 905 9. 909 10. o00(0o B I,'10. 322' 52, 1 t G 2. 3 3 S.642 4.4118......-,..-.-........_ — _., _ _..... _':)-' —~)..:-;.*-,,-.-,^ - _ - -, -,SF C 1;:l^ * 3 5;:^ 5 2 )* 0:;** * 5 0 * *s 1*****: 10.00 5000 D.......* 5****.................... E ~ 6 63 X * -^A * ^^* ^ * t * 36. CO O 23. 3333 F 8 I -52;j'***)'* 6,8.333 **t****** 1C.OCCG 28.0000'.t 7 2 T3 1 33 *^- ** 7** 1 1.4286* S** ****( 1.(0 H *******t * **t*;t*4 s- 4'4. 3. 8500 2.62 0 3 3. 8462***4****** _.- _ ~ - *^ +. ^ a - 4 _f_^. _4 -. -i -_ f 4 i i * 4 _ _ * + * - y* -* V i f i - i - _ K ------.-0000-z(O***-**********4-* 2C.CCO0 7.1429 12.7273 L 7.1875 9.3333*4**8c* *r;*4 *** * 45 45.5555 8.8889 M 2. i 53-******t** 6T ee8**** * * 34.1176**** 4**** N 1. C;00 9. 3750_ 16.2500 7.2222 2 3. 57 14 ***4** ** 0 6..53. 14. 545 5 16. OOO********** 14.5455 25.7143 p 66._0000 4. 5714 1 7 77 778 7 20 0**** *** -7.6667 0 34.4444 2.0714 18. 3333 1C.6667,********* 3. 3333 R 21.6667,-********* 27. 42S***2*****4 19.230 8********* T 14.6154 1. 3333 18*3.88 9*******4** *******;********T: UI 20.J000 4********* 24. 0000C*******^ 17.89474***4***** V 13.3333 400 I4.O)0 1 1.1 1 12.5CT 0C.2593 5.7 14-3 W 5.7143 4.5556 11.66 7 **********:^ *********** SHIP *** ***4'4*4 *4**-****I -**** — 4. f000()*** — *** *o", ** — ****

-~264RATIOS C u/:Pb 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JLLY 9 AUG. 8 AUG. 29 1 O.C384 0.3625 0.3455 1.5COO 0.1077 0.2273? —-- 0.0938 0.0611 -0.3667 0.0538 - 0.07C4 0.0737 3,,***** 0.2400 0.7000 C.3421 0.3565 1.0417 4 0.3250 1.5000 0.1136 C.C976. 0.2636 0.2353 5 0.8571 3.1183 0.3167 C.1676 0.4154 C.1583 6.1000.-35 4.78649- q 4.2857 — 0.4773 2.1000 7 ******************* 0.3556 C.3939 0.359.3 C.3556 8 3.7143 13.1818 3.*?000 1.9-cJ1 2.6154 8.3636 9 3.7'778 9.0385 15.8621 3.3636 7.5000 21.1321 10 2.5000 20.3846 1.9231 1.G231 38.5714 2C.0000 11 0.1526 0.6636 0.2294***************************** T 2........ ~ ~ * 3 ***. 2 2...6..25 C * — * * W* * *, -, 1 * ***4, 4 13 0.01.39 0.4235. 0586.********** * 4 *** ************* 15 0.1692 0.5000 0.0682 ****************************** 16 - - 0.0393 0. 2195* * ^4* T4 ** ***,* **************** 17 0.1250 0.4583 0.0682 0.2065 0.0153 0.1060 1...8.....000- 0.72 T3 C.467 C6-C(34)~ ~*~****~** 0o.0875 19 1.3437 1.6098 1.0556 ***8***** 0.5071 0. 0444 20 0.1786 0. 30]56. ~1273 C 0.130 8 0. 053 8 C.108 3 21 ****** ** 4 ********** 0.0909 C.1437 0. 1172********** — 22 * **** —* ~ * ( * *4 *** * - 0. 1933 - 0.1548 O. C6 C* ********* 23 * ***** **** *** * *4* 0.1343****e***** 0.2041 0.1714........ 4......** *** *******..., 03267.1...277 C.3125 C. 1442 25 0*********<***** 4*** 0.3913 C.1882 0.4778**********.26 - - - 0.61 5 *********.2.~ 8 1 C3 C. 2 500 o0.5658 0.c 5O6 000 27 ***** 4 * ** ****'** *******4 1.2222 C.8250 C.2750 A. 0009*****0**** 0.1167 0.C722 0.6294 C.0659 B: 0. 0842 0. C10) C. C3CC C. 3289 0.0643 0.0357 C. o0,298 0.4286 1-. 0583 C C381***, ***, ~ **.; 30. 0 - 3. 0441 0.0296 C.1000 0.0687 (0.0541 C.0778 E q/Q^5'^4+^V^^^.^^^^^^^^^^~ n3C.1600 f.?130 F 0.0274********** 0. 0256*** *****4* 0.0355 C.C35C G 0.C82? 0.0632 0.0192 C.1C67********** 0.0562 H 0.2765 0.0200 0.0233 0.02P4 0. C312********** I ^^^^^^:<<^^^^^^^^~*^^^ -9994849 ~ C.017 J 0.0403 0,1379************* **** ***. 0.08^)***~**&*A K n3 2..C392.*...4*- -* -.48C C.C C.04 5 0. 0.-73"7 L 0.06O7 0.0933 0.0347********** 0.2278 0.1000 M 0.0138**'******* O. C344********** 0.2636 0.0198 0........ 533- - 0.1.333,. CC762 0.2,549 C.0941. C.1385 P - 0.066C 0.0800.0432 0.3COC C.1353 C.0821 0 0.2657 0.0446 0.0478 0.2286********** C. 1437 R 0.1444********** 0.0864********** 0.1471********** T 0.0655 0.1571 0.0850 0.0325********************.U 0.0486 0.1200 0.075C C.0227 0.1172********** V n.1500 0.0817 0.0930 C.C750 0.0926 0.0 800 W 0.0444 0.0506 0.06CS9********* GC.09C9 0.C75C SHI*P ** * *-** ^ * -; ** —* * *. - * * 0. 131* ****** —*-** *-***4 ***

-265RATIOS Cu/S.P. 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JLL~ 9 AUG. 8 AUG. 29 1 0, C635 0.1706 0.3248 C.4688 0.0707 0.1689 2 0.3704 0.0505 o.3198 0.2344 C.1180 0. 1522 3 ***.****** 0.1832 0.8203 0.4676 0.5541 1.497C 4 0.7222 1.4685 0.1953 C.1500 0,3816 0.2759 5 0.8571 1.7160 0.2CC5 C.C939 0.3462 C,0785 6 1.5493 3.6816 4.7120 1,9200 0.8203 1.8026 7 3C*****,* **** **** 0.2892 C.1347 0.5079 0.3678 8 8.'3.-'- 8-371- 8.0556 2.571t4 2.COCO 3.7363 7.54Y6 9 8.1928 4.0870 6.8657 5.0000 9.8361 1C.2752 10 5.7692 4.8624 0.7576********** 27.0000 11.4583 11 0.3816 0.4771.1711 7ll' * ******* -****************....12..........**~******* ~.11i-3 *0. 216 q**** ** ****** * *************-**-** 1? 0.0650 0,3850 *.0667* **4*********** ********~***~* 1!4 *********4 ^^^^******* *************** * *** 4 * ********** *** ****** 15 0,4783 0.1765 0*1500**** ********* ***** ************ 16. 1375 0.1169.***** ****4 ***4***** ******~******* 17 0.2273 0.2018 O.1282 ___0 38********4********* 18 0.2755 0.2791 C. 2991 C. 2 5 ******************** 19 0.7818 0.6735. 59?9***** **** 0. 154 3********.20.. - 0. —- b... — -2 2.- 15 91 o0.1349 0.0565********* 21 ****************** ** 0.1299 C.156P 0.1875*******4** 22 *** ****** ***4 ** 0.2788 C.1182 0.1347 **4******* 23 ~*****4***********,. ),1424.********* 0.2564 C.2105'24- "` - ^***^*4t***9 c~O-;i`bi; ~ - 38:Ij * C.18i5 C.2632 0.0926 25 (**+0 0..2 224 0.20***** ***-****.26 0...T-b**'*4**',.4219 0.'2857 0.75443 0.5111 27 0ti******** 4*** *4***4****4 4*. 0.67?35 C. 3929 C.318e A 0.0784**********, 04468T C.1831 0.0725 0.2710 R 0.2832 C.Oe82. C595 C.2%3P C.113tC 0.0701..C 0-.1"i228-...2182 - -33 C.C4 — ****.** 0- - -. 863 D0 0, 1.200 n.0272 C 1368 0.1833 -.0823 O).1117 E. -. 0.2 7? 8**4 * ** -: * * *. O 01029 F 0.1311 4:4*** r).045,********4* 0.0595 0.0642.0G 0.2 761. C0.06-63 o.C4CI C. 1053.**^******* 0.1259 H 0.9400 0.0136 ).C328 0.C2?44 C. C54 S**********..i.. * * * * * * * * * * " * —* *' * * s ~ < I 9 I ^ 8 8 I ^ I 4 4 *' ~*-;* *' *4 * 0* 21* *.........,- 25 1 J 0.1506 **0.055** ************* ****3 0.1145********* K 0.1209**4***** *. l 0 ***^^ 4*cl**^^T^*O C23 r T -T.1C4 L 0. 1273 0 o0611 o.0367~********* C.3644 0.1101 M - 3.0 (-576, ******** 3. C33c( ^********** C.3412 r00456 N 0.0986 0.0652 0o,1232 C.C756 0.2143 C. 0.0956..O -".963 C7 f( 7-0 "C.060 8 0.1204 0.0920 0.1011 P 0.2340 ):. 2 2 7 O. 55c9 C.35?2 0.1299 0.175 0.-................... 04769 - l —.) 270. 146 8* 4******* C. C979 R 0.3636********** C788e*********. i192.3***4****** — T- — i:c0. 2065 0.1447 0.2099.C38***********4********** IU -- -0.2400 0.1047 0.1983 0.0338 0.2329**********...V -......-,5263- -....02- 025 15 027-...2.~.7 5 0 7 0.127 6.1351 W 0.1527 3.02, 5 C. C64 8C**** ***** 0.1242 C.1135

-266RATIOS Cu/SO2 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JULY 9 AUG. 8 AUG. 29 3 ****,e**** 11.4286 33.8710 9.4203 273.33333********** 5 92.3077 120.8333********** 1.29 17 135.OOCC********** 6 6e******************** 48C. C0*******~** 70. OCO0.********* 7 ** *** 48C.CCOO********** 970.OCOO**********....... i....~' * * *-* -,-*'" -'-,- ~-~-'*-*''' - 377, 77~ *,' - * * 9 ******** **:**************** **** ************************,***** 11 14 5.0000************ 26.*O0************ ******************...T2.. i-*8.. *. 13 ****zc***************** **^i************4*********************** 17 * ************** **4************* 2330**********5.0****).90ql 21 *.************* 65(.0000 ~.CCCC 75.OC.O33*3***** 0(*? 23o!<7C1r <( i 2 17*C**20. 000C 2.* * 7 19 q* i22.O.CO**** *****7 23 *.** 1. 05q7**** c 4* 2j.500C*1*6 7 ** 2 5.)00 1:0.9091 F24 *7.)40,3** *4****** *. l I I ***** ** 6C.OOOC 51C.CCC* ** ***1* * * 25 11.5625^^***** 2.4 2.6**.****4****** 26.66 7********** 11.25a00 26 7.C07 5 *z^4* 33.7 50C - 2I5. 83.3 7.8777t********* 27 35.74 * *4 * }. ~4**4* * *,*************** **** *.67.********* A..........0' *'****** * 6 *3-**..,..O..16..25C00 33.3333 72.500 0B _ 22.k 571 17C."CCO 2.5556 7.1429 90. 0000_ __ 5.7692 C ]..592 7.3n3R3.14.*OO 24.ClCCC4*'******* ** UCOOC 0 _ 6.12 1.0597 2.1667 3.6667 15.3846 19.0909 F 17.0 OO,***4 **4**11**** 9.40 *]. 12.2222 4. 11 76. 11.5-25 2,6667******s - 26..6667**' ****.11.2500o H 17.4074 3.2553 2.4839 2.3333 2.8571** **********.C 1. j 35.7143 120.018*********.*********** 31.6667********** K**?.5000************************''2*0000**' * * L 10.0000 69.3333 2.2 759*' ***** 30.3704********** S M 8.o 00********** 10.3333********** 3e.6667 2.7812 N 14J0.000****s****** 10.4000 5.4167 82.5C00 3.3333 o 32').OCOO********** 8. 0300 - 32^5000 "53.3 33'3 9.o0000 P 330.0000******************** 1 C.CC C 11.0eCC C 46.0(00 o 3 3.75l00 3.6250 2.1569 - 22.7 1I********** 5.2273 R 30.5fe?*~***~*~*** 3.7255********** 125.0000**********'T 1T.)000 l1f.lO00 14. 1667 2.1667******************** W 50.0000 4.5556 1C.7692******^*** 9.0909 1C.5CCC SHIP **** ****** * 4 * * * **;ir *** * *** ** * ^*^< **** * * * *** * * * * * * * ** 4 *4* * r** * > *

-267RATIOS S.P./Cd X 0.01 1968 STATICN NAY 21/22 JUNE 6 JUNE 2C JULY 9 AUG. 8 AUG. 29 1 23.9583 34C.C000 39.000C 26.6667********** 123.3333 2 62.3077********** 202.3529 26.6667 123.8461 36.800C 3 ****************************** 26.7308********** 57.5E62 4 43.4483******************** 108.0000 138.1818 181.2500 5 _ 35.8974 169.0000 278.C000 1.2000********** 345.7141 6 109.2308 251.2500 ~238. 7500 104.1667 213.3333 179.2308 7 ****+*******4*.'**o* 415.COCC 33.2758 159.1667 174.0000 8 41. 33334********* 420.0000 PC.7692 113.7500*******t** 9. 30.7407 164.2857 111.6667 77.8947 ********* ********* 10 48. 750C********** 660. 0000****************************** 11 63.3333 39.2308 38. 0000 4*4*********************** 12' t18.2857 16. *T273********************** **************** 13 40.3000 62.3333 ***4*********4***4*** **************** 14 **4***. * *I ********* ****-***s4****444*********** 44**** 15 30. 6667, -****** ** ****************** ** *** ****** **** *$* 16 114.2857 171.11 1 ****************** 44***** ** *4***** 17 55. *000*****4**********t*$*4******4+****4*4**4***4****,** 18..*.,-**** 50.5e2.********* 4*23C84******************* 19 61.1111 t*******t*****4*4+**********a***4* —*44***4**4***** 20 6 0 600.C 16C — On0 11.2821 6C.0000 124,0000********** 21 ******** * * ****** 25. 6667 1?.22224**(*****4******$*** 22 *********4********** 35. 8621 5* OOCO******** ***4****** 23 *****44**4****4**4 **** 27.7586 7,/47q*****<4$$ ***&'** * ** 24 **** **** ** * * *- ****** 45.71. 23.75CC 81foO0 0O 2 **4*****4*4***4ta**** 26. 1204*****: *44*t**4*********4*** 26 136.00 nO***4**4**q* *^**4 9C.0OOOO 56.428H****4 **** 27 4***,4** *** * ****4******* 44***44**** 84.0000 4C.5 P2 A t***c**4t*** ** ** * 70~ 5000 33.8095 125.455 36.8965 R 3 5 36.4516 8.**** 87.50C0 85.35t 7 62.9412 C 40.7 1t4? 91.6667 11Ti,3846 **** ** 57*.3913********C D *3*******4c 130. 5Q7 443** - * $* 27 4 2727***t4***+* *4,i(0IIC E 25. 712043 **: $ t 4 X;* 4 - ~3.t33 33 3._. 2 2 e.6667 F 72.85 71 2 6. 00 14. 33 3 *4* * 168. 181.8 4 3. C C C C G 28.51C )?2T.11 1******** 108.5714**** ***** 95.3333 H ** 7. 50C) IC 7. 050C0 7C.oC!OCC 53. 1429 j 2 1. d842 1 *4***:44'; 3', 4545****c4**** 207, 50i)0 4****** K 7...' Li - *4 * * 3f 6.2500. 333 1 2 2.85 7. 121. 8182 L 565.2500 152.66674**t***4*****44**4 125.002 O 80.7407 hM ~t 36.57789 2T6.6:67 2C 3.3333**4* ***** 100. 0o000*****4** N 101*.42 86 14. 75r01) 131.8750C 95.5555 11C.OC0** ****C**..... - 72. 222 115.OC....~_O.n000 72.6667* 4* ****-'.**^ 391.6665 R 59.583345****4t~*3* 344. 28 56*'******** 1001 0 ** I***** T -- 70.7692 126.6667 9. (007***o***4****************-****** J 8 3`.333334**** 121.n ******* 12* 76.8421,4*******:4 V 25.3333 265.7141 52.7778 166.6667 72.5926 42 28 57 W 37.4286 172. 2 22 2 i8S.CCC* ***444***c * 4***4 ***4 ** SHIP * t 3i * 4* * t * * *4 * * * * * 4 * * * 4 4 ^** * fl 4 *4 4 *' 4

-268RPATIOS S.P./Pb X 0.01 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JULY 9 AUG. 8 AUG, 29 1 0.6053 2.1250 1.C636 3.2000 1.5231 1.3455 2 0.2331 1.2111 -.iT467. 0.4000 -0.5963 0.4842 3 ~******* 1.3100 0.8533 C.7316 0.6435 0.6958 4 0.4500 1.0214 0.5818 C.6506 0.6909 0.8529 5 1.0000 1.8172 1.5444 1.7838 1.2000 2.0167 6 0 —-71 2.1848 1.0324 2.2321 0.5818 1. 1650 7 ****4.**,********* 1.2296 2.9242 0.70?4 C.9667 8 0.4429.63- — 64 1.1667 C.9545~ 0.700 1.1091 9,.4611 2.2115 2.3103 C.6727 0.7625 2.0566 10 0.4333 4.1923 2.53 85 * 4***** 1.4286 1.7455 11 0.4000 1.3909 1. **** * **************. [2 0.'3282..2.-6324............'CT~ r,-, -, 13 0.2143 1.1000 0.8793,************4***************** 15 0.3538 2.8333 0.4545************************4** 16 0'.2857 1 78****** ************ * ******************** 17 0.5500 2.2708 0.5318 1.5435******************** 18......42. - i-6?' -.- -2- - 1. 91313 70 17C** ***C**-'*- *q1 1.7187 2.3902 1.q444********** 3.2P57********** 2....... P- i.6.33'33.8',0060.0.962 n.0,9538**,******** 21 *********.**4***4** C0.7000 C.9167 0.6250********** 22 ********4*********** 0.6933 1.3C95. 40040*********c 23 *********2*4******* C0 q'29 1.9286 (.7959 0 8143 24 * - *******^*4** ** 4C4 --. C. 1.1 8 1. 5 5 7 25....-** ************** ** * 1 76*9*** 4****** - 2, 38.9****-..''*' 26 0.531 4***-***.-6667 0.87-0 1.(395. 9783 27 **.: a;**(t* 4 4 ** *. o.I ( * **i * 1.814 2. 1 r CC C.d625 A 0.1257 1.2429 0.2611 0.3944 C.4059 0.2432 R 0.297-4 1.CC95 C, 5C43 1.3816 0.569C C.5095 C 0.2426 1.-9643 2..6 2C~ C C.7778 - 0.. 5' C.4 C088 D 0.3676 1.0875 C. 730)8 0.3750 C.6568 0.6963 E n, 3 64 * * * **4 * 4 * * ** ***** * * * 2.0333 2.C 6 9 6 F o2.4 0.910. 281 9 8 * ** C* 5 6 C. 5450 - --.2978 0.952 C.4778 1.C133e*****7**** 0.4469 H.2941 14667.7 12 1 1.1622 r.5687 0.4227 J 0.2677 2.3563 j. P792*****2****. 7217********* K 0.3020' 1.463 1.225C 2.06CC 0.687C.C.7C53 L -,. 5',455 1.5267 0:.9474 1.9545 0.6250 0.9083 10 n.239 0.8 1C167167 2.5789 0.7727 C.4333 N 0.3021 0.9583 0.6206 1.4C98 C.7000 C.6d8C n0'.2'717 1.7-AR3.?524 2-.' 1176 i -.235 1.3692 P 0.2820 1.2 2750 C.773C C.85C0 1.04 12 C.7643 0 0.5571 2.4769." 7- 1. 571 ***'' -1..46 -87 R 0.3972********** 1.095C55 3.54F4 0.7647**4******* T )0.3172 1.0857 0.4050 C. e375***** ******4******* Ii 0.2027 1.1467 0.3781 0.6727 0,5034********** V..'). 28 50' 1. 5 50-0 0.. Z 441-9..0...0 - 6....0. 7259. -0.'-5921 W 0.2911 1.9136 C.S3c1,********* 0.7318 C.66C7 SHIP *****' 3 i*a<** *

-269RATIOS S.P./Cu X 0.01 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JULV 9 AUG. 8 AUG. 29 1 15.7534 5,8621 3.C789 2.1333 14.1429 5.9200 2 2.7000 19.8182 3.1273 4.2667 8.4737 6.5714 3 ********** 5.483 1.219C 2.1385 1.8049 C.668C 4 1. 3846 0.6810 5.1200 6,6667 2.6207 3.6250 5 1.1667 0.5828 4.8772 10.6452 2.8889 12.7368 6 0.6455 0.2716 0.2122 C.5208 1.2190 0.5548 7 *,*********,*******_ 3.45E3 7.4231 1.9691 2.7187 8 0O1192 0 1241 0,3889 C.50C0 0.2676 C.1326 9 0.1221 0.2447 0.1457 C.2000 0.1017 0.0973 10 0.1733 a02057 1 3200********** 0.0370 0.0873 11 2.6207 2.0959 5.8462************** ************** 1- -- ******** — 6.8 46 4.6111 ********T******************* 13 15.3846 2.5972 1 5.* OO ********* ******* ************ 14 ************************************ ************************ 15 2.0909 5.6667 6. b66 7 **************************** 16 7.2727 8.5556**********4****************************** 17 4.4000 4.9545 7.8000 7.4737********************...18- 3.629 6.. 58E-33 3. 343 4. oo0(O*****4*** **********19 1.2791 1.4848 1. 8421********* 6.4789********** 20 5.2000 4.3636 6.2857 7.4118 17.7143 ********* 21 ***0****t4**** ** *** 7.700C 6.37(8 5.3333********** 22 ***** ****** 3. 5862 8.4615 7.4242********* 23 ******2**** *3*3** 7,0213****4***** 3.9030 4.7500 24 *. *** * ~**, *******~**,*** 5.33'3 3. 8CCC 1.. 8000 25 ******************** 4.5()00***"**** 5.0s000****t**** 26 8.5f0*O****1***t* 2.3714 3.50CO 1.8372 1.9565 27 ******444 ************ * ******( 1.4848 2.5455 3. 1364 A 12. 7536********* 2.238 1 5.4615 i3.800 3~.0897 B 3. 5312 12. 476 16. 116 4,_?2 0 8. 8 51 9 14.2667 C..129 - 4.-033 1..7143?c.4i67** ***~- 11.58 33 D. 3333 36.76!6 7.3077 5.4545 12.1500 E.9524 E -3.,9;3"-*** *****- 5.&4';1 i. i't F o.'.00 *********?(2.6097 * 4***4 ** h 16. 12 15. 5714, 13.6216 15.0R833 24.9275 S.500C0********* 7.9444 H 1.0638 73.3333 3a.5195 40.9524 1 8.2C0********** I' 1<({.? ^ t$Xt ** * * ^* ^ r l~ * E 3 9 4 **' 8 ^ *** * &.2273,J 6.6400 17. 833******************* f. 7368 ~ ******** K 7. 700**:********s**4*** 4.2c17 15.ECfCC.5714 L 7.82-261 16.3571 27.2727*****4***** 2.7439 9.0833 M 1 7.3750r4***4**l** 2q.5161 ******* 2.9310 21.9101 N 1'.1429 1 5.3333.3.1154 i3.23C8 4.6667 1-.4615.0 5.70^937 ~ 12.8125 16.4375 8.3077 10.875C 9.88-; P 4.2727 15, 9375 17.875C 2.8333 7,6957__ 9.3C43. — 0..-. 2.0 (968 5 15.5 172 37.0909 6.8125******** C.2174 R?.7500i********** 12.6842********** 5.20c0********** - -T 4.8421 6.9091 4.7647 25.7692*******-*********** ~I - 4.1 667 9,-5556 5,04] 7 29 9.6000 4.2941** *4*****.V 1. - 00 0 1 Q8.-9796 4.7500 13.3333 7.8400 7.4 000 W 6. 5 00 3 7. B04 9 1 5.5 4 327 * * * * ***** 8.0500 __. C9 5 "<SHI fP H * 8 - ** * * * ** **$ * +* * + * * *** ^"^ *- 3J( -* ^^^ ^ ^ 3f^*b ^ ^-*-^ **,>-,t* -*,0*,K-,,*,

-270RATIOS S.P./S0 X 0.01 1968 STATICN MAY 21/22 JUNE 6 JUNE 2C JLLY 9 AUG. 8 AUG. 29 I C7.6923 70.4167~********** 13.7500 390.COCC********** 6 <<* **************************************** 10* l. ll* ********** 7 ****4************* * C.OOC********** ******** 191C.0000********** -- **************************** 4******** s j1*1. 1111********** 9 380.* 000********** 2. 0000ii**4*** **4*********** 4*****4******** 10 *********************************************************** 11 38 O*.9000********** 152.00(0**** *********** *************** 1 **************** * ***** ***** ***** * * ******i**************** ***** 13 ****4 ******************************************************** — 14 -— *****'' **** **********4* ****~**44*4*** ****************** 17 ************** ******** ************************************** ******4*******************************4444*****4**************** 22 ** +***{************* * 1040.0000****** r163.3333*********** 2........ - -0******. 0 1 57.5CC 7.7778*******4* 6 AN i1.7333 348.0nl0 141.nn o 0 60.7500 46C.0000 267.5000 22 *8** 714 3 2 12 C 0 -. 4 GOc 3 3C.C000 796. 665 82.3177 23C. 3 t' - i2.-3529 — 50.;00 9 7.COOC. C 7000 33 231 82 o 56.8182 38.9552 15. 333 2C.oOC o 186.9231 170o9091 G 41.8.750 4n.72222,********* 253,3333********** 89.3750 H 1R.5185 18.7234 J975.8064 95.5555 52.CCCC 62C.00a0 2i, ~*44**4**** **:c******- ******* $***4 *4.OCCC ****** *********** J 237. 1429 2050.C00I 31.n00o00 ****^ ***** 276.66654**4**4**4*4 a..K 1. 72500333 T5, 833-3 1i-.nOCna 85.87f333 46c.8333,) 27*******-o t L 7Fi. 2609 152.6667 62.0690 43C.OCO 83. 3333***23******* - - 139:.0000,********** 305.COC' 98C.CCCO 113.3333 6C.9375 N 142..COO..********* 84.4.000. 71.6667 _385.0000 34. 8718 n0 15 63 00f' i'. 3Z ** 52 * ** 31.50033 2 70.0C0 58C.6;2 89.000009 P 140..0C 0 * *********4 ****** 51C.CCCC 885. COCC 428. 0C0 ci R __ 84. 176n***22***** 47.2549 275.CCCO 650.00*******83*** - " 920.0000 76C. 300 67.5000. 55.8333 47.142 ********** J 237 142.54***5****(4* **7***nO*i***4**4** *4* 27665** 4*** 4*4*4*4 K',4 1' ";~ -, 3;-, ~, ** **,.* **4 **,* ** ******,***,{t**4** ~ **,**, W 327.5000 172.6222 16.153 43.O******O 73.31818 3 92.*5C SH P ***** 1 * **** ****** *** i *. * * *. * * * * * 3 *375 N 142.!*111 - 32.3529 ** H4,400 71,6C67 383C.000 24,, 876 n 5 6. 8 1 2 3' 9 t --- 2 *- *-*i 3 3 3 2 ~- C. C - 0 0 —! 5I 8 6. 2 3 I,C)M1909 41.875f0 4,rl 2220 8k- i 153.37143****$**** 8.4CS71 -T7 2609 52 666 7 9. 0 n 76 $. 9 7 0 5; 3 3 4 7. 83 47 5 *** 9 * a I t 0 327 *e- 500n 201.2500 8 II 0 155. 7143153* 719 4 C5CG W 327.5000 17 2. 2 2 2 2 1 6 6.. 5 3 E..8 le...n... SHIP ****ts**********r*****+**+*********

-271 RATIOS S02/Cd 1968 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUC. 8 AUG. 29 1 **~4**4****** *************************************~~**~***** 2 ******************************************************* *** 3 ***************** ^****4******* 1.3269**4***********3**3** 4 t*************************************+****************** 5 O.3333 2.4000********** C.9600******************** 7 ****************.** n0.250C********** 0.0833********** 28-~* * *******M********~* **.**7*9*^* *3*1.1250********** 9 ******$**~****+**************t ******4*s** *********4****** 11. 0.16.o7******** 2.5000*-*********.*******4-********.- - - ^ _..- _ ^ - ^ - - — 3 _'...............3.. 4 o* *,, * * * * * **',,'.. * *. -.* 4.......- * -' t 2-,-* * *-** **.. 13 ^^48 <t****4**4**^***4*+*********4** **4******4**************4 15 t ^****************** ***.348***********42727 *4*4**4*4*S**t7.16 **.** r~ **2 3'**,* *********17** **.*** *4*4 * *** ***4 17 ***8(****-****4 *********4**4***4*4***4i4*44*4*4***4* 4*4** 4*** 1 8 * *** **********- - **.* ** ********'-** —-4 -**~***** -**** _.,...._.. ** 19 44**44** 3****. *******4**4t**** 1.,**:4***.****.4******8*** F2.0 -7* 6 3.*** 9fO:.7C********* n.C 21 ***..4446**.44*** * 0*0667 C. C2784*********4***I.**4** 22 **********i********. t,3454 4* i***4*0*** * 4*** **48* 23.**4 2**1***** —**S* 0,1376 C.r357***. *7**0*4****4***44 24.1.i44********44******4* C.1429 C.125C*0*** **** 25 4t*,..2*44,4*****4***+*'.*4*66****4444****** **84**4******4* 26 3 3 2400(t^t***s******* C..714 7.642 94*** t**** 27 * *.4 *..4 * * * *' 4 4$ * * * * * * f * *,* * * * 4 * 4 *' * * *;4 0 * * ** * * * * *2* 44 *1 A *0 I C 8,** *** * ** 4 4 **** * C.n0o C.3*81* C.2727 O. t79 R. 4516 o. 708-3' ******* 2167 2,17*C71 C.71647 C:f.?.8033 )7690241.*****44*4*4** * (;.1739* *4********* D 4* 4 4:.'4^* 3. 35 ^)44 4*4***4*. 3 5 3 0 ^:< ^ ><< I a O. ^ 5.^ D **4**-****************;**** 4**44*******4***4*******4** F ).476, 9(2 3 _9 _. 70sC**44** 4*** n.d 182 a PCCC — G r C.6C9 5.00n *44**4*4t 0**.'42P6*4**4***4* 1.0667 H *44*x<t9i4(<ii<*$ 1*.5500 1.125% 1.3462 C_0!857 I * *****4. **4^**-*********** * **$********** *4.***^***4****4 *** _.*****4* J CJ. 39214 I. **** 6** 6364***4**** *75,0)4**3******* ~K 44 *C0 4*4** 4' 4 1.7 5 5?C l.oCCCt 1 [.7143t444*4*** L 0.7108 1.O0(K,4*4* 4*4**444***++**** le.50,00*****t*** M -.-12t',34*4*4***** l.b666144*4****** c 0.88244**4*4*4** _N V )714*t* ***$* Vl5625 1.33333_ CC2857**444 **** 4 "0 -. C~1~2~*44*4**4 2.n(C)4o04*** ** C.5277 2. 3571 P 0. 2OC^ % 4 *C *4*44t4*t4**** C. C4CC*4*4***** J.l66 7 R 0.70834*4*4***** 7.28574444**44* C.15384****44**4 _-T 3-,.0769 Q,1667 1.3333*^e**4**+*4*4********4***#**<* W 0,1143 1OCOo 1.CE33*6**7***4*44****4**44*444*t* SHIP' 7**** ***4****** * * 0642*9 4 9 9 ****** ii***4*******4 7-7 -- - -— ~ —---- ---------- -- ~ —------- -~ —-------— ~ -— ~ — --------- SH P I 8 a" 5[" ~~ " "6 ~~ Q" ~~ ~~:~~6 4~E O4 O E;4 ~~ 0~$ 3 ~~. "~C I4 a.3810 64 4~s 74

-272RATIOS SO1/Pb 1968 STATION MAY 21/22 JUNE 6 JUNE 2C JULY 9 AUG. 8 AUG. 29 1 ******4**~****** 4***** 4****************4******************** 2 ***************************************************4 **i***** 3 **44**$4 * 0.0210 0.0207 0.0363 O.0013***4****** 4 ********* ********* ****************************************** 5 0.0093 0.0258********** C.12S7 0.0031********** 6 ****************************************************-** 7 *****C*******4****** O.?********** 0. 0004 ********* 8 ****-* —******** 4******** **********r*** 0.0069********* 9 - *****$********4**********************4********************** 10 ********* ****************************************,13.*1*******+************** _.0 ************ *4**************** 15 4*****************4************************4*********** 4***** 14 ************4************** *****4**4***4********************* 15 ************:******$*****4********************************* 19 ******'**********44****4.******** ** ************************ 17 -- 17 ******* *******$** ** **1*****8*C*2*1* *.********** 22 ** ************* (0 7 4 ** ** O. OOO3.****$* 23 ***** ** *** ********* 3.0057 _ 0.0071 0.0082 0.0157 2 — ******************, ********* 0.0021..CC62*t******** 25 ***4*****c****4***********4******4*****4****44*****4********4 26 - *. oil 3L*********** i C83 C.OCC5 0.01168 #****** ** 27 ******44************************* ******4*****4*****4**4***** 27 $*tt*$tt***+******++**+** A 0.0107 0.0036 0.0019 (.0044 C.0009 C.0009 B Bn'.''037 C.0005.('117 C.0461 _ 0.0007 0.0062 C ).'115 0.060 7 0..042 C.CC16 0.0017 C.OOL8 D 0. CC,65 i0.O?79 0.3)4h2.0187 0.0035 C.CC41 F __ i0016 0. 186 r). n028 ***:*****3 0.0029 C.CC85 G O').0071. 237 9l*4't,, ***4 0 O040.********* 0.0050 H )..159 O.C763..CC94 0.0122 C.O109 C.00037 I *4*4+ *4******4*t**4*+***4********+************* J 0.0011 0.0011 0.0(.)29********* 0.0026****4***** K \)'C17.012 C.C07 CC. C24 0.3104 * 4***4***' L:.). 0070 0.0100 0.(0153 C.0C45 0.0075:***:***** M'). )fl)2 -**44**** 0~.C033 C.CC26 0.0068 0.0071 N O. ^^02*********3 0.0074 0.C17 0.0018 C.0195 0'). 0 i.)2*44 **** (.0095 C.0078 -.00i 18 0C.01 54 P'..o,2** ***84*** ******** C.CC 17 0. c001 2 O. CI R'0..0O),n9 0 CO.0123 1.C222 C'.ClOO.***4**** C0.275 R:., C047,***4*t**** 0.0232 C.C129 0.(00 12***4****** T 0.0003 0.0014 0.0060 0.0150***************** 4*44*4*********4** ******************************************* _., **** **4~** ****** ^-*-*t **** *******************~*** *** ~*4~****~ W 0(.009 0.0111 C.C0J57********* 0.0100 0.0071 ShIP ** 444*44 44 t *** *4******* * * * *$*4 * * ** * **4** ** **

-273RATIOS S02/Cu 1968 STATICN MAY 21/22 JUNE 6 JUNE 2C JULV 9 AUG. 8 AUG. 29 1 *************************** ******* *'*'2 **** * 0 *'**** <****** 2 *********************************7************************* 3 ********** 0,875 0.0295 C.1062 0.0037********** 4 ************************************************************ 5s 0.0108 0Q083********** C.7742 0.0074********** 6 ************************* ********** *********************** 7 **** ******** *l********** 00.0o 0********** 83 *******-****** —****-****** ***v.*** **,********** n..********* 10 ********^* *****4***+************4***********+*********** 11 0 * 00604********c, 0.038 5****4***********+************* 14 *'**-**** *"*-*******'*********4** * ******0**********-*-154 *********^********^**********^*********-***-***-*- ******* _. 16..-, *********......... *... 17 **^****t********g***t********** ********* i8 4**+4t*44 *****************++********+********$a************* 19 ****t*4**4*******t 0)._C026***t***44************4********** 21 ******************** Cf.200 0.0145 0.Cl33*s******~* ^ r"22 *** 10 a I **4*X**X* *** *nr~~' 3. * 7.'-,*' * * ~ *,, 23 1 i. 4 2 6 ******* 040400.0,917 24 0.01**67 0 *fCC***4****1Qol C2CC********* BR ).:37. n".0 59 C,3913.1. CI O. 4ll 0.1733 C.3 -B5 7.1T417 -0.714 C.C417f******* ^0.500 D0. 14t7 4 7 ). 437.h15 C.2727 0 ) ^5C C.0 24 F I;). n5FI8***4*****, Q1 298-****4**** 0.0 18 C.(429'' a). C 6h5 n 3 75 * * ** * C.0375********** 0. 88 H *', -)574 3.9167 ).4 0?6 G 42F6 e C. 35C30***4**** I ** 1 2 H jO 3 n4' 4;$***t*******t44*** 4 * *** 316*4******4 J J).28( 0.r P**4*s*@*t*t**** fl.C) 316qp4*** K i".4'n.^4**4**4******4*** C.C5CC C. 24C'********* L O. 00.. 107 1 0. 4 94 ******** (. O 32944******** M;. 012 5********. O 6 9****'**** ). ^59 3 359-6 N ). 071 **** * * *.. 96 2 _.1846 0.0121 C 3C3C - 0 ).i ~ 3- ***4****** i0.1250 0.03C8 0.C187 0.1111 P,).V 030****;** **********__* C.CC56 ). C07 ).0(2 17 0'. ).i?12'^').275 59 1.4636 C.C437****4***** C.l913 R 0. 032 74********* * 02684*****4****'". 0'980 ******** T *t;j.00 53. 0 091 0.0706 0.4615***7l************** U *** *4e*4*2*** 4 **** *2** * *j*****4****4***4* *9* 2* C*** 4O W _ 0^3703 0.2195.__.92q44**4*4;* O.110r C.0952 SHI.1P **- * * * * * 4 4

RPATIOS S02/S.P. 1968 STATION * MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUG. 8 AUG. 29 1 *-*4*************************************44********************* b 0.0093 0.0142********** 0.0727 0.0026********** 7 **00************* 006*********_l * C.0005*********** 9 ************************************************************ 115 *-***02*********** **** 0.*******************#* ************* 11 026********** 0 6********************066******* ****** **** -T2 * i* 3*** ** ** *i~^**** * * *. C2 *.-*iF*0 14 *****'******************0. q,**W******* O.O***** ****^*i <* 23 ** ****'r l**** * *:******** * C.C*6 1 C.CC3? 0 *0103 0*19*3 1874 4 0. 4-,';-'~e*- *:* —*-**-,'*-*',~-** C4C1 *.C* 0,*',)053****** ******** a 21 5 4 ****444 4442********** 2. r006 C.CC23 0.0025 0?114* 27 ********4**********^4**4^** f* O******************1************ A23 A{. C852; 002- 0.006 C.CC113 0.0022 0.0103 24? ~*******************(** o. O**** C.C31 0,00Q536******** 2~ 0.C ^^<r^^^2 0 *** **,. C C C63 3.1 6 1 0 0 5 3 * *4 c4 BA.12:.004.C5 C. C207 0.0133 C.C3 022,0037 _ B -,0124'.CCC5 C.C233 C.O333.13 i _0. 0121..C.047-,C4 7-' 0. 309.006. 67 C0. 0020 0.0030 C.i-C43 D COC176 0.0?57 O. n36 2 C.0500 0.0053 0.0059 F.0065.018 O,. r )53********.0049OC 0.0c156 G - 0.'239 0. D2q4g****2***** C.OC39********** 0.0112 H.05.40 0.0534 o. 13?2 C.CICS 0.0 C192 0.P0016 J 0t.,042 0. 00,5 0..0027********** 0.0036********** K.1 51''.oC86.C7? C.0117 C. 0 1 52******* L (~. C128 2' 0.r066 0.(0161 0.0023..0120***'***f** M r).0"7,********* C..CC33 C.C010 O.CC88 0.0164 N -)n.C007***4*** ** n.0118 C.0140 0.0026 0.0287 On O... 0'6'****:**,'* 0- 076 C.C037 0.0017 0.0I? P O. 07 ************** **** C C.CC2C 0.0011 0.0023...... 0.0 -123.- 0.C5-. 0.0125 O oC.0o 4******^* ~ 0. 0187,R O.,01 3********* 0.0212 C.CC36 0.0015, ********* T 0.0011 0.0013 0.0148 0.C17I C. 0212.*.******** J ***************************************34********************* W 0.0031 0.0058 Qo. 6C,********* 0.0137 C~.1C8...S-~V- H - PI-**-.** ***~-,'/P,-.' —,,~;*,' / 7,:; **,i44 4* **,,,,,* *,,-,- * *,*** *****

-275

-276IV.2.2 Fortran Program for Computing Ratios and Histograms

-277$SI(;NN SN87 1=1M P=100 $RIUN *FnRTRAN DIMENS'OIN OAT(h,50t,5),l)M(6,50,20)I DAT(65,50,5),D(300,5) ___ DIMENSION R(300,_2?), X(10) __tSTIJT. (2,20).RLO_20) ____ DIMENSION FREQ(20),PCT(20),STATS(5),REAL(300),UIRO(3), S(300) READ( 5,100) ( ( (DAT( I,JK ),I=1,6 ),,1=1,50 ),K=1, ) 100 FORMAT(6FIO.O) rn002 K=1 _ _ ____ __ _ ___ _._ ____ SIJM=O. Dn o10 =1h,................ - i- —.- DO 10 J=1,50 S IIM=StIM +!)AT( I, J,K) IF()AT(II,J,K) )85,11,85 11 AT.(I,, K)= 0.000000) 1...... P5 IF(K-4) I), h 86)1 A. I)AT ( I, I", K ) 10 K_.. I.... T....-... 10( I AT ( I, t,K ) = )AT( ( I, J K ) A? rOCNT INIJE n1nl? K=1,5..R.Tf..(,. ] o. 1..) T F ( 6!............. o - -- ---- ------—.-. —.WRITF(,l 101 ) 101 FnKRAT( //40)H1 EI FMET: 1968 _ N( -M-3 ) 102 FORMAT ( /7H STA' I{IN vMAY 21/22 JUllE 6 JUINF 2() JUl.Y 1.9 All, P AHI(;. 29 /) 103 F)R iATT ( 16,?X,h 1I)) 12 WRITE( 6,103) (, ( I.AT( I,,,K),I=1,6l,),J=1,50) j = 1 L i) 14 Il, 6 f) 134 1=1,50 9 n 13 K 1I ___________ _ _______________ 1' i)(,f11,K) =!AT( I,,K) 14 j I n+. r )' [', - - 1 CAL. RAT I 1( I), R,NN ) tn 17 K= 1,?2 I0) 1 I =1, 50 I I L..=J I t IF 1 5,j'=1],') li ( I ( tfi, I,) I Ll..,K ) 1 1 I L = II IL +50 1 6 J I I, __ ________ t WR I T F 6, 1 04) W4R I1 F- ), 1? ) 104 FfF rvAT (//41 HI RAT IS / 1968 WR I T E( 6, 1] 5 ) ( I, ( l)I( I n, I, K K,lI, =, 6 ), I = l t O)... 105 FFRiMAT ( I,3X, 6 Fi0.4) 1.7 C fTl N T It Il:.__ HAt=0n Dn 44 J-=1,20 I)n 44 1=1,? 44 S lllT(.i.., j I. 4h COlNT I t) FNU _ RITE (6,312) ____ _ 3 2 FfRMIAT ( HI )... 41 J -l.0.............. KnT=l In 40. =,3.0..... I F (HAH)71,72, 71

-27871 IF(R(IJ)-STUJT(1,J) )40,74,74. 74 IF(R(,J)-STIIT(?,,J) )42,42,40 72 _. C._ __cT. NTI!NU F.__ IF(R(IJ)-10000.)42,40,40 4? _?_EiL REAL-__ K T _RI J.LL____ __ KOT=KOT+1 40 S(KnT)=l.. KOT=KOT-1 -P.T=KnT...-.. ___ _ ___. NOVAR=l tlRO(3 )=10. IF(HAB) 65,6665__ __ 65 PnrT=BID(,) 66 1I- MP=5.*(_ALnG(POT)/ 230) +2.. 77 tiRO(?)=TiMP 2.2 __ Fn_ RM T( X 0.2)............................'' IB =tURn(?l OiH 0(2 )=I H()_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ CALL TARI ( REAL., S,1,IJB)R,FRFO,PCT,STATS KOT 1 ).......... _i,2 4 )... E...........................-__.._.... 204 FORMAT(//31H? HISTfOrRAM O)F RATIOS / /) R TE....... (6,?01). WRITE 6, 200) ( STATS( 1 ) I,11,5 C=nr. I)IT=(STATS(5)-STATS(4))/(IRfl-2).. WR ITF ( 6,?07 )DIT' 207 PFnRMAT( 27H ITErKVAL VALIJES= F10,4) WR!TF( A6,?03) I. n=o.rn 43 T=l,TRn I ITF( 6,2?)2),FT F0( I ),PCT( I JF(PCT( I )-6.)61,61,6].2 A? R=k+FRF0C!) tilt(J, I)=h r F i I.. rlM', ) 4 = A3.64 II IT ( 1,I )=STATS(4 )+(-) -?') T 63 L'I=L t+ 1. SlIT (2,J), =S'rATS(4)+( I-.1 )*DIT 61 C=IPCT(I)+C ~~C4? cFlNTIN li F.RITF( 6,?05) ".......... _.......................R..T...T........... 20.5 Ff)RI4AT( 35H TOTAL )?20......6 FORMAT'lOX, T 10 Q5x,.F 1, _.__ 0...X..............-..._....__.. WP.ITF(6,?2?) B 41 C NTI NF I_____ ____ HAR=HAR + 1.... I. F(. HA P-4)_45, 5, 46.......... 46 C fiNTINUlE.20 1..........F. R FA T i( H... _ TL.. __..._MFAN.._ SA..... STA.N DVE _ T.Av........ MnAX 200 FQRMAT ( IX, 5F10,4//)___ 202 F(IRMAT( I7, 3X,F10.0,,5XF10.1) 2?3 FORMAT. /38H INTE VAL.... FREOI)NCY PERCF NT... F NI I)

-279-,, S URRO lJTINE RAT I!O) D, R.tNN) _...... DIMENSION R(300,20), 0(300,5),X(10) C NN= NUMBER nF STATIONS..DETERMINS SIZE, NO OIF ROWS, OF IN C PUT ARRAY DAND nOUTPtJT ARRAY R 33 Dn3n I1=1,300 _ __ DO 30 J=1,20 o30 R(I, 2_J)=7777717 77.7 ___ __ nn 20 I=l,NN nnlo.J=?, 5,J 1= I-I................. I. F(_PJ.I..,l)-0_5 1h_1Q,1.0....._..........___..__ _ 10 R( I, ) =D( I, 1)/D I,J) 11 X(l)=D,(Il) _ X(2)=0n(,3) X(3)=l){, 4) X(4)=D(IT,5) 1)( 1? 1=2 1,4 — 14=) +4 IF(D( I,? -0,5) 13,1 2,1.2 1) 14.=1 9,4 JR =J+R. I'' I +........................_ _.._.................................................. IF(f) 1,3)-0.5) 15,14,14 — -- - 14 R ( I,r, ) =1)( I, 3 /X{ ) _ 1t X(3)= I)( I,3) 1) 1.,1=1,4 ___________,112=11+] IF(n(1,4)-0.5) 1.,16. _ 1 S R ( I, J 1? ) =1)( 1,4 )/X( ) 17 X ( 4 ) )( 1,4) i1)I 18 J1=1,4 IFi( 0(1,5)-0.5) 19,18,18 18H k( I,JI16)=I)( I,5)/X( 1) 19 (f. f lj I i' l If?n (C. (I' T I \l J. FT Fi k $F!I)F I LF

-280IV.2.3 Raw Data Sets —Computer Input (CDC 160-A)

-281im~tIN C\~rn SCAI-FPFAK ARF AA SId I: P"EAK AHF "A IF PFAK ARFA Vn, SPTkF NO. PITF HITE HITE NG 952 -1 1CO 0 0 ICC 19 3 o 100 5 10 0 0 956 -3 200 8 200 34 43 200 30 42 0 100 960 -3 1CC 10 1 ICC 70 7 100 61 03 0 100 hq4 - 1n 20 3 100 11q. 13, 100 134 iO.0 200 961- -3 2CC j1P 23 20 111 127 200 135 173 0 400 972 -3 500 15? 50C 5 If lp 500 117? 154 0 900 q76 -3 1CO 1 16 1000 0 7 IOC 1000 11' 14. 0 1900.0. -;,10C 5 7 1.0 10 14 1005..0. 0,P' -? IOC 1C 6 100 55 63 100 55 93 100 oR(3 I 0 50 14 17 5(00 37 3'q, r,03 20 3 Q 670 0 9?C -?2 1C F ICC. 7' 5 100) 5:3 95 0 100 C;6 0 100 11L 1I 00 C 500 104 136 660 0 1COO 1 10 11 1 50) 37 4l1 500 112 1*8 660 0 1 O04___-_2___1Ce' LC 17!___1C6_10056950 100 t~ l1qO 950' 100 1CC4 0 100 c'00?1EI 2?C 500 156 207 605 0 _1011/, -? Ci. 1', 21 lt, _rIC j i 5.'2 6 0 100 1017 0 2CC 47 5C 3 3 525 0 10 l 1 AL.... 7 L 1 10 12C Li 525... C' 2" -? 5C 1"'1 /-, S,C 1'i " 4i 77 0. 100 12,c, _- _ l...__5 _=.-..L-.. - C': _L.... 0 -1.... S.75 __ Q i n1'7 3 q 1.!,.? 74 1 -1 11 _____ 2 _____ L _____ L _____ L ---— L-2 2 I0 1 0 CC; U 12 ___ 2 __J. _ 0 1' 0 Pl,\ ('rF'; f'[Air F::, CA.Ii C PFtK r,r cF A c F I nFAK APf'A VPI SPIKE HIT[ H I 1F H TF NG 53 - 1 IC' 24 3C 10 1. 1 c, -7? -2-...1_I C,.1:5_ 45 9 C_';1 -2 10 1' - 1~' ct,':( 1. 0 4 85 0 100 c:. 1' -1 v 1' i. 1 I'- ln q7 133 0 2 0 t:'; - " C I!? "' 7. 7.?'11. 5 0 I 400 _2-',ri_.rL- _5 L ['1 1. 5: (. 98U 1539 1 _____C___90. %77 -_ 1CCC 1'7 iC.:.2 10C0 1012 157 C 1900 ~_ ]_ ~:~ ~ 1___1....1')~:'"' l....]Jf_!Z:.' 1 2 1')3 _~__J C 0 I O C 5 - 2 lC' 1 C 1 0:. 1..) 0 55 3 0 100 ( C PC I I' C t 3 500 14?5 595 0' —3 -2 100 0` \r 1" 002 1 0 100 4 1 0 iCo _ -.__I.... 1i. 0..f..f.?.. 60Q5.....- Q. iCrl 1 1 (?:: 02: C ":. 42 10',) 151 202 605 0 J-i'L - 2 ci? 1.7/ ___ *.: 7 97'c, 5.'4 1 43 0 2?00 ICC 0 C -?,.L'0. " 7 7 0.:? 7 106 520 0 1C1 4 -2' =. -2 2 C,1 C ir lCI) 4 76. 0 100 1 C 1,' 3 l'.' 61. n 27 48 545 0 1?2 I 21 p 2_. 2 7 14 =5' 10 64 1164. 4 5 10r2,6 -: )"., I 2i?? 1C, 49 q.2 100 39 70 0 100 K3I ( 3" 0'' ^ 21i r L 134 l^ iC) I- 1 12 570_ _n ~,__.__-,''~ _~__ _. 2d ic/._.~ ~ l' 13 4 1 i I 1 12 5_.a 7Q 103' 4 5? 26 ICr 4' 55 n1o 35 72 C 100 -II1 2 0 r. c o c o

-282RLJN rnnF SCAI F PFAK hFEA SChI F PFAK ARFA SAI F PFAK AREA un! SPIKF NO. HITE HIE HITE NG 954 -1 100 3 IC0?2 25. 100 6 12 0 0 Q.q -2 100 P 19 Ic C PP 100 R1 12. 0 100 <62 -2 100 20 1OC 91 84 100- 5 137 0 100 Ch6 -3 I0nn? 3t4 Inn 16 1 I5 100 1i,-5Xl a 700 970 -3?CO 21 41 20 156 155 200 189 264 0 400.74 -3 50C 19 3 500 132 124 500 f 211 0 900 974 -3 1Co 1 1 IOCO 123 127 1000 160 214 0 1900 QP2 -1 100 C 5 io 0 11 I00 7 17 0 0 P6 -? 100 9 17 100 i5 P7 100 78 97 0 100 IC; Q. 50 10 17 5CJon r 7r Pi n 24 35 6RS o 994 -? 100 5 14 100 73 65 100 73 116 0 100 Scc U (1 10C 17 5CC 3. _ JH_ 0 1 C 64_ 620 _ 100? 1 IC t 19 500 4C 4P ICOC 1R1 228 620 0 1CC6 -2 100 18 100! C 63 100 77 109o 0 100 l010 0 C 1 30 5crr 40 37?n0 52 91 535 0 1015 -2 f 19 2 0 7' b 10(o 70 n 105 n l00n 1r,?3. " Ic.100 171 15F 100 9 160 575 0 1(27 -2 C _ 1 C- PC P. 130 68L 10_ lo a l 1C31 C CO I,) b'50JC:7,? 500 2R 41 67C 0 1 C 3r —. _ __ 5 1.IL._ ( c _17O __.4 __ 010 Q 0 -111 *): C C C C O 0 0 0 -F' I Cr.LF SC \\ Ir f 7.f * i-f <1 C',. L:r Ir p P crAl F PFAK APFA nl S.PIKF NC. HIT- HITTF HIJF NG c.5 -1 1C l riC 21? ()10o 3 11 0 0 5'. -? I__'] 1P J - ( p, - 100 62 2 q7 0 100. - -2 1' 3 17 Il 5 Pc lPq 100U 3 IC; 0 100 _,:: -3 l I'i irC 6. 14C 1o 1317 224 200o 71 3 2 1-3 2 1H ) 2CC 1 7 13 I C 154 215 0 400 c -3 __' r C 1 1' 500 13 173 C O S7:) -3 1COr 17 4 1: 1,4 134 C 1'o 148 216 0 1900 rl'. = -I 1CC ('. 7 1.1 _ J 1. __ 1 00C..10.L. _.'9,q7 -2 1 C!. 3 1' I).42 P? I100 69 123 0 100 co1. c0 I ~ r:~C 5C 1 f'7c 500 10P7 171 700 0 0c'% -2 10 2 I 1? 1.0!() 0 1?P 100 57 q4 o 100.'_...._._ ___ -___....1._. (CC. T L 37_l W3__C L__L.3_ _ l_32..._.. ICO0 1 1CC t 3' ('OC P 41 0OO0 106 1 5 620 0 107 L_ 100 / 1 CC 82 100 6P 124 0 100 1lo.l 0 50:'.' iC:. 10'00 17 33 575 0 1012 1 5.? 4P Icrc r 42 3<; 5CO0 39 67.75 0 1 t 16 -? r0 0 1' 10 65 64 1)0 56 96 0 100 1C24 1 C _ 2_7 I. 7 i 130 124 100 94 165 575 0 iC2" -? 50'43 3 1O C 75 73 1O0 63 104 0 100 1 32 _ -- _.- 4? ^_500 135 122 500 47? 60 Q 1Can 3 5C "^ 1C 6 4 5? 10 O 53 72 0 100

-283-.':N rnriF SCA F PEAK ARFA CrAIF PFAK ARFA rCAI F PFAK ARFA VIm SPIKF Na. HITE HITE HITE NG 1C66 -2 100 4 37 ICO 66 14C 100 78 218 0 100 107'1 -2 100 1 35 100. 2.12 100 R? n750 n l 1C74 -2 IOC 11 51 100 123 253 100 169 493 0 200 107-P -3 200 14 45 20?0 1]1 24t, 2n00 177 4q.H, n400 iCR2 - 2?CC'7 1?200CC lC 55 5o00 149 478 0 900 1ap6 -3 OO... 11 _:4 10C 1iCC 1 2I C icon 14 A A4r?. _0 ] j90 iC90 -1 ICC 0. 1CO L ]c ]1O 5 1R 0 0 4n -2 - C I" 3 nIn1 1C IC 74 21R 0Jfl I9 0 5C 3? 0 12P 26E 530 107 322 670 0 r11 - - 1. ], 9 7 37 Cr. 125 25 00 1 15 350 Ia,n 7 0 1106 -? 50 53 1?q 1C. (4 131 100 77 241 0 100 il_____~_C. 0 50.7 1 5 3____ —....._ 62_5_ 0 111 -? 5. 13 54 lC i 11 0?p 0 1. 0 100:121.. _12. t 1'$4?2 (_:0 A43 1471A_ 555 _ _..125 -1 5'C (0 3 1 c 31 100 3 0 0 _12 -2 2 11,45 ] C 55 lin. i oi 1 162, 3 100.132 50 11'5 2 r 3 1 200 173 575 0 _HR_:. _ ~ s/ _ r- K,"F SC'., Fs F p,. S ^Ai F., (AI F Pi-:AK K AP;FA V/C.I SpIKF PC', ITE T 1[E 14TF NG LC7 -2 100C 1 II:; 73 ]1:0 6 C. +214 0 100 LL___-_..... __ l'C 2 1. In 100.___2_ 7.10 107r:! -3 ICC 1'I2 I."0 1?.'?." 1"\ 100 n 1.8 560 0 200'L7'0I -' ) r, I n Yn?,c0 2(... (' 654 J 40 0n tCti3 -3 50C 13 41 IO1C6 1 ] 500 173 4q1 0 900 1 C 8' -_3_ _'?_5_ 1_ Si7 —_.ILluS I0 1100.2_4 2 - __1 Q__0 -19 C l -1. I-C 1. 1 C'1CC3 l 10 3 S 0 ~Lrc C r-. 5. C? 7Z'-rr c(__. C. 2 100 Ir0, c ~ I7?;. IC?c " 110' 1 ^c 3 7^ r_ 124;? l C1. 605.... 1:5? 1 C I 7 1. q4M,: 1. ft 10,(r 16 461 605 0 11l1 "': 1? 4'; 5,.' i'( "(,t 6.)00 141 398 610 0 iU I.f _- _-,-.._ _ 9_ _____ _____________ __ o!114 1 ".: ('!'H..u.,-, ~ "'. A3 Icr( 6.q 169 6! ) 111l -' C, 1 1.1 5 1(',. C F 100 45 ]71 0 100 112?! 3 9 L,'._ __Z 3__...... 53 _ 1 1 2' -.t L'1C 11!*^-i^jud ^^ i3U *3.iu

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-289-l1 Crnnir-o F SCAI fF PFAK ARFA SCAIF PFK ARFJF grAIF PF4 AK AREA Vft3 SPTK9 NO. HITE H ITE HITE NG 1266 -2 50 30 74 1CO 112 21 100 85 272 0 100 1270 -3 50 54 125 2C0 4 1 9C 00 9A 2?3 C 00Q 1274 -3 5C 51 130 2CC SC 17e 200 89 274 C 200 127 8 C S 0 7FI o 500n__ 5n I100 14 25 71n ) n;1282 50 7 16P 1iCC S5 199 500 102 238 710 0.12P3 -?,50,15,,'l I 1Cc a. 132 100 42 1f Q 100 1287 0 5C 19 56 500 79 15F 200 46 1 6 650 0 i129q -7 5C 14 57 ICO 14 41 1 nO 5 19 1n00 1296 -3 50 15 54 100 fe85 16 1 tO0 68 236 0 100 12 9, 5t 2 n n 6. C6 7 i l 1^4 5s0n) 1 i 4H 6n2 t. 1301 -2 50 1 P 5C 50 h1C 3C6 5C 1C9 394 0 100 13C 50 24 6 4 5C(; 79S 16 20 rLr 685.0 13C9 1 50 21 6e rCO 71 156 1.''.) 130 328 685 0 1315 -2 50 11 55 5C 1;7 3C4 S 0 0 L' 71 C 10'0 1319 0 uC 1.3,?201) 78 156 100 62 240 580 0 1324 -? 5 10 5 147 14 5,; Sn 34 6 0 n1 132.' 0 50 iP h'p 20 1l 31,4 1.() 121 406 650 0 12!312 1.5 1c 4...?ri4 2 200 61 1 95 5_. _o 1336 1 S 1C lC 75 C' 16 C 3C2 200 86 245 650 0 -11 2 0;', C_ C. 0 0 0_ _ 1i 33 -2 5C 11:) 1FC 207 iQ0 96 32 0 100 1 42 n SC 4 4 2 ^ 4-.. 2 C.co 16 43 640 O 1347 -? 50 9 32, T 1 5 5r) 65 25, 0t 100 1351 _i r ): 3tl 2CC' _ 6 132 5)) 00__ 555 Q 13'5. 1 5(:1: r 8 ( C c; 12P (rCO 167 471. 55 0 -11? 0_ C (C ) C (,C 0.__ 0 ) 0 0 RI; cr;F_.sr, S.p r.Ag A sr, F PnAK A: SP l F'PFAK AF^A VIl SPIKF Nh1. 1-1I TTr- PF TF Hl TF NG 7 --... 7. i! 1267 -? IC 17 63 V iC(: 1 1 10 4s 178 0 100 1271 _-? 5.? tI l _?"'' (, 14" _ 2. 0 63 196 0 200 12'? -I 5 1 ]! ( 75 10 r O00 66 194 C 200 ^17~ 3,....5C 47 n ^...1.'('; 165 "p0 127 34,7 f6 0n 2lt -?2 C 11 7 1C 7 154 100 51 1.85 0 100 12.t'' 5r 0';, A'C: 7' _4_ 200 42 17 580__ 0 12-3} -? 5C 1.2' " 110 71 1 F i)O0 48 174 C 100 L207 C 5.2?? I C? 5'0 1 ) 31 5" 15 270 625 0 1302 -?'5 17 4/. c 161? 30. 5 0 1 1 37? 0 100 30, 0 5n 16 t 7U. 1. I 7' 7 5<:0 _. 66 0 1310n 1 S0 14'1. 70e " 15 31C 10000 60C 0 1?1 1_. SC -'I1 2('C r7 7i__ _ 1 l 0:_ jO 157 3P4 660 0 131t, -2 5C q 70C' 144 23 50 97 358 0 100 13270 10 50 11 55 ICC 1?4?44 1)0 102 324 570 0 1.?' -2 5C C n 0 143 2P? 5C 97 35? C 100 132'. O.C C 14 3 200 16-7 323 20?6 12? 555 0 1 3 i 1 5 3 4 2CC 163 31.C 10 41 131 555 0 1337 1 5C 1'cL 23C 47 154 555 0 - I 2 C,;! (}) C C 0 0 0 0 133<) -? 5C q'4 C 07 16F S 71 2440 100 1343 0 50 4? 500 61 105 500 98 252 630 0 1348 -2 5C e.36 50 E4 16,2 50 56i 196. 0 100 135? 0 SC 9 49 200 55 116 1CO0?120) 340 690 0 - 1 0, C 0 0 0 __ 0 0 0 O n

-290miNr(Ofl F tCAIFP F' E AtPFAK RF SCAILF PLAK AREA SCAL F PEAK AR VJl SPT NO. HITE HITE HITE N& 126? 50 12 36 CC 7'c 17C 100C'I 0. 38 131. 0 14 127? -? 50,.78 107,5 5.____0 100 11 86 0 200 1276 -3 C 3 78 100 114 254 100 100 372 0 200 12R -p 50 1'A'q 5 100 FA'100nn n AA 10 _ 12P5 -2 so50 1 9 100 58 1?7 100 34 127 0 100 12aSt C, 50 14 42 SC 77 176 200 71 214 710 0 1294 -2 50C 39 100 52 118 100 32 116 0 100!1298 0 50 13 400 0500 1C7 25 S00 61.171 625 0 P03 -2 50 1.4 40 50 1 2'7 50 75 274 0 100 137 0 0. 1 40 200 72 6,F,00 o R.O 0i 1311 1 5. 43 CO5 0 23 53 10;)0 680 0 i1314 1 50 7 7 2cC. 42 112 1000 133 _ 3.95 6 80 0 1317 -2 C.. 36 50 IC5 224 50 71 268 0 100 1i21 0Q 5C 7 60. 1CO 131 267 100 40 1' 7 520 0 1326 -? 50 6 41 0 IC7??3 50 62 238 0 100 r143l __C 5C 9. 43 2,10 6.8.... 3l.C, 200 123 _61 720 0 1334 1 24 36 20CC 13C 42. 200 163 4g2 720 0 -1 r' C: C 0 0._0 Q a 134A -2 C 50 142 0 50 186 0 100 134 4 50 11 5: / n9! f0 12 ___3 69C 1'46 1 C it 11 4?') 117 25.?20 40 117 90 0 14, -,5 7 3 0.. C 166 50 47 172 0 100 13: 0^ 5C 7 1?CC 35 71 100 42 152 64C 0, ='!. 1, 2 0 C C C 0 0 O o _,IN Ctlr F srAI F PAK p.IFR, srCi F PFAK ARFA _ AI- F PEAK APFA Vni PIKF -NV. HITF l: I F HTTF NG 1260 -2 0C 10a 4 IC, I. 13 t 100 47 160 0 100 1271 -2 50 _ 3.4 / 122. 1 100 127 363 0 200 1277 -3., 37 01 lt 2l4 24 1, I 127 376 0 200 21 2l I.. 1l _. 5 17, 7 00 4, 1.C 63. 0 1286 -2 50 14 /5 100 61 126 100 34 136 0 100 _1 _.21, C OC 21': rOC 4 147 2Q) 66 9lC_ 7.00 0 12 9 -2 50 1I?2 10) 64 13C 1)0 42 156 0 100 13CCO C 5C?' 70,-c. 1f6.2i2.C__ l.4... 640.0 1304 -? 5C 1' 3 C.25 23 5C0 83 27 0 100 13Cr 0 5 1,2.., C 17 4 C 6 34 570 0 131?5C 16 1C 1 2I5 1)5 0 51 115 570 0 131 - C 1 3 l 0 5 0 12 2?37 5C 33_ 219__ 0 10.0 1322 0, SC In'4 1C0 100 97 3C04 610 0 1323 1 50 13' P 2'CC c3 1!3 10) 76 216 61C 0 1327? 5C 14 54 0 128 247 5C 83 307 C 100 1331 C 50 1, 57 O 2 (_..... 2ro 0 45 1?3 740 0 13?5 1 5 C C, 5CC 8C 17C 200 59 154 740 0.__ tJ r,, O.. 1341 -2 5C c 3? 5C 7e 151 50 5? 180 0 100 1345 C. s 11 2 CCCr 3 75 ICOO 9 245 715 ___Q 130. -? 50 9 30 5 78 151 50 52 186 0 100!13-q C SC I0 2. C,, 4 4 204 4 1' _0 n 640 0 -11 2 0 0 0 0 C C C 0 0 0 0

-2 91Ru CfrnDlF srAr F PFAK AREA rCAi F PEAK ARFA SCAaI F PEAK ARFA,,v SPIKF NO. HITE HITE HITE NG 1376 -2 50 11 95?;0?00 0 100 180C -3 50 41 214 50C 63 16q 500 _103 252 0 20n 1384 -3 50 98 320 500 98 257 500 174 446 0 400 1 R8 — 2 Cr 37 I-AO 2CC 127 0n,;nn20 14Q 1R- i tin i1392 0 50 2C ICR 590 (Ef 174 1COC 555 n 13q. I 4 75 500 3, c1 1iro00 555 1398 1 r0 C 55 200 6? 174 1000 If8 466 555 0 1 3qq -2 5C 11 1C? 2C0 6 17 F?( 95 3O C tLn t403 C 50 17 116 5o00 152 40C 500 61C 0 14 r7 1 90 20 1Ch S9d 1"iS1 40C I MI 188 st tt' 61 0 4CH -2 0C 12 q3 1op 1 33C 200 c5 308 C 100 141? n0 0.2 103 500 2C0 5' 5' J 0 55 162 540. - 1416 -2 6C 14 9? ICC 173 377 200 75 238 0 100 142 5 16 1 3 50 4 1C7 200 98 327 49 0 1424 -2 5C 14 101 1Ce 13C 317? 76 223 C 100.4? 28. 0 0 i12.1 ni 20C I4 4 f 200 I 8?1 2 530 1472 -? S..C 1 82 100I 100 172 45 0 100 1436 0 5 Q 1'C ) 2 C 17 33 2, 85 25 47C 144', - -?2 ( 9 3 10 l 1 26 2 100 137 393 C 100 1444 _ 5C 13 l 2 12 __ 00o 6q9 22, 450 1448 -2 C P 64,c lC 24 i: 127 414 C 100 14952 C4O i,,0 24 3 1,.12 20C 74 23 3 54C 0 14' 7 -? 5C 9 7 1(, 11? 1 29 15)C' 127 404 0 100 L4! 0 0) ___ S'.,5 C 1 5__ 5 _ 2 i _. 1466 -2 5C 3'3 1';.;4 216 100( 1013 332 0 100 1 4 7 C _ __ 0 _ 5 (. 7.:4__ _. 3.i 4' _41._._4_____.C._.0. 1474 -? 5C0 12.; 1 O 0 140 434 C 100 1471 () 5C7r 12 7(l _ 2;,;:'_;0 10 4 0 l8( 71, 1- 1 C 1. 7 1 2 11 2 425 0 1 4 -? 5C 1,; 1' L,?1]t 1.3 4 LA.._3 G 1 0 14:.7 0'; i 4''; C) 1C 1'4 0 20 10 343 470 0 14?2 -?2. ____1 7 " __11C 717 7 14 312 -0 4 _Q 0 _ ) 149/' -' C 4 1.44 I.C, l 2 )0 13 9 4.04 0 200 -] \..._C' ( " C C C 0 0 =0 0 0Q

-292RiJ.U: COIDF CAL F PEAK F.ARfA6 rAF PFAK AF SCAIF PEAK ARFA: AftlL SPTKF NO. HTTF HITE HITE NG 1377 -2 50 27 1- 2?C 131 262 200 158 462 0 100 [1381! - 5sC 6C 236 c00 71 142 500 84 238 O 200 1385 -3 50 1 3 5CiC 100 206 900 127 347 0 400 {13 -2 50 &, 2 147 200 1 10 22, 20 Q 4 313 C 100 13C; 0 50 2? 137 9CO0 71 14; 1CO0 6900 0 1 3:7 1 5 0 4 C 5 co.. 36 L 00 180 on. 51 5 690 0 14C;0 -2 5; 1; q,. 100 13?;AC 10C 140 439 0 100 1 -0 ti 1:' 1 I ";;^ C 72 161 200 61 01 115 0 140) -? r 1? 1f l( 1 0 14C 274 100 142 466 0 100 413 0 C o ^2 1207?,30 21 4' 2 01 9 3 272 420 0 1417 -? a0 14 c7 10 174 26i t100 121 402 0 100 1421 0 5(L 32 1.6: 7 Ou 144? c 5___ 28 -L -54C _Q_ 142? -2 5C 1 12 10 163 34C 100 145 4 73 0 100 _i_2 q; _. C _ _. 71I__ C 174 _7 87 _272 480 0 143-3 -? 50 1) 71 1(00 12';?5 trio 1 37 41 0 100 14? n 0 C 1:7't 6, 1 3q 2.)0 74 246 41.0 0 14 -1 -?'; I? 1 "4 l 261 10C 132 418 ( 100 L14 n ^0, 2?,< SFC q3 1.2?OC 290 q3 3 3 _____ 14'49 -2. C': I, l 1''" 61 10i) 1?4 3i u 100 r.14^. fr.?. 2.'.2p l_. 2?,:7 7?CO 177 _..4._ 445_ _ Q4 14 -? C;, I o01 1C8 3 4 0 100 1__ -—: 3 \ 0 5C_ I=.[_- Pl L 2)LH.1 625 C159 51 0 I s46' 1 50.?. C,, {'.. 14') 2C?00 75 2c7 515 0? 2_ r, - l _..._. 1 2_ 244 1 )0 i10 4' __ _ 0 10L0 1471 0! 5( 10() 4' S 3 1. 3 20() 44 1 79 4?5 0 4L 7L _-Li2- _' _-. _1 f _- _7___ l - -1? 2 " 1 212 3 10.._2 100 7, 0 C 1... -(; 1CP?C 72(n0 72 251 450 0 14:'. -: r?2 }: 1 f S, 4 17C nn.4 24 277 5 0n 14', -n?. 17'.?t 1'(, Vi I 7C 0 Zn o 4 277 515 0 --......::...._ L 1 ~,~, 1.3_0_ _ 1..........LZ~_L....1 _L. 3 _ 41.3 4? 2 7__....-. 0 QQ 42_ 14 7! -i:C' \ )7?1:? 31. <:'!:.~? ~.24 2 C 115 3.44 C 200

-293RllhN CllF CAiF PFAEK A-RFA.C. F PFAK ARFI rCAI F PFAK ARFA,Iunl _p(Rk NO. HITE HI TE HITE NG! -. _ ^. 1378 -2 50 13 80 200 74 191 200 105 284 0 100,1382 -3 50 35 14 2 5CO 36 4 sOC A 62 156 0 200 1386 -3 50 78 229 50C 0 1 157 500 104 279 0 400 1iqno -? 5 If, 7g9 20 49 [C. 200., f. 1.71 0 14inn 1394 0 50 7 72 500 5 14C 200 79 223 53C 0 n1401 -2 5C 6 s.9 IC!O 100 1.02 2276 0 10o 1405 0 5C 7 60, 2CC 213 611 200 72 ls5 540 0 14 10 -? 5C 4 6.4 1o 12 4CC 200 112 3log< C 10o 1414 C 0 4 56 C00 7C 175 200 54 143 455 0 i141 -? C A 77 1i n 1Ir.r 10 1in4 2?R C 10n 1425 1 5 14 70 50n E2 205 500 18 40 550 0 1426 -?2 5C 6 f l CfO. 202 1 (i 110.309 Q 10 1400 0 5n0 0r 22C 1C1 246 200 s 7 147 435 0 1434 -? 5C 1 45 ]1C) 77 18C 100 115 320 0 100 1438 0 50 6 5 5000 44 1C4 700 74 205 425 0 144.? -2 5C 4 4 C IC.7C 16tE r e C 222 C 100 1446,5 50 5 6, 0n 5? 129 200 4 15h 4915 0 1451 -2 5C 7 r~ 172 4C4 100 PR 11 0 100 1444 0 50 7 4' 0(0 IEE 5C5 200 50 128 485 0 145 c! -2 __'-? l C s..' CC0 aL__??7 C I1 0 146, 0'C 2 1 C S, 27C?00 47 1 440 0 1 46 -?'O_ C 3 47 10tC 73 I 174 I100 P 217 100'147? 0 o 0n 2'3'C o0, 14 7!0o) N6 264 435 0 1A427 6 2 5C Lt L * r_ F 2C2 o I I0 30?oo 14P, 0.' i) SC 1 12 9 1 7 1 c,1 1;) II79 1 39 560) 0 14. - 5, 427I _1.. 1 _ 1 J.. b, __ u Iuu 14.'. 0 SC c 4' 7 37 1 74 4RC 0 i14l 1' C 2 C ") J? 4 00 23 4'. 480 0 1 q' -.? 5C c 5? C' 1 21? 1:i) 113?44 0 100._.5 _.;.._ _.._ _-" 7 1 ir..7 247 ___ _ 200

-294PUN CODE SCLE P^EK ARE SC.LE PE. K E ABE. SCFLE PE EAK AREA VOL SPIKE' NC, HITE HITE HITE NG 1379 -2 50 25 1C2 20C 96 215 200 132 353. C 100!:83 -3 5C 51 17 5. 0 4'8 101 500 69 173 0 200 1387 -3 5C 105 268 500 82 178 00 119 3CA 0 400 1 1 -2? 0 _ 2 _ 2C.0 -64 12.6 200? 79 27' o10 1I95 0 50 25 100 200 120 26C 200 120 319 640 0 1402 -2 50 70 100 13 247 100 12 363 10Q 14C6 0 50 7' 1.1 lo00 47 q 2?C00 75 230 420 0 1411 -? 50 1 7?2 100 112 24C 100 125 347 0 100 14 1 0 5 33 115 5CC 11C 246 2;0 87 250 495 0 1410 -2.0.. C C5, l 113 24r,, 1. 15? 4 5 0 100 1423 n 5C 3( 10o 500 I12 24C 7)0 96 266 540 0 1427 -2 1 P.f 113 231....100 143 393 0 100 1431 5o 2 c 44 ( e 1 Er 2C0 C e 240 480 0 1 435 -? 0 65 1CO 107 24 100 124 346 0 100 143. 0 50?(, 2CC 1P6 4C6 200 81 210 555 1443 -? 5C 1 4 0 103 2 100 126 345 0 100 1447 0 0Q 2? r ( C' 76 161 200 80 215 555 1451. -7 5 1 1 I00 1C F 2?2 100 12 _ 335 _ C 100 1455 0 5C 2?' 75?0J 200 84 217 490 0 14566..1 5C 27 7 3 0! _.l 1 3 2a6 2 20. 102 2P3 490 0 1460 -2 5C 14:, I('C s; 21t Q100 121t 3 C 100 140.4 0 5C 2'5 0Q 500 142 32C 200 70 199 465 0 1/46r; -2? 9C 3 ItC 75 1 4 1CC 5 20C 0 100 17. 5.. 4.5Q_,_ P.' 4 17c 200 41 1 4 10 1477 -? 5C 14 1 lt 1(i 112 31f 0 100 14 l _._ ] 1.' C __1C, 1 177 20C 6f 203 445 0 14Pe, -? 5C?(. 7 100 c5 1o96 1(0) 102?P8 0 100 14.Q ^ _.. c.;. c,^ 106 27E_ 2)0( 67. 211 495 0. t 4 -? 50 17, 1' ( c 2 1?3 10 113?21 C 100!1 4 F -3 rC" l? 1 t,.L n 4 107 2 7261 0 20

-295i iN- -r'rlF SAtLF PF AK AR.FA SCA F PFAK.AFA SC F AK ARFA VCI NO. MITE HITE HITE NG |1500 -1 SC C 53 IcC 37 ICe 100 15 70 0 0 1504 -2 50 212 123 100 130 321 100 148 447 0 o00 1508 -3 50 53 C14 200 110 271 200 152 407 0 200 i51i2 O., 5C.i 26cq 50n 2..33 5. 0nn. 211 6i41 4A RQ 1516 -2 50 14 100 100 132 3?4 100 141 432 0 100,,52.0.. 50s 16 1Cq 5CQ 55 137 200 67 247 500 1524 -2 50 11 18 100 121. 321 100 122 400 0 100 152F 0 5 " 17 1.5 200 147 36C 100 120 444 490 BUN cfr(F SCrAL PEAK. RFP SCAiF PEAK ARF/ cfAIE PEAK AREA VnOl SPTK NO. MHITE HITE HITE NG 1501 -1'C 0 21 50 43 111 50 18 78 0 0 1C -2 50 C 1 00 1C2 22 100 92 l__.. _ __1._ lO^n -3 5C 31' 1 6?rC 27 234 200 105 2S7 0 200 _9517 -? 5C 5 7? 10 1 04 222 100 97 314 10n;25 -? SC 15 54 1e 12c 2c 130 124 376 0 100 15?;. Q O,? 17?.0.12e 2 2 10 e4 04 lI ^1I 1C 2' 116 2C 12?75 20 94 276f 465, NPIN rl Cl',F.FA F PFAK'AF:A fC l F' FAK ) AF rc.I P AK APFA nil cP PKF IC. TFITF HITF HITE NG 1IC _-1i 5'; ( l' C'1 11,3 90 30 113 0 0 15l -2_-2 5C; 7 1 C CS? _E I1L;0 i 02 0 1 00 1.1n -3 bC, 4,6 t.?r P 1,C 200 1C6 27? C 200 ]1 4 n r! r,-i.. cs 2?f o 2:0n I16 i.42. 4Rn Q 51"' -? 5C IS c7 1CC c6 2C2^ t C 1C5?74 0 100 1 5' ___ 50 1 15 I. 77 n 20 c 5. l5?o 0? -? 5u (: i.,C 4'66 1')0 124 324 C 100 Lj_,:n r'. r': 7 r:.- r 171 2q0 1 58 57._ 4h C 17 iRtN Cfir F SC bLF Pr- A'- k.i^,r r FK AP- PF C SCAI F )FAK APFA V/l SPTKF N.C. I- ITfF l-TTfE 11TTE NG 1-53 -1 C C t 3 r 3' 87 50 15 66 0 0 1507 - 5 1: 1(0P. 19 1 1 C O 90 2 (.. 9 C l0Q; 11. -3" IC' 1''?'CC 72 lh1 2?0 87 2?0 0 200 1515 ) 50 5' 156: tC C 52 11 2(.00 105 309 490 0 151o -? 12 800 ]C 89 1 P 100 90 266 0 100 1523 0 5C 2. 1G4' CG 615 14 2 20C 60 184 525 0 15?7 -2 50 12 1 1 CC 52 20?2 CC 03 268 C 100 1531 0 _O 15 7?CC 72 16f4 20)0 46 140 480 0

-296RIIth CnEfF,CAIf PFAK AiRF A.C, F PFAK APFA r SCA' F PFAK ARFA.. se J PTK NO. HI TF HIE HITE NG 1533 -1 50 C n 50 114 50 21 190 0 0 153.7 -2 50 f 21 45 tO10? 223 100 100.;5 l _J10fl [1541 -3 50 56 114 2PC 106 23 200 133 360 0 200 r]fi4IS n c nc l isn 6n I 27 e, ro....nQ.. e - C jl 11 A I l 460 0 n,154. I 90 64 127 500 - -C 20 374A 450 n 1549 1 C: 64 14 C CO 137 3C5 200 188 506 450 0 - 5153 -C -C 100 121 345 0 100 15-7 -2 50 18 37 101 101 217 In0 126 365 0 100 155e2 0 5C 23 4 3 5C0 46 7 200 69 209 425 0 1562 -2 sC?6 47 100 ll?42 100 125 374 C 100 1i946 _ C'-t0'L. 5. A. 7:;5 1519 200 71 220 485 0 1570 -? 50?'C 35 1 C1 2 1 O 1C3 306 0 100 1574 n 50 23 6 0CO 210 443 2 e 2 237 515 1574 -2 5C 23 4 0 1C 111?34 100 115?6 0'100 15Z^ 0 50?F 4 5F, 1 1 281 20(0 f6 242 510 0 1Se6 -2 SC0 3I 7 1(iC; lC 100 111 324 C 100 1590 0 5c 1.. 4 9 I 3 21?:)o, 8a6?4 4o0 0'154 4-? C CC 1( C 212 100 114 327 C 100 1 59: l__ ___ I 0__ -0 -2__ 2 P 246_ 49:O? 1. C 7 7' r 122 27C 20C 96 271 490 0 16!6 -.__ 5C _5 15.31 - 0 114 7.100 124 37C C 100 1611.0 C C 1S' 3 5,0 lq7 424 2C 380 235 46 0 1i.-. -2 5C 4 44 I e,11..42 100 r17 344 0 100 161' I 5C 1.F,3 )' 22c 4 C 200 174 55C. 510 0 I ~1 C2.S-_: 0 _/ 2.__ 1n.ICfl_ L 95n _ 31 q c QO 1625 0) 5 3. rCCI( 1??7 20 77 24 45 0 c.1 -',, r __- 1'.,_ J " _ l_. ~' 1 ~ 3. _ __19 1 __ 7 1 00 1633 0 5C 1'1 2 I. C'100 126 396 420 0 16'7 I- 5C.. 1 1: 1'. l L q8 31 2 C 100 1641 0 50 13 {' 5; 154 33F 100 1'1 476 500 0 J'4....:__' c'. 7 4 _._.Q...~.... 2 7 ____C () _ 7 O_. I64 -t C'- h 2CrC -r 1F 200> S4 5 C 200 If' —- L — _ _ _: _:2.. _- t l......(:'C?0__ C_5?_0 _.._._. 3O__ Q, 16'7 r) 5 7 ( 7(, C' 3 2? I C -0-' 0 660 0

-297PUN.rODF SrA F PFAK hRF CA LEF PAK AREA sCAIE PFAK AREA flU SPiK NO. HITE HITE HtITE NG 1 534'-1 SC -o -O 50 -0 -C 100 38 142 0 0 1538 -2 50 _16 17 CC 125 244 100 116 400 0 100 1542 -3 50 49 76 200 108 2CS 200 120 345 0 200 1546 0 50 -n 50 74 132 200 133- 38 q 450 1550 1 C 49 76 500 74 138P?O0 132 403 450 0 1554 -2 50 17 21 1CC 130 245 100 128 405 Q0 1O il 55S O 5C 20 27 200 liC 212 200 67 202 470 0 15563 -? 5C 1.H 24 I1CC 125 24P 100 114 368 0 100 15.7 0 50 25 33 5CC 204 386 200 *5 227 420 0 1571 -2, 0. 2r 295 1 1 5 100 12]3 25E 1(). I. 36 l 0 00 157 0 5C 32 40 500 129 236 200 130 423 54C 0 15795 -? 50 28 37 7 100 13? 2.C t10 111 3'74 0 100 183 C 5c 3h sn 5CC 16tl 32 200 61 245 455 0 15P7 -? 50 1 I 23 10. t13~ 275 1.00 110 370 C 100 1.591 ( 50 26 31 500 173 162 200 69 258 470 0 1595 -2 50 14 18 1 tCn 13 3 26h 100 10 23590 100 i'i59 O 50 34 43 5CC,3 117 397 200 79 278 480 0 16C3 -2 5Q0 16 0 C 14 C. C 2.? 1)0 106 _367 O (1607 0 50I()?.3 6 C.5 232 466 200 66 n u 4' 0 161? -2 50_ _1L 2 1IO 131 2; 1.O 100d 50 0 100 161o 0 C 3C r 4 232 447 2?0 71 252 515 0 161, 1,C. 2(3:7.( 111 2 20 70?2 2 15' 0 162? -? 5C P 1 4 l 14-?022 100 107 360 0 100 1626 C C;r f, 2 2L C 5 14 27E 200 66 247 40 0 1630 -? 50 13 16 l1( 132 271 100 88?73 C 100 16_30f _.. 5C( Ip 2? 0.. 0 iC 1c 3 200 69 219 460 0 163a -2 50 11 13 I i 1 14 26C 100 102 35? 0 100 1_4?2 0 0 3n 7 PC; n 17I P 33p 2?0 74 25R 4A 0 0 1646 -2 %0 6 1'10 lA 226 100 77 2?9 C 100 16. 3e -0 _ ffi 34'S 2 112 21F 22 2. 4 200 165,4 -3 C C. 5',4?)OC 176 347 200 148.43P 0 300 1_658 0,0 72 17 50C PO 15 2')0 1 5;9 490 440 0

-298-'.RUN CdF"F S-CAl F PFAK ARFA~' -fAI F PPFAK FA -ASE PEAK ARFA VfUL SPTK NO.' HITE HITE HITE NG t5.5 -1 Io - -.. 5.3 8C 50 5, -Q ~. -5C- 3' _.. Q 5 7 1539 -2 50 25 41 100 11e 217 100 106 339 0 100 1543 -3 50 5; 50 200 1C2 184 200 01 293 00 1547 0'50 7C 117 50C 65 114 200 124 362 460 0!],e ]','71 2.... 2co 1-7s.'Lq _200 13:2 134: 4aa' 1555 -2 50 24 8 tO 100 7 20C 100.100 320 0 100 1560 0.0 50 26 4_ 2 2C0 14?7 2272 100 106 344 515 0 1564 -2 5C 24 38 1IO 113 201 100 87 284 0 100 1569 0,50C 3R8 61 500 17 37_ 200 _._ 72 229 405 0 1572 -2 50 23 3 1000 101 181 CO 85 278 0 100 176 50. 25 22 50 1i 2 0_ ) 52 191 465 1580 -2 50 23 37 Io 1CE 1 P4 100 93 266 0 100 1 54 -t 0 50 3 48 500Q 157 2 00 131 420 415,1586 -2 50?23? 7 1iO 118 234 100 97 305 0 100 1592 0 50 3. 47 500 n 101 1 00 167_ 4 5_.0___.._0 [1596 -2 50 22 35 100 116 2? 1O00 Sl 292 0 100 1600 0' 3Q r,,:c;2r L?r I 247 45Q Q 0 p C?9 P, r'C 2C~ _..6 200:)1 247 450 0.., 1604 -2 50 20 34 1CC 117 215 10 91 301 0 100 16C 5C. 3 rl CC. 15 284 200 7.3_ 241 530 0 1613 -? 50 24 42 ICC 1C7 19q o100 6 278 0 100 1617 0 50 C 81 1000 -C -C 200 I.L2 2 C9? 485 0 1619 1 C 46 73, 1)CC 14 277 2(00 118 341 485 0 1623? -?. 2, 4 4c rr 4 _iC e _ —7 304 C 0o 16 27 0 5C 3'V1 Ou 113 20?20O 7C 213 400 0'31 3L-. 4 _' 3 ___ l'294_ 7 100 1635 0 50 3?;, 14 0 1. 1 45; 490 0 1.<)? 5 C i2 I 42 1 3C _ 2 43 l n ^.1 22 _3 L 10 1643 5 2C;?n 31 5.'' 1 34 1:l 6?0?2 919 0 16442 ] SC 2":!2 "3~ 10C o 2c7 1 5 0 1657 -? r 1 InC 1C C^ 1c 100 81 23 0 100 1_s1 _a C.C 4.C;_ 91_.__. 1? o' 8 C 237 1 2__Q 16.5 -:: C.. 12, 70 C 142 2' 20)0 154 403 0 300 -0_ _ C 11......___12_e...___R_ __L o? 236; 6C8. 605 0

-299aRN -t r ~0p -- rAitIr P.AK At'FA sr ai F PFAK ARFE'rAi F. PEAK ARFA 1 r, 5P1I NO..'HITTE TE' HIT NG 1536 -1 50 -O -0 50 41 95 50 43. 158 0 0 1540 -2 50 23 3q 100 10?o2 20C 10 96 315 0 100n 1544 -3 50 53 92 200 93 174 200 96 282 0 200 1548 0 50 6 1 108 i 00 61n 12C 700 109 338 -a440 0 1552 1 5, 61 1 R?CO 16l 34?n0 1OR 310 440 0 1556 -2 50 20 35 1 00 2CC 100 103 326 0 100 1561 n 50 22 39 200 162 319 10O 103 354 500 0,1565 -? 5C 21 34 1 iCO 103 204 100 96 308 0 100 1569 0 50 34 53 5o0 113 222 200 28 156 490 0 1573 -2 50 19 11 ICC 93 178 10n 69 262 0 100 1577 0 sC 34 3C 5CO 142 27C 200 3R 18 3 490 0 581 -? 50 24 4'0 100 111 22C 100 78 285 0 100 1585 0 5C 3? 56 50C 91 178 200 77 323 410 0 1589 -? 50 31 53 ICC 119 1 l 100 68 256 0 100 1593 0 5C 40 70 50C 112 21F 1(o 124 448 425 0 1597 -2 5P 17 2q9 I CC 97 4 1 00 66 251 0 100 1601 C 50 32? 4 C(c, 144 2?C 200 3q IPO 395 0 1.05s -2 5C?4 42 o10 103 205 l() 64 249 0 100 1609 0 50 4 P 1 50C 21 457 200 145 453 510 0 1614 -2 (0 33 9 C.C 16 1 )C 00 571 40 0 100 1620 0 50 51;i 50( 167 346 1I0 63 239 470 0 1624 -2, 20. 3 1iC c ICF 217 no 61 _?0n, a 100 162 0 50 21 3 500I 0 142 282 1)0 72 296 370 0 1632 -2 5 0 1: 2i ICC 102 196 100 63? 53 _ C 100 1636 0.0 1:.500 72 146 10C 109 36 450 0 1640 -2 50 -. I CO 1__. 227 1 7 5 _ 1 16441 0 5C 1? 24 1CC?C4 -C 100 90 324 540 0 16443 1 5C C C'2 3 2CC I(IC 1?' i (1 ) 0 105 366 540 0 164P -2 5C 15 23 I rC 1C 21C 1')0 61 243 C 100 1 5.> -3 50 37 ( 3?cC Pc 174 2?C 67 217 0 20. 1656 -3 SC 61 10! 2CC 12 265 2o0 125 35R 0 300 1660 0 5C f 11 1C ^ l 1 9 7 200 142 416 480 0

-300-...~."T1..SCALF PFAK IAREA', CI:PP-AK ARF a.fSAI PFAK ARFA'P $PAKF * NO.; HITE HITE HITE -' - 1661 -2 50 17 35 1CO 8E 183 100 t24 371 C0 oo 1665 -3 5C 32 62 200 73 163 200 114 302 - 0 200 j 1 in' -'9 J 254 a inn 1674 -C -, P 1=5 1?Gl 77 171 ln 7? 754 n 11n 1678 0 50 14 26 20C 213 5CS 1000 237 576 635 0 1681 1 0G 1? 24 _ 50GC.. 1C., --- -0 6,35 0 16R4 -2 50 8 16 100 81.1C 100 124 362 0 100 16 fE8 0 5n C 15 35 en. 136 327, 200 Q 45 1 f3 515 0 1652 -2 50 5 13 1 C 71 154 100 75 229 0 100 1696 0 G 50 10 500 60 142 200 47 151 600 0 1700 -2 5C 10 iCC F3 173 10C 79 250 0 100 17C4 0 50 12 1 )CC l t4 27C 200 7 240 415 0 17CS -2 5C 5 1 I1CC F3 182 100 76 241 0 100 1712 0 50 6 2 C C0 1 I 463? 0^ 27 79 495 0 1716 -2 50 5 9 ]C0 7e 172 100 73 231 C 100 1720 0 50 12 25 1 0C0 7 2C06 100 117 474 455 0 17?P -? 5C 4 I ICC 76 16 - lOC 77 243 C 100 _172 0 90 6 10 C,'0 105 234 1n 1060 4CR 525 0 PUK CCDF SCALE PFAK A/iFA SCALF PfCAK AREb ScALF PEAK AREA VOiL tSPKF N-. HTTE H rE HITF NG 166? -2 50^ 25 48 1CC c 4 17 100 130 353 C 100 1666 -3 5C 3 8 75 2.?( 78 F liSC 200 116 2 O 200 1670 0;, r5' 1? 387?n(0 160l 44 710 0 16.7; -2 50 12 7? - 17c L 32 ICO 1l; 315 C 100 167^ 0 5C 17 33 20C -C -C 1C00 139 335 615 0 168? 1 cr /14. rrC r C 90 8c 10 ( 131 317 615 0 1685 -2 0 11;)4 10C 81 167 100 119 314 0 100,16Ee 0 C l'- r 5_,4F __ 00 126 36 535 0 16C,3 -2 50 110 2 1( C 1 74 ICC 106 78 0 100 IC C7_....' j) 2 (4 it,'; 7(00 56. 164 450 0 17C1 -2 50 7 l lC C.:6 145 100 95 254 0 100 1.70i. 05 5 12 l C 17 4953 200 63 e180 510 0 17C0 -2 5C 6 14 lC 67 146- 100n 9 2 52 0 t00 1713 0 50. 1n 1's (.C 140 113i 200C 70 167 440 0 1717 -2 50 6 1 4 1 O 2 1 3 100 91 244 C 100 1721 0 5 7 1 1 rnCC e6S 6. 150 417 470 0 1729 -2 5 C ICC 66 51 100 111 28 ( 0 100 1733 0 50 5 r 50 1 C..25 8 2?00 69 200 49Cl__

-301RBlliu rnF -CAl F PF, K - ARF- La fAI F PFAK ARFP lfAI F PAK AIRFA lI -Y SPTIKF NO. HITE HITE HITE NG 1663 -2 50 35 60 100 1 31 223 100 123 355 0 100 1.667 -3.-. {50 5C t_ 20 I 2 115 202?00n 10? 28 0. 2.0 1671 0 5C 84 146 50C 138 24 200 -0 -0 635 0 1673 I 50, 7 12 9 5cr 1!A4 24. s on II0 1. 74, a5 168h -2 50 17?8 1CO 105 176 100 86 266 0 100 160 o 0 5t 4 7?Cn 224 431 100 130 415 535 16'4 -2 5C 22 39 ICO 1 9 2C2 10C 84 263 0 100 16 -P 0 - C 3.5 5r00, 20 3d.2 200 73 217 470 17C2 -2 50 22 36 1CC 134 231 ICO 101 302 0 100 1 7-11. 0 51 42 67 5Q0 f 38 4t7. 20Q 87 256. 4R5 0 1710 -? 50?f 4o 1CO 124 2? C 100 92 2?5 0 100 1711.4 0 50 3q: 1 IQCr 23L 47C."C 66 213 46C.1718 -2 50 2? 3h6 1t 125?14 100 99 30n C 100 1722 0 50 355 5 1 C 0 1 ^2 1)n -0n _ 440.n 1726 51 C 30 4, C00 I 342, 2C 14? 30 44C 0 173'; -2 1C' 20. 2 _ 100 132?23 1.C, 117 35; C 100 173h6 C C 4? (5'50 2 3'r0C2?l30 lip 312 540 0 1737 41 n' 10C(: 121 225 200 I14 370 7 54L C 0 FJUN CO ]rOF S1CALr PcA,"r Sp^ 2 Pf<K ArA[ e SCAt IF PFAK RF6A Vfn. SPIKE NC. IT'H lTF ITF ING 1664 -2 3? 1C C7 13 100 68 211 0 100 166 C -3 5C ^_. 2 C, " c 167 2()o 73 2C C 2 167? 0 53C. (-,1 I. CJ0 1 C7 2~'7 1 ii00 167 415 625 0 167 -2 50 S 14 1 7 1l7 1100 7 67 212 100 16pO 0) C 644 1 1?' -C -C ICO 7 22 540 0 16-4 1 5C t4 11^ 5 12 t? 1Q9 C 200 73 212 _540 0 16P7 -? 5C 1 "'2 ICr q7 173 100 64 207 0 100 16cn 0 5 C C 5 3 I AC 13F 200 L42 137 510 lfsr -2 50 13?2 1 c 16 lnn 55 193 0 100 1 6q 0 5 C -r CC C._,1 I f q O 2 20?C 36 1 34 4 85 0 17C3 -2 50 16 27 1C( -C - 1000 60 193 0 100 1 7C 7 0 51 17 5, 7111 5 _?I _2 _...1..___(: 1711 -? 5 1), I 4 In C 131 l AS 100 5 183 0 100 1715 (C 5C 3( C:'? n 7C 21Y 47 2310 3 7 11 3 495 Q 1719. -2 5C 13 24 1C!' c7 l12 1COC 7 194 0 100 172^ 0 0)? c r I C 0 75 1 52 1 00 -0 -0 510 _ OQ 1731 -2?'5C 14 4 0 116 l 1)0 9 31.0 C 100 1734t 0 C __' 57 SC 1? 3:.?0 7C 2 14..530 0

-302IV.2.4 Key to Data Location

-303Table IV.2.4: Locations of raw data points Station 21/22 May 6 June 20 June 9 July 8 August 29 August 1 1669 988 1031 1195,1212 1287 1328,1332 1218,1222 1336 2 1670 989 10352 1196 1288 1329,1333 1213 155337 5 990 1098 1197,1219 1289 1330 1102 1223 1334-12min. 4 1278 991 1280 1220 1291 1351 1282 1224 1335 5 1671 996 1281 1221 1299 1342 1673 1000 1225 6 1403,1407 997,1001 1099,11031230,12534 1297 1343 1279 1659 11052-5m 1238 1298 7 1100 1231,1235 1300 1544 1104 1239 15346 8 1672 998 1101 1232 1305 1345 1002 11051 1240 1509 9 1678 999 1110 1233,1237 1306,153101351,155 1681 100 1241 1313 16571592, 1396 15398-3m 10 1679 1008 1111 1246 1307,13111352,1393 1682 1114 1314-5m 1397-5m 11 1680 1009 1112 1683 1115x2 12 1688 1010 1113 1116x2 13 1689 1011 1121 1012 14 15 1690 1017,1021 1122 1394 1126,1394 16 1691 1018 1022 17 1019 1123 1247 (1308) 102 (15312) 18 1020 1124 1248 (15319) 1024 19 1029 1132 1320 20 1050 1178 1249 1521 21 1179 1254,1255 12572,1658 22 1180 1256 *: 5 minute plates ( ): 1967 data

-304Table IV.2.4: Location of raw data points, continued Station 21/22 May 6 June 20 June 9 July 8 August 29 August 23 1181,16443 16441 12571 24 1186 1262 25 1187 1262 26 1696 1188 1264 1322 1355531354 1323 1395 27 1265 A 1697 1414 1453 1514 1567 1600 B 1698 1415 1454 1515 1568 1601 C 1699 1420 1455 1520 1569 1607 1456 D 1405 1421 1461 1522 1574 1608 1412 E 1704 1575 1609 L615 F 1705 1422 1462 1576 1610 1465 G 1706 1423 1463 1523 1616 1618 H 1707 1428 1464 1528 1577 1617,1619 1620 I 1617,1619 1625 J 1712 1429 1470 1582 K 1713 1430 1471 1529 1583 1626 1660-9min 1532 L 1714 1431 1472 1530 1584 1627 M 1715 1436 1473 1531 1585 1628 N 1406 1437 1478 1558 1545 1633 1413 1482 1549 e 1720 1438 1479 1546 1591 1634 1550 P 1721 1439 1480 1547 1590 1635 1551 &Q.1722 1444 1481 1548 1636 1726 1552

-305Table IV.2.4 Location of raw data points, continued Station 21/22 May 6 June 20 June 9 July 8 August 29 August R 1723 1487 1559 1592 T 1732 1445 1488 1560 1643 16442 U 1733 1446 1489 1561 1593 1491 V 1736 1447 1512 1566 1599 1642 1737 W 1734 1452 1490 1598 1641 1602 SiM4: 1189 S1M8: 1194,1210,1211 S2M8: 1404

-306IV.2.5 Flow Rates

-307Table IV.2.5 AVERAGE FLOW RATE'S,cfm x10 STATION MAY 21/22 JUNE 6 JUNE 20 JULY 9 AUGUST 8 AUGUST 29 SPECIAL 1 670 670 670 640 650 650 2 710 595 600 590 580 555 3 - 685 670 685 710 720 4 710 700 710 725 700 740 5 635 660 635 635 620 640 6 61o 605 605 715 625 630 7 - - 620 680 640 690 8 625 620 600 640 685 715 9 635 620 625 645 660 555 10 615 605 610 600 680 690.11. 540 520 530 - - 12 515 535 540 - 13 55 575 555 - 14 - - - 15 535 525 530 16 510 545 545 - -- 17 570 575 565 575 580 575 570 18 575 575 575 575 580 585 580 19 580 575 575 - 580 590 570 20 570 570 585 585 570 590 520 21 - - 570 580 580 625 555 22 - - 515 4)10 40o 600 520 23 -- 540 630 485 535 485 24 - - - 300 390 570 485 25 - - 505 - 560 65525 26 600 65 670 610 640 27 - - - 555 535 595 A 450 455 44 5 48 0 450 B 470 495 485 490 405 395 C 485 90 490 500 490 495 D 54o 540 550 520 515 530 E 45 - - - 510 510 F 510 550 515 - 465 465 G 485 540o 480 525 - 515 H 460 530 446 4190 o 90 4 70 I - - - 455 J 485 480 44o - 510 K 440 435 425 465 455 480 L 460 480 435 460 415 0oo M 495 470 480 148o 410 370 N 420 4i30 42 425 450 420 0.455 25 450 450 470 46o P 57'0 55 50 46o 480 490 Q l4440 I1T5 44 ll,40 - 450 K. _510 - 47o 147() 50(o T 525 535 515 5.5 515 UJ 490 I4 94840 5009'I25 - v 51, 559'5 4 85 485' 48o 4 9o W 5 540 l495-. 4 0 o00 SM: 0. ^81y,48/:4/,,-;';21..: 1...5,8/30; ].;M4: 302, 6/ — /6+

-309IV.3 DATA ANALYSIS

-310IV.3.1 Data Reduction Program (160-A) IV.3.2 Calibration Factors IV.3.3 Program for Editing Cd Peak Heights IV.3.4 Corrected Values for Cd Peak Heights

-311IV.3.1 C D C 160-A Raw Data Reduction Program. dimension ida(14,42),cap(7),dat(7),ave(4,22),ratio(4,22) 103 pause 2 k=xfilef(2,l ) 10 pause 1 2201 continue 141 continue jockf0 endfile 3 2001 format(/) 145 write output tape 3,2001 124 format(50hl all data are scaled to 10 microamps full scale /) 1006 format(l 3i6) 221 format(59h cd pb 1 cu ) 122 format(78h run code scale peak area scale peak area scale Ipeak area vol spike ) 123 format(78h no. hite hite 1hite g ) 2211 read flex 1901,(cap(i),i=,6),al,nut 1901 format(6f6.1, fl. 07, i2) if(nut)1 41,141,143 143 do 146 j=l,40 read input tape 2,1006,(ida(i,j),i=1,13) if(xeof(v))l 42,146 142 146 continue 142 nut=j-l jo=l do 24 j=l,nut if(ida(,j ) )33 334,333 334 jo=jo+1 333 do 24,,i4,10,3 ida(i, )=(ida(i, j))*(ida(i1, )/10) 24 ida(i+l, )=(ida(i+l, ) )*(ida(il,j))/10 if (sense switch 2) 43,42 42 write out put tape 3, 124 write output tape 3,221 write output tape 3,122 write output tape 3,123 write output tape 3,1010,((ida(i,j), il,13),j=jo,nut) 1010 format (13i6) 43 write output tape 3, 1067 write output tape 3, 1066 1067 format(// 39h data are in nanograms per cubic meter ) 1066 format(// 72h run cd p 1 cu /) jirO=0 28 j-jo 27 if(ida(2,j))21,22,23 cc test node, if-, data is a blank, if 0 data, and if - rerun or so:-lke. 21 jin=-j

-312IV.5.1 Data Reduction, continued. J=J+l if(j-nut) 27,27,1666 23 if(ida(2,j)-2)22,212, 31 212 read flex 1901,(cap(i),i=l,6),al,mut 5J~+1 if(mut)27,1 666,27 c if + code, if 1 rerun, if 2 return to start, if 3 spike. 31 do 32 i=1,6,2 ka=4 cap(i ) ( (ida(ka, j ))*(ida(l 3, )))/1 00 ka=ka+l cap(i+ )=((ida(ka,j ))*(ida(l3, J)))/100 32 ka=ka+2 Jim=j j=j+l if(j-nut) 27, 27,1666 22 ka=4 k=1 36 if(ida(12, j)) 3434,30 34 dat(k)=ida(ka, J-ida(ka, jim)/10 ka=ka+l k=k+l dat (k)=ida(ka, j )-ida(ka, jim)/10 ka=ka+2 k=k+1 if(k-6)36,36,133 30 bob=((al)*(ida(12,j))*14.4)/35 3 m=1 kill= jock= jock+1 33 dat(k)=(ida(ka,j)-ida(ka,jim))/(cap(m)*bob) ka=ka+l m=m+nl k=k+1 dat (k)=(ida(ka,j)-ida(ka,ji-m))/(cap(m)*bob) ave(kill, jock)=(dat(k-1 )+dat(k))/2.0 kill=kill+l m=nm+1 35 k=k+1 ka=ka+2 if(k-6)33,33,133 133 write output tape 3,1011, ida(l,j),(dat(k),k=1,6) if (jock) 988,988,989 989 ave(1,jock)=dat(1) ratio 1, j ock)=are(, jock)/ave(2, jock) ratio 2,jock)=ave(l,jock)/ave(3, jock) ratio(3,jock)=ave(3,jock)/ave(2,jock) 01 11 format(i6,3h,6f 2.1 ) 988 j=j+1 if(j-nut) 27,27,1666 1666 if(jock)6611,10,6611 6611 write output tape 3, 2468 write output tape 3,4268

-313IV.3.1 Data Reduction, continued. write output tape 3, 8642, ((ave(kill,J),kill=l,3),j=l,jock) write output tape 3, 8462 write output tape 3, 8888, ((ratio(i,j),i=1,3),J=1,jock) 8888 format(3(6h,fl 2.4,6h )) go to 10 4268 format(65h cd pb cu 2468 format(48hi average values in nanograms per cubic meter 8642 format(3(6h,f2.1,6h )) 8462 format(// Oh ratios /66h cd/pb cd 1/cu cu/pb /) end IV.3.2 Calibrations for Raw Data Program ( Cd, Pb, and Cu) Starting Run Number! 952 -90o./ 100./45. /49 /48./68./0. 000127/23 O./O./o./ 9553 70./150./47./51./51./87./0.000127/23 o./O/o./ 0. o./O./O 9551 100./ /60. /79./64./59./107./0.000127/23 10661 90./230./6o. /111/69./200./0. 000127/1 7 1067 1 io./27C./53./91./60./209./0o. 0O127/17 1068 135./275./77./12 4./75. /257./o. 000127/17 1069 70. /27C. /6 c. /98. /535. /183. /,. C0,o0 27/ 7 1150o 50.,/9c.. /.57. /96. / 9. /244. /o. C00127/1 2 t1151 50./1 0C. /45./1 1:2 /81 /1 e80./0. oo00 27/ 2 1152i 5r../70./57 /71. /3./191./0.000127/12 1153 50/.4o./52./78./o. /232./0. 000127/12 1198 50/./80./49./91./76./222./0.0o01 27/1 1199, -60. / 90. /45. /69. 699. /77/0.000127/1 8 1200 6)./140o/42./92./50./126./0.000127/1S 1201 50. /15 3/35../ 6. /5./ 155/0. o 001( 27/I i 1266/ 115.2 5 o./7./1././29476./. C. i 7/,20 7( ~./''4./55./o1 C/.-45.; 5C0./0o..!c27/,0 (; * / 7 *' C) *_/ 1267 1.. 35 / /' 77 /21'.,/o oC. C 27/ 7'2,t /i 7. /, c. /5o. y /1' c/. /o. C;o, 27 /20 1268. 20, ",,:,,.,,,,,,, c1.U~~~~ t,/!', /'; / C * /i _5 /;'-t'' -7t; Q * { /.. / 1'_'9j, C-,....,' O,rteh Jnf!./ —f -t5^Z^O./O

-314IV.3.2; Calibrations, continued. Starting Run Number 1376'' 70. 265. /83./245. /217. /494./. 000127/32 O./0o/O./ 1377 1 65. /50o./93. /1 6. /104. /266. /0. 000127/32 15378 1 O./531./62./1 358./100./24o /0.0007 27/32 1379 130./60o./85. /92./ 25./345. /.00o 1 27/32 1500 155./355./90./215./156./367./0. 00127/9/ 1501 145./280o./92./246./] 1 3. /286./0o. CC127/9/ 1502 135./290. /67./ 42./ 01. /242/. /001 27/9/ 1503 205./230./56./131/,/8./189./0.000127/9/ 1557 1 25. /177./94./2(-7. / 6./289./0(. O 27/20 1558 1 48. /212. /1I /2 /)j. / i./294. /C.01 27/'20 1559$ 118./1 75. /89. /1 6. /1 4. /271.. /b.0ooo 27/, 1560 15 /2o8./76./157. /94. / /26./0.o C7 /20 1661 30. /75 /5. / 43l. i 1 /23. /0. 0001'7/ c 1662 5c0/130/. /130. /1 C 2. / o-. 20./.0c2 7/20 1663 85./.99./18./ /217 /. 0001 27/20 1664 9c. /I. /85 t178. /. /0o.00 271/2 IV..3 160-A Computer Program for Inserting Peak Height Cd Values Obtained by the Horrizontal Line Method into Raw Data Program. dimens ion ida( 1 3,4 ) pause 1 k-=:xflef (2,1) ~9 ~ pause 2 endf le 3 read input tape 2, 999 do 11 j-1,40 read input tape 2,1000,(ida(ij),i=1,13) 1000.formant( 15 6) o999 -ormat(//) if(xeof(v))10,11,10 11 c ont-inue 10 nut= —j-1.r.' t;e output tape 3, 1001 w^rite output tape 3,1002 1001 formatt('7h rim code scale peak area scale peak area scale Ipeak area vol spike ) 1002 formzat(78h ( no. hite hite lhite g /) 1003 forrmat(40i6) read. flex 10053, (ida(4, j),j=,nut) write output tape 3, 1000,((ida(i,j),i=1 3,),j=],nut) go to 9 end

-315IV.3.4 Raw Cd Peak Height Values Obtained by Ho rizontal Method. 0/6/ 0/20/18/15/15/5/10/1 4/8/11/11/ 0/9/18/-0/16 6/ 18/20/ 4/12/12/21/18/15/1 6/o/ /3/0/0/2/7/20/2/3/5/ /3/2/ -0/8/8/20/21 /19/18/0/8//10//56/6/5/ 6/1 8/16/1 /20/ 4/ -0/8/13///2/4/4//20/28/0/9/33/42/4/ 4/4./1/14/37/11 /0/14/6/7/53/47/1 3/12/0/11 /1 / 3/3/15/1 6/13/11/0/1 3/22/23/12/11/12/13/11/12/11/ 10/10/21/20/15/15/0/31/37/35/20/24/21/18/19/0/12/ 4/4/1 3/1 3/1/1 /1/o/1 5/i 7/1 7/1 3/11/ 0/1 /3/1 4/0/1 5/ 1 /9/1 3/18/1 6/14/9/28/5/7/7/12/ 3/9/1 5/1 7/15/3/10/1 7/3/9/3/5/ 0/i/6/1i /5/9/22/28/7/8/6/ 2/ 2/8/14/i8/1// 3/1 /7/14/3/6/7/31/ 0/2/9/12/2/5/5/9/1 4/1 / 4/8/1 0/6/23/ 4/ 7/ 2/8/1 4/19/8/i5/1'7/4/25 /27/24/2/2/7/-0/1 2/11/8/ -0/1 /7/1 08/6/7/7/9/1 3/1 4/7/7/21/11 /1 7/22/ -0/2/7/1 0/3/-0/11 /8/1 4/ 4/1 3/7/6/20/41 I 7/19/ 30/54/51/78/73/ 5/19/1 4/1 5/20/1 824/21/11/ 3/1 0/ 8/ 8/1 9//11/14/9/8 // 17/38/40/47/11/19/12/22/17/ 6/i 1/2/9/ 1/9/ 4/23/21/0/9/ 5/8/9/ 12/78//3/3/12/1 4/8/1 3/1 4/1 o0//2/6/7/6/9/24/0/8/1 1 /1 /7/7/ 19/36/37/13/14/21/18/25/16/18/16/10/8/1 3/1 4/19/11/0/9/ 1/9/10/ 1/41 /98/37/20/4/o/1 1/1 7/20/1 2/22/1 4/1 6/1 4/12/ 2/1 4/9/13/i /9/8/3/6/ /12/17 7/1 9/1 5/ 40/ 27/60/118/25/22/4/ 15/1 5/12/25/i 4/32/19/19/10/15/ 2/22/9/23/8/18/20/5/10 /7/1 4/20/27/1 7/47/ 1 3/35/'8/1 0/7/6/7/4/4/ 8/-i t/t/5/1 /6/4/5,1/77/'/'i 13/2/6/ 11/4/9/9/9/25/ 25/51 /1055/5/25/18/24i/1 3/33/30/36/19/29/11/26/I5/20/15/23/27/! 4/2/5/10 /14/17'26/33/1 7/4.1 / 0/22/53/31/ 4/16/117/ 7/26/33/7/41/ 0/9/38/45//22/5 /22/25/ 0/19/46/60/1 5/31/20/20/ 0/1 940/53/12/28/12/1 /

-316IV.3.5 Program for Calculating Correlation Coefficients

-317CGCC OIHIMENSICh A(e), e(6), C(6) T2-CCUZ CIMEMPSICU LIS3CC), k1(3o'U — I COC3 CIENSIiCh X(3CO), (3C0(J) W(300), U(300),XS(300), YS(300) ".CCt-C4 L9CI IEES ICh' TE(PFI6) LCCC DIlENSILN A (et, (: ) e,VAR(6, ) VAL (6'CCCt ClCI_ _ _ t'. LIN S N CCCE C IENSICh NIC S) C-C-E- L"TrA m "'C-C P- E CL -P s$c1 "/CCCC cr 1 i=t.R'rcn C' —~Z = —- T7 TO COil 1 REAC(5,1CC) (C(I,,K)tJ'l16) L012 — ICC'-'LP- "(ecP~I"C.' -T.......... C013 UC 2 I=1, CU14 -O l - - U-Cr-''-,TTY —----------- ---- CC15 tv(J)=C.O CC 1P. --- GJ ):= C017 H(J)=C.C CCIF- Vet1 ( J- I C' C CC1 _____ CC 4 K=l, O __ CUo I I'L I F - -— TJ7 ---— 1 —--- CC2 1 5 h(J)=.\(J)41 t — D 2 " ~ 2-.- V'-J ) TT-(' -I' -,J kT -- -- -- C023 4 CLNTINLE — L' 4:- 6',-' —- ------- CO. ~(J)=}V(J)/jA CCz7 TF:=([( I,,K-)-(<J))/V~ (J) CTt"iR (....'I'- -V T'' -- -''-'-'''. -' -... —. CCiS o CN'l IKLU.CC -- V/t( Jl}:C: ([/3j'77v - --- ---- -. —-IT!._'" COJ 1CC F l ( II, 1 X ( ), J xI 6):CC?. wF~Il'({,, 1) ('v\St (,), J=l~6~ -C -- C i.d' ~[ ftTH ] TM AI ['.I T7' f. IT Fr T —. —CC3 7 h1; 1TtV F,C ) -C...' 3-'e C' CF T{'//)........... —.. — 3-Fi.- - -......-....... —.-.. -....-.. -..... CC, CC 1 K =1, EC "C-^C-^(j.- -..- -.' - ---.... - -,-'- ji7 -.....- -'. - -...-`-. " "".... - ~.... —* ". —. —-.. —'.-.-cl-.- -....<c ] 1 IT~P(J)-(1l( i jw~)-PX (J) //~{Jd LC'3 13 1TIFP (J -C.C "CC-~................-~ —-TTCC1VT I, I'F............................................... cC~^, E CCh INLE CT4Z6 h...... F E( 1 EI- -.'Tr'r r FF F ) 3 — s --- T, --- C cq I4 Ce\1l I LE ____ CMD 2 4c -Z-TTNlt Ci41S hPITL(t,2C4) - r --. —.......-.FTrFrr..FTr. -". -F ——'R' —-—..-.... —. ——... ——. —.. —. —. —-. - CC.I IC c; I1=1l C:ZZ..-.......- -- ---. —. —.. ——.. —-1.-....- 6C2 -PTll({,4C1]) SS( I, h II) CCfr; _J =C

-318CCc DOC 1C J= 1, Xt -- KC — CC5E CEC 20 =1,:C CCS; - - -- — I',J KII v C ZCt(-K I It- - -tl CC60 2 1 IF(C(II,J, K )C2C, 22C Et CC.2,, j=JJ+ cc t3XKK = I IJK CC~. __ h (K t-)=C( I,I.C C" ernr ---- XS('JJ})(<i —---- C 6 t~(dS {C= (,1.) CC 6_ CS(JJILLL ): C'C / - C i-KKj=C.-'-, —. —. CC68 k<KKI=C, C -CC. -------- l JJl (' Lid=L K —--- —' —-- CC7 7C ( JJ =C C Tm ---— C 7 ML —- ----- -------- CC 72 CA.LL CCIRP (FC1 SL CF y,V ktUKK) TU2- J)..J)=K -- _._ CC]4 E(J)=SL tC L J I LT —-F —- - CC76 1C CCKlI CLE 1 tL IfhI1PLl-.i l J-1A, I- ---------- CC 7 khP ITE(,tCI) (E(J), j l,6) t.-T9 kVIE ——, Ztli I(CJ), J=i6b)' CCE0 CPLL CtP(, P.,SL,CF,>StywctUS,JJ) TCC'-1- - -T-'-"i 1' -r..n. -.'t.T —CP —-.-.... - CCEf2 C1 FCHM2i'T (/,Z ix, (t'.t 2 ) tCCJ ~~ —— T R "- - ~ — ------- -.. —-- --- CC, 4 S ICP LCLt — tt;A

-319GOOG1 StIBRCUTINE CCPR(P,C, SL,CF X,Y V,,N ),o-iME'~SN C,~ XUCC.), (3COJ, W(30),V(3O0;:COC'3 A^N IN -OCC5 S)t=C.CCCc7 St=OC.O CCC'; CC 1 J=1, N:TG —Y(J)-T —--- - - COil S>X=Sx)>+X(J )4 (J) "Ulz-.........5'"=sEx {x~ja(J).......'0013 vY=SYY+Y (J)4V J) C015 1 CChTINLE O -' 7-Ftl^ ---- T C —----- - - ---- C017 B= XAN* iX- >'SX -C 1TB8 - ET~:'iWSY,''T-3'VCC19 BCl =SCP RT( h)4B Y) C o02 - — RTTCF —-C — C0o2 IF CF=( SY*S>X- X_4S, )/E>X C C22 L - —.F^-T-T...-.. C023 SECHC.C CO2 —4 LL J:,,CC25 _L=A_(J)- __ _ CO26 XTF=~N J —'f(-..c CC 7 T),:YI- 1CP*P1 /E X X -CCZ8 ~ — --- ~~ """^T V^TUITVY T7 EY -- LC 0C C 1L CR= I It ) TTTM E - C031 CL=SC I (-C- )/ECT _ TJT2- -ETl7rn - -

-321IV. 4 HISTOGRAMS OF DATA

-322IV.4.1 Pass Number 1

-323PASS MreiR 1 IHISCtGRA A C^ F RIhIOS g/.u HIlSTCGI!AP f fTlOS tl/S.... TOTAL fAfN SAN EV I TOTAL P^ AN SIAN CEV PtIN PAN _ 17.11CB 0.LC7T 0.1251 0.0009 C.8C65 471.8081..4E61 9.5710 0.16 = 2.CCOO _ INTEPRVL VALUESs 0.0732.IN1EAL' VALUES' 5.7647 INTERVAL FPECUEkCV PERCENT INTfPVAI FECLENC' PERCEhT _ 1 ~ 0T b _ _ 1. I12 7 PCF. 50.?5 A. I 2 3, 45.3 l,. 12.s 4 15. 9.4 4 5. 512 5 7. 4,4 4 0I CsC 3- - - a, — - It- -- — C 6 2 3 -_. 3_. 6 2,__ 2.*3 2..L3 7 7. 2.3 q 2. 1.3 2.3 9 2. 1.3 0o. 0.0 1. 1. 0. 1C 0. 0.0 12 C. CC TfTAl TfTAL __ __ l3.C 159 s103.0 14C.00 hISTCGLRA CF Rf1r3 S CAISP2'_1 HISTCGPAm rf RTICS Pb/Ld TrTAL NMEN STANb UfV __ lh _ PX TTA. P EAN S.TAh CEV P-IN PAX.?.6644 C.. 1.65_J 0. 161 0.?.Cl1,_5 C.1C37.5..724 }, _1 46 L._!4 722 5.CCCC.lCCt.C.roO_ _. INTMFRIL VAlbES' G.CC53 IKTEPVAL VALLLESs C,4545: -FfV L FFRCbF^CY PEiCt ITE P ^AL \ FECLUEf C PEI CET _1....... __ C_. 0 0 1 ~ 00o 7 76. 48.4 2 67. 4C., 3 41. _ 5i.5 3 56. 33.5 4 IF. 11.2 4 27. 16.2...-......._ ____..._._.e _ _ __ _:. h 7. 4.3 6 4. 2.4 ".__:_.__,__.1..._. ___ 2........7_._ _. c*__ 0.0___. C. C.0 a O. C.C 9 1, C.: 9, C 0.0 10 1. C,6 10 1. C.^... _ _ _.-^ -_ -~.._ _ -. --- -.... _. - _._..._._ _ __ __ __ _ -- I 1.'3.6!C. 0.0 12 n. 0.c 12 O. 0.o.1..C___3. _. 6'___ TfTAL __TAL --- 161 lCO.C 167 100.0 148.00 161.00

-32 4-.HISCGRAP Cf PIOS P,/ =hSTA fi F f PilCS pt-/ TCTAL'pEA STAlh CEV 1l PAX TOTAL 0 - EAh STIA CEi Ik PA>: 57.9133 l.e17C 14.C742 C.o02. 1C.44,3 1 63124.67l.'530.5C1S 1C36.e.23 1.1C83 6CCC.CCOC ITEPVAL VALLES-'9.2203 INTERVAL VALLESs 599.228. TINTFPVAL FPRECUENhCV PERCEhT INTERVAI FPECUECV PERCENT.... {! _~._o.1 1......... ________________ 2 12C. 54,8 2 94 79.C 3 56.. 25.6 1. _ 4 - I. 1.8 4 ^..4 5 1. _ _6.8e __ S __ __ c..__ 6C 3. 1.4 6 2 - ~. 7 7 C. C.0 8 C. C.C 8 C. 0.0',, i 1.4 _ S 1. Cos f,____________________________1.4_________ ___________|j(________C8____~..0.8 1C C. 0.0 1C 1. 0.8 12 C. 0.0 12 1. o.e _ ~ s...13- - -.. J —..__... C__.: C.5-..._....... *_ t __ AL 1. -.CC. _____ _____ _ t_ _ S__. rTTAL (19 100.0 219 I1CCC 107.CO?cf.C HISCCGRAM CF RATICS PbI/P_.,ISTCGPA1 L CF;ATllOS /cd TCTAL MEAN STAN CEV_ If _ AX CA_.... EA S TAN E v _PI ___ _r A, 2.7. -..... _44C.C73 0.23 e5.._._9545 _ f75q, l7. J.7 1 5. 6.. ~^ 40C 112.CCCC INTEPiAL \VALUES C.7015 INTEPVAl VALES-' 10.1o CC INTERVAL FPECUEINCY PFFPCET "INTfPVAL FRECUEKCY PERCtNT 1 C. _ ___ C._ o.0...1 _.__..... I. 0__.6 2 R8. 37.S 7 13S. 87.4 3 74. 33.0 3 5. 3.1 4 30. 13.4 4 3. -1.9 _ _ ____ ____liJ__.._._ 2. __________~. 1.9_________ _ __ 6 13. 5.8 E 3. 1.9 _ __2.___ 7 _. 21 _____ 7 _ 0__ O, # e. C.9 8 1. 0.6 9 C. 0.0 9 1. C.A l C o(). C. 10 C. 0.0....... i_1 30.4.__ __. _..______._1 TrTAL C^ — rTAL _ _ 22j_4 100 oo.o 05S _ 1CC.C 189.00 139.00

-325-, HISTOCAP OF RATICS f.ulP _ HISToMAd IOF RT IOS''l-a TCTAXL PEAN $TA CEV FPIN PAX, TOTAL MEAN.STIN EV 1h PA - 241.7263 1.1129 3.5CE1 C.CC99 3s. 514 6549o.433' 64.3466 1 13 C.2553 91C.0000IWTERWAL ^ALLES- 3.5C56 ITERMAL VAlUES' - 56.S745 INIFPViL FPtCUEhY PERCEIiENT ITFPVAL FPfCUEkCY PERCENT.. ___.. __. 0.5 1 0.9 2 2C4. - 932 2 ee, 8153 4. 1.8 3 II. IC0.2 4 4. 1.6 i..._ -_-j ___ -._ it _ _ C.5 5 4. 3,7 - 6 1. 0.5 6 I. C.9 -...._....._______, 2__,, _i______ __7 7 0. 0.0 8 1. 0.5 8 C, 0.0 9 0.. O.0 9 C, O.0 * C. c_ - -- - ------ cO:n TAL -ice Ic — l. - TC -- t1 C. C.C ____ _2.______9________?C4.CO n-ISTCCRPA (f A7If1 Cu fP_ %h1S TCG.RAm cF A ICS f.______C ICTAL PEAt, SAP_ DLV Plh... T VAL. MFTN STAN CEV PIV IX... 5.C CJ...7C_._,.8__ o..,0 0 __?:.! 2,.CCC_ 19!c583?,0.. 2,._5 1._, Q.850__ S.42.6EcQ. O, ITERPVl VALLtF S.4533 INTEFtPV L VALUESr 60.9415 - INTERVAL'..FIECiJEihTC PER(CEI'l tRVtI-NT F hECIEh CY P:tCthT... -.-...1..............- 0.5..___.- —......1.. I 0.6 3? ]~ -1 2. 91.4, ". --- t. 37.9 — ------. —------ -- 3 f. 2.5 3 49. _.0.4 4 3. 1.4 4 21. 13.0 __ _ _.-. _5___0 _______._____ ____ __ _.4 _._ _.. Ce,3! 1.4 6 7. _.?___ 0. 0.0.__ ___...... 8 C. 0.0 8 3.1 9 o0. c.C q o. o.0 I o C. 0.C Ir.O 0,. _..... 1._._ _o___ __ _ _;__ C. 5 I 3_ _ o-.-_L -.-____* - c... _._ ___0. _.0 1? C. 0.0 1, 1..6 _.....t._C _. _ _._.. 0.6 _ TCTAL TCTAL 21 CC. C 11 10oo.0 192.00 1q43.0

-326HISTCGRAM4 CF PATIOS $f/PA,. A.l —- HISTCGPAM CF PATIOS $SF/ Xa.d _. TCTAI PEAN STA^ CEV ~ p l PFaX TOTAL PEAN STlJA CfV Pi PAl - _ 4n.00764 CI.94C71 0125 4.1923 37509.9062 30*9S9 436.O27 11.7333 212.CCOCINTEPAL VALUESs 0.36(7 INTEPAL VALU(ES 210.e2E7 INTFRVAL'FPECLEhCY PERCENT INTFRVAL FRECLEkCV PERCENT 1 c. o 00 _____C._. I. 8 46. 20.5 2 76.. 3 64. 28.6 3 21, 17,4 4 45. 20.1 4 7. 5. 5 25, 11 2 S 4. 3.3 6 16. 7.1 4. 3.3 I_7 ]_ [4 _L-_6.2 7 C. 0.0 8 8. 3.6,. 3. 2.5 q 2. C, 9 9 2. 1.7 I! I. 0.4 1 72 1.7 I; C. C.c 12 1 c.e 1 3 1. o,__ 4 TCT.- -.,_ TrTAL,121 100.0 -224. 1'0.C q 7.cC 21C.00 -.ISITCPRAM c ra fTCS SP/f.u oY.o l HISTYCGPAM CF PJlOIS Sf /Ci _ rclAL ___ MEh N_ STAN C _ ^_____paX ____-. TA..... T __._L f __.. STAK_LV P_ h P_ 1..413. 8.37.t4_.....9.__..C.C7,.7 ( 1 -_ l..... OF................ 8.....Cl.ga _ 1 _.5_CC_ INTERVP L VALUES 6.(C663 INTERI3l MtLLES- C.S423 INTEVAL F'HEC'UEhC1 -. FEPCEhT IKTFPVAL FFECLENCY PEPCEIT -- - -— 0 —. 1-^ -~ --— 0 e i! 1. S _ 1.2 i1'. 54.8 2 52. tC,5 ____ ____ 56. 26.7 _ lT7 1Sl8 4?3. 11.: 4 s, 5.e 5 5. _ 2.4 _ __ _._ —__ 2__ 4____ 4.7 -6 --- -4. --. - 6 2. 2.3 c_ _'.....__.*. _..........4.___..._..._...__. 7 _._ t.. 1.2___ _ 1. C.5 O0. a.c.. 0 5 3. 3.5 n1 1. 0.5 IC C, C.C II 0, _~_ __ UOU. 0U.0 I t ~ 1.2 -0. - ~. -M ---- -- - TfTAL 13 1. _. _ _86. l __ _ 1 — 00.0_ _._ Tcr al _ _ ____ 65.00 21C 100.0 iq4.0o0

-327HIST!CRA4 CF RATIOS _q/P&..H.41STPIAp OF PATIOS of'/. f,3'7,_"IA TCTAl. Eh SIAN DEV.PIN. PA__ X < TCTAL EAN STAN OEV Pl AN _ 1.2503 C.ClC! 0.C162 C.CC02 C. 121. - 1.5373 C.C127 0.C154 C.0005 0.C852 IhTERPAL VALUES- 0.0130 INTERAAI VAL.ES, 0C.C085 INTEPIAL.FRECUE~CV PEPCEhT MkIEVAIL FPEOUEKCY PEPC6AT ____1. 0.8 1 1, 0.8 2 53. 78.2 7 64. 52.9 3 _ 17. 14.3 3 _ q. 4.C 4 3. 2.5 4 1 12.4 5 2._ 1.. S 3. 2.5 6 1. 0.8 6 0 O.o 7,... __ 7 3. 2.53_____ A 1. 8 80. 2.5 q C,.. C.C.c _ 1. 0.8 o1 O. 0.0 10 1. 0.8 11 0. 0.0 ___1 0. *0.0 12 L 0C.8 12 1. 0.8 (oo......____......._____'__ tOPTAL, ___ 11 1 00.0 121 ICC.0 110.00 1 CR.00 ISTCCRAM CF PATICS S/~Cu _1.STCGRAi rf RATICS CPl. __________ _ 1CTAL ptha STAN CEV W!N IAX _AT C LA._...._ 6 ___ S__s1At CEV mi...__...', __ -AX.. J7.7.... _..5.C.. _C.CC.._. 2575? CS G151..2.. 233._ CLC..C.,.c.CC -0INTERVA1 6VALUES- lS.it l INhTE6tL VALUES C.0181i ikTTEPV- i FRECLETCY FERCENT I~tIEiRVAI. FRECUENCY P'PCENh..._...c.__- --- --- -.- __..... -- ~. ——........... -_-............}..................... =__ —........... 3 P. 7.4 3 21,. 1...2. 4 2. 1 4 4. 2.4 _.5....0_., _Co( _____.. _5....____,? 2~ 1.2 6 C. C.o 6:. 1.2 7 C_.......C........7............__.......0. R C. O.0 H 1. C.6 9 7:.').0 9 1..6 10 C. 0.0 10 C. C.0.....1.LL c. o.C I0 0. 0.0 12 1. 0.9 12 C. C.C 1 C0 1ft,.C TrTAL C4.o0.__________________C 155.OC

-328IV.4.2 Pass Number 5, 6% Significance Limits

-329PASS MMBBR 3 HISTOGRAP CF PMImC1S C C hISTCGRAP cF PAJOS TOTAL PEAN STA ~ CEV MIIN PA TOTAL PEAk STAN CEV PIk PAX _. 12C9 C..C514 C,4Q7 C.OCOS C -1436 52.9969 0.636 C.6C38 0Q.117 2.3333 INTEPAL VALLES- 0.0143 INTEbVAL VALLES- 0.277C INTFRVAL FFECUiECY PERCENT INTFRVAL FPRCUENCV PEPCENT __I 1...., O, I 0,_ (_,0, 7 21. 1ft.S 2 12. 21.8 3 14. 11.3 - 9.16.4 4 1i. 15.3 4 S. 16.4 5 14. 11.3. 6 12. 9.7 6 8 --- 14.5 ___?_ 1....__. 7 4. 71.3 8 12. 9.7 2. 3.6 $ 6. 4.8 3 5.5. IC 4. 3.2 10 1. 1.8 11..._ __._ -5 _ TAL _ 12 1. 0.8 55 64 100.0 _'T, __ 1S.Ca 124 780 10o.0 I 12. -l HISTCGRAM CF FAIICS CdLSP- h bISIVGRaA CF RIICS bleCd l^CTAI __FAN STAN CtLV _ I ___I.P A X AL N__ STAN CE PI ___FI NpA.SC.076h 0.0C63 Cc.CC4C __.lC C.C1 61.15.197,927tC.75'1 60.5136 5.OCCC _231.2CCC Il........T__OF~L.....PE___.f__ $AI~ Cl5'~ _J!h IbTERr l VALLEtSt 0.o015 INTFRAlI VALLES e2.62!C TEIkVAI. FPRECUEhC PERCENT INTERVAL FRECUEFCk PEFPCENT i o, 0...._._ -..!^ -.......... -- -... —.- —...- -.^. -_-. _._.. _.~_._. -- _.._.-. 3~~0.___C _ __. ___ l_______.C 2 1C. 9.? 2 11. 7.8 13 5: C.1 3 19. 13.5 4 le. 16.5 4 le. 12., 5. _......C_....5._ ___.. __5. _.......... - -.-.. —....-.-.. 3*..... - - Z7n.__ _.___._ _ ____ __...{-_.. _.. _.2...... _.....___ 13,_ _._ _. _ _ _ s.....2_ e. 8.3 8 13. 9.2 9 te. 5.5 S 13. _, 9.2 I0 1r. 9.2 10 6. 4.3.1..._.... __ _ 4,6_ _.. 11 1 I I. 7 e 12 2. 1.e 12 1. 0.7 ~es< -9 ltIn.o 141 84% 100.C S6.CC 114,.0

-330HISC' RAA# C RBIT1S PblNS u.. -...: ISTOGRAP OF 8A1105 PIOS. S TOTAL PEAh SThA CEV Nlk pA MTOTAL PEAf STAN CEV P NI PAX _765.14;3'.C33E 3.9483 C.0259.13.125C 5524.3359 871.687 43.44449?.7Ce 3 18 e,671 INTERAL %ALLFSm 1.3099, INTEPAI VALIUES- 1 — IS.8 INTERVAL FPECUEhCY PIRCEhT'INiTPVAL FPECUENCY PEiCENT 1 1, C.7 __ 1 0. - 0.0 2 32. 21. 2 6. 9,5 3 19. 12.5 3 7. IL.t 4 24. 15.8 4 12. 19.C I 1. CC7.9 h 45.S6 S.;4 —- - -- - ---- ~8 6. 3.9 A 12. 19.0 9 9. 5.9. 48 1C 12, 7.9 10 l. 1, 11,L__10. 6.__. __ AL _____ 12 1. 0.7 63 5% 100.O i.. -._...._. 5?QQ9.00 _ _ 152 69, 100 0 1 26. OC _,.!e__.c_ _. __ ____ -____- ----------— ___________ HISTCGRPAP CF FATIC S P /SP %_,, ISTICRAP CF PRAICS Lu /rd Tr'TAL PEAN 7SAN Ct: IN 1PA. TT__.......P._.._....STA N C E.V PIN PAX 1....... 29:. C... C C.. 3?, 22.................l......7.,_197_L..., 1. LC 4.C.CC IFTFPVlP L VtLLES 0.1143 INTERVAL VALLESw 2.7teC INTERVAiL FECUERCV PERCENT INTFRVAL FRECILE IC~ PfEPCEKT I Co. 0.0, -----— _ C.C 2 21. 14.3 2 12. 10.8 3 16. lG.S 3 It* 1j.5 4 16. 10.9 4 e8. 16.2 5_ ___ 14. l.5 5..... —___ 13.5 6 137. p.8 6 13. 11.7 7 2 2. __ _____ __ __ 1 7.._ C. P 8 IC. 6.8 a 5. 4.5 9 6. 4.1. 7. 6.3 10 11. 7.5 10 7. 6.! U ~ _......L_._. _.i 17._ i__1.6 I]_ 5I,_- S. ~.5 12 1. C. 7 12 2. 1.8 CT. ______T... 1.... 10___L____ 147 669 100.0 III 7o 100.o0 14C.OO' qq.00

-331HISTCGRAP CF PAlICS.-I., HISTCGRA~ CF RATICS aj^,tr TOTA - PEAN STIA CES Ni _ PA N^> TOTAL PEA ST^A EV, PIt. PA^X 9.,5s5 C.C765 0.C394 C.C.99 C. 183 8C4.C?74 11.6531 S.5e67 0.253 i,78CC INTEPRAL VALLES- 0.C148 ITFPVAL VALLES- 4. 18e INTEPVAL FPECUEkCV PERCENT INTERVAL FPECUEICY PEPCEhT - -— I —... —- e........ _ -. 1.4 2 S. 7.2 2 21. 30.4 3 9'. 16,0 P 9. 1.0 4 13. 104 4 15. 7 5 17. 13.t 5 5. 7.2 6 le. 1414 6 4, 5,8.7 I 1.... 12.0 It 6. e 8 8. 6.4 8 2. 2.9 q 7. 5,6 9._ 7.2 IC 7. 5.6 10 1. 1.4 _.. _ 1O. s.C -_. ____ TAL. _........ CT AL__ 12 1. 0.8 6S O4 Il'o.u. L-___- ___ - _-._ _. -_-_ —-__ 12' 57! 100.0 r_ _............_... _....... _.. _ _ _. HISTCGRAP CF PFIICS Cu/SP' HISTfGRAP CF PP11GS SP /C y, o. TOTAL PEAh _ SIAN CEv PIN I__ A......J.L_._ t A _ STAN CtV IVI. P.A_..... 9......C.1335 O.c? C. _ _. C?2 _ 94 3,7,.63.._ 66.4_,A_.A, _ 6 1.n. 1.! INTFRVIl VALLES O0.0276 INTEfVAL V\LLiS- 1. I 4t. _..__............... _..._ _... 0 _. _._ I TERVAL F~tCU~ A CE PRC~hT INTEPVAI FRECLFKCV PECEW __,1___'. (. __.__. __.____ __ t&..__2............ ____0___; 17. d.1 2 J13, lo. 3 3. i1.4 24. 19,0 4 17. 11.4 4 14. 11.1 5. 15.4 A.C. 14.3 22. 14.E. 13. 10.] 7 10... -— 7. —---- 7 6____.. —._- -___-........ P 13_ _13. 8.7 P 14. 11.1 9_____ 1,, E8.7 9 10. 7.9 10 5. 3.4 10 3. 2.4 II 1_. 6.7 6. 3 J ____ 111. 3__ 12 1..7 12 1. 0.8 14S 71% 100.0 126 78% 100.0 1 ^3. rr __ ____ _ _ _ _______ ___ ______i??. cc ___ ___ w_____________._ __'- ~ ~ - ~ - --' — ~ - --

-332HISTCGRAP CF OilIS SPIPb HIn.ahlJ hISTGC6AIP F PAICS $S h Jl.a 1TOTAL PEAN STAN CEV lh PAX TOTAL EfAk STAN DEV PIN PAX 90.1424 C.662e C.2399 E.23i 1.CS55 225.5195 15.1322 42,1723 1.1733 Ief.15l I1TERVAL VALLES- 0.0842 INTEf AL VALLES- 10. 151e INTFPVAl FPECUENCY PEPCET'INTERVAL fRECUEICV PERCENT.L...._ _,0 0.0 _ ____i ____________________________. 1.0 O.c 2 IS, 9. 1..0 2 9 3.0 3 12, 388 3 1_~*_j _ 4 14. 10.3 4 12. 11.4 r,__ _ _ 13C.,. 6 k15. 11.0 0 14. 20.3 7 2._ _...7-_...* 7 3.. 4.3 _ _ _ 8 iC. 7.4 8 20 2.9 1 ~~~ ~~~~~ ~~~~9 8. 5.~~ ~~9 ~ 9., 1.4 IC 16. 11.8 10 8 11. t1 C.Io_____ 8* -_ _Loe. - l.-JI 1.. j.... I. _ e.e It. 1.4, 12 I. 0.7 TTAL... 0........ T' 1C__ 136 61A__ O1.0 62.00 127.00 _ ISTCGIAP CI- AIICS SP/u Xld.dr hISTirCfAP CF RATICS SICJh i(. TALt IAh SThAN CEV_ PIN PY__ TUTAL E. AN STA CELV _h _ PX_ 5PI..C?2 4.. J.11 _2.t46.O.C1Q___~ 3e. 2.C137.cE. 6_ c4. C.C12 1. 125') INTrERVAL VAAlfS - 0o.e7CC IhTEVL VALLES. C.13P? i-TF PVAL F.r -LF tKCV PERCEKT J TFPRYL FPRCUEN( C PEPCENI I........ I....-..1_...i..^ -..o _. _............... —. --- —. S3...... 7 2 23. 15.9 2 19. 31.7 3 9..2 3 9. 15s. 4 17. 11.7 4. 5.C._... -4.-... - - - -_ _.3........ 1.1..71.. -~.'a.3........... t It. 12.4 6 5. 8.3 7 1115 7. 11.7..? __............._.._ _. _ 1 t7 7.... __._..___.__.__3 __ ______ P Ini. (6.9 8. 5.0 1 1il. 7.6 S.,.3 1 14. 9.7 1C 2. 3.3 1......7 6l.1. 7.?.- TCTAL 12 1. 0.7 6t 7f 100.0 T:IJ... __ --..-.- __.._.-1._____ —__ 145 699 1]0.0 14,3.oC

-333HISTeGRAP CF RATItS i H/P IS-CGRAP OF R TIOS l/_ P..a - TOTAL EA6N STANI CEV "IN MA ACTAL MEAN STA. CEV p N - C.3696 C.004! C.CC33 C.CCO2 0.0111 0.4075 C.0050 O.C031 C.CCCS C.C124 - INTERUAL VALUES- 0.0012 INTERMAL VAIUES- C.CC13 INTEPVMl -FRCUENCY PERCEkT INTFIVAL FPECUFhCY PERCECT 1 tl.o12 1-0, 0.0__ 2 1. 22.1 2 18. 22.? I 4. 1lt.3 3 16. 19.8 4 12. 14.0 4 1. 12.3 3___ __I. a_. ____ _________ _______ 6 5. 5 6 12.. 1 —-. I 10- 7 1. 1.2 -~ 8 < 5.8 8 3. 3.7 9 g 4. 4.7 9 4. 4.9 -6-. -.C M1 10. 12.3 _~_UI____ __ _ 1...1112 1_: TC'TAL. —-.. TfTAL 6 100.0 p[ 67/! cc c'-70.'Io" 72.00 t.ISTCCRAP CF PATICS 50/2/t.a,ISIL:I;AM CF PAICS Ci/,-PA - IC.TAL_ PA. STAN CfE PI/_P C, PA TC~ TA -..... _ S.TA. CEV....C A-.__2s.?A~_~_IL..SeLQ'ifS i 4.iCC C. li1I I C-,715~'.2CC17 J.CC21 C.CC24 C.C 11iTER-vAL VALLES= 0.3122 INTEOVI VALLES= C0.0 C 1 1. 1.3 ____ __ _1. 0_... _.. C.........C.-. 2 22. eA.E 2 12. 10.6 3 12-. _ 15.6 - 13. 11.5 5 1_ 9.415.6__~________ - 7__.5___ 18. 14.26 — --— 6.~ 7.P -1 9.7 _.__ _....A._.L.-. -...........- ^........ _............8I. 8. 9 7. q,. 7.1IC 5-. 6/.5 10 c. c ~TOTAL ~ 12 1., 7OTL 7 I.0 9,7L7.OC -113 7.7 I, 8c c.0,_________7o _____ ______________iZ12.00___

-334IV.5 CALIBRATIONS AND RESPONSES IV.5.1 Finding Calibrations and Correction Factors The calibration factors used in the computer program are obtained by either (1) running a reagent plus blank sample then adding a spike and subtracting the former from the second run, or (2) by adding two successive spikes (100 ng) and subtracting as before. This is done because the first spike run must contain the proper amount of acid and therefore the blank aliquot is the best source of a near sample run. The additional signal from the second run is due only to the spike and not to carry-over, cell contamination or blank. This is usually called standard addition calibration. This procedure is instituted prior to running the sample sequence of blank + spike + reagent, and then running a subsequent sample as mentioned before. An initial accurate calibration is provided as a starting basis for data reduction and scaling for the computer. As we have seen, the cells can deteriorate at a nearly constant rate over reasonable time spans (see section IV.5.3). The method employed to correct for the decrease in response is to take the first calibration numbers and use them as standards and add a correction to each subsequent run. The details of the procedure are as follows: Draw a graph for each spiked run in sequence. Draw a best-fit straight line, neglecting large deviations as these are usually caused by contamination and/or carry-over and are not usually due to cell deterioration. Find the average

-335decrease in the standard units per subsequent run from the straight line graph to obtain a percentage decrease per subsequent sample runs. This midpoint should be calculated from the initial calibration value as used above in the first calibration. (One can do this for all elements and methods and arrive at an average percent.) Take this percentage and multiply it by the number of runs the data point is removed from the initial calibration point, and increase the value of the data point by that percent. A typical value would be 5% per data run. These results are shown in Table IV.5.1. This procedure improves the data points so that the accuracy of the data point is more dependent on the original calibration values and less on carry-over and cell deterioration.

-336TABLE IV.5.1 % DECREASE PER SAMPLE RUN Starting Cd Pb Cu Run No. Pk.Ht. Area Pk.Ht. Area Pk.Ht. Area % 952 4 - 4.7 6.7 5.1 5 5 953 3.1 7.1 5.1 3.6 4.9 5.1 4.8 954 - 10 3.9 3.9 5.8 3.1 4.2 955 - 1 3.6 3.2 3.3 2.9 7.3 1066 - 6. 4.7 5.7 2.8 4.3 4.6 1067 - 5.9 7.9 3.3 9.5 3.5 6.0 1068 - 13.5 6.1 2.5 8.3 4.1 8.3 1069 - 4.8 4.9 1.9 (19.3) 6.9 4.6 1150 - 12.5 5.9 6.1 10.9 2.6 7.5 1151 - 12.5 9.0 9.6 9.0 3.8 8.7 1152 - 5.9 15.0 17.1 10.4 11.4 12.2 1153 5 1198 - 15.9 1.0 2.9 2.2 1.4 1.9/4.7 1199 - 16.7 4.2 3.9 7.4 7.3 7.9 1200 - 5.5 5.2 4.2 14.8 4.6 7.0 1201 - 2.1 0.8 1.2 1.5 3.8 1.9 1266 - 4.2 2.2 3.6 4.2 2.8 3.4 1267 - 1.2 1.9 1.4 1.7 0.6 1.4 1268 - 2.7 2.7 3.0 2.9 3.0 2.9 1269 - 0.8.3 1.8 4.2 1.3 1.0 1376 - 1.7 2.7 2.2 2.8 1.3 2.1 1377 - 2.0 1.4 0.8 1.4 1.1 1. 178 - 2.7 1.8 1.4 1.7 1.4 1.8 379 - 2. 1.0 1.0.o 1.7 0.7 1.4 1500 - (8) 1.6.6 3.2 1.2 1.6 1501 - - - - - 1502 - - - - < 1503 - - - - - - < 1533 - - 1.1 0.1 0.5 0.7 0.5 534 -0 0 1.1 0.5 0.4 1555 - 0.4 - <.5 156 - 3 0 0 2.2 0.6 1.1 1661 - 0.1.3 2.3.3.2.9 1662 15 (15.6) 2.8 2.3 3.5 2.2 2.6 1663 - - - - - <.5 664 - - 1 1.3 2.6 1.2 2.0

-337

-338IV.5.2 Sample Calculation

-339IV.5.2 Sample Calculation ( T Area Used _Aliquot a -Total Exposed Area Total Amount of Solution Equivalent Volume = (al)(Flow Rate)(Time) = (m3/min)(min) 3 = m Calculation for Run No. 1008; Variable, Pb: /.2 in2 0 aliquot = ( i of filter paper 100 of solution 9 X 7 in2 2 ml 0.000127 parts 3 volume = (0.000127 parts)(59.0 ft /min)(24 x 60 min) 35.3 ft /m 3 0.306 m From peak height: concentration = 32 units on a 100 pa scale concentration = (0.306 m3)(45 units/100 ng on a 100 pa scale) 3 = 236 ng/m3 From peak area: 81 concentration = (0.306)(49) = 541 ng/m3.

-340IV.5.3 Sample Plots of Spike Runs 1-4 The following plots are curves similar to those from which the percentage decrease in sensitivity in Table IV.5.1 were calculated (runs No. 1835-1912).

-341600 ~t u Pb 3 E 300 i - I ~ Li_ < 100 \Cd LU\ 60- o 0 ~30_ 60 0 12 3 4 5 6 7 SPIKE NUMBER Figure IV. 5. 3.1: i:ikLe r'ur., i:8,-L:L"?,': Ce:-ll L.

r r-E / I IJ'A4 0* (/ HO E' l Ell |C | CI1 II II.i-i. Cl) co LO CN)c) 0 0 0 0 0 0 0 0 0 -( w r - ro wW 1H913H >V3d

-343600 300 0 _ _ O 100 <a 60 0 30 0 0 10- o\o -_,, i!, I I I I I 12 3 4 5 6 7 SPIKE NUMBER Figure IV. 5.3. 3: pike runs, 3t 9iL, 8 -.;-.

-344100 60 E E 30 w10 aw 10 6 o0 O 1 2 3 4 5 6 7 SPIKE NUMBER Figure IV.5.3.4: Spike runs, 1835-1912, Cell 4.

-345IV.5.4 Sample Calibration Runs The following six tables are samples of 10 minute calibration runs using four cells abstracted by both the peak height and area methods. It is obvious that the area method is noisier and thereby less accurate for the lower values (say less than 3 pgm/10 ml of solution).

-346* Cells I x 2 300 3 + 4 E X/' 60 0 1 I 30kI 0 I0 30 60 100 200 Cd,ng Figure IV.5.4.1: Sample calibration runs, Cells 1-4, Run No. 952-, Peak Height, Cd.

-3476 / 7X <t 1.0. I - w Ox Cd9ng.1 1 |___________________________________ 0 30 60 100 200 Cd,ng Figure IV.5.4.2: Sample calibration runs, Cells 1-4, Run No. 952-, Peak Area, Cd.

-3 482000 1000 E600 E / w 300- Ld 0 / / a3. l00 60 ~40__.... L I. I _1. I.......I 100 300 600 1000 2000 Pbng Figure IV. 5.4.3: Sample calibration runs. Cells 1-4, Run No. 952-, Peak Height, Pb.

-3L920 10 I _ 6.0 0,_ i < /y~x.6 i _ _ _ _ ii' 100 300 600 o000 2000 Pbng Figure IV. 5.4. 4: Sample calibration runs, Cells 1-4, Run No. 952-, Peak Area, Pb.

-3502000 1000 E 600I / r~~~tn~Clng L, 300 LU OL 60 100 3:00 600 1000 2000 Cu,ng Figure IV.5.4.5: Sample calibration runs, Cells 1-4, Run No. 952-, Peak Height, Cu.

'rd'asV Fag'- 6g,'o *fr un t'-T s-[TToD sunn. uoT!.a qT'[oe a-i ctus: 9S''S'AI ans TJ 000 o0001 009 00 001 O.-.-.-. _~ -. —-- -- --- I I I I 4 19 ~~~I~~~~~ ~- -9'0U 0/ 01 XI /OZ -I,'.. i~~~~~~~~~~~~~~~~i,,,/... i~~~~~~~~~~- +-/

APPENDIX V ANODIC STRIPPING VOLTAMMETRY —THEORY AND OPERATIONS -353

APPENDIX V ANODIC STRIPPING VOLTAMMETRY —THEORY AND OPERATIONS V.1 DESCRIPTION OF ASV AND BASIC THEORY V.1.1 Description of ASV Anodic Stripping Voltammetry is not a new technique of analysis for trace metals. However, certain modifications were made by Matson (1968) which allowed an increase in sensitivity of about 100 times for metals forming amalgams with mercury. The basic theory is that the ions when plated into mercury diffuse uniformly into the mercury medium. However, if the mercury medium is too large when one strips or reverses the polarity slowly, the diffusion time is so large that the response is quite slow and the resulting peaks are broad. With mercury plated on the composite graphite electrode in very small droplets, the diffusion time is increased markedly with the metal ions being able to diffuse out of the mercury droplets quickly, forming sharp peaks and quick responses. Figure 2.6 of the text is a sample stripping response curve for some of the mercury soluble trace metals. Figure V.1 is a schematic representation of the external electronic circuit. Most of the circuitry used in this study was from the Heathkit Company, Benton Harbor, Michigan, with an additional modification in the switching arrangement to allow four modules to be operated in sequence. -354

-355V.1.2 Theory of ASV Operation The purpose of the following section is to present a brief description of the steps and a description of a simplified theory of a plating-stripping operation. No attempt will be made to give a complete description of electrochemistry as used in this study; it is suggested that the reader refer to basic texts such as Nicholson (1964). Figure V.1 represents a description of the ASV cell and circuitry and the plating and stripping steps are explained as follows: 1. The Plating Step: In stripping voltammetry the plating out is hastened by the stirring which brings the ions into close proximity to the test electrode. A large fraction of the total amount of a trace metal in the sample is concentrated on the test electrode. This amount plated produces a measurable faradaic current when it is stripped off rapidly. We should be aware that the systematics of the electrochemical series often do not carry over directly to stripping voltammetry. For example, stable complexes require more energy than simple ions for cation reduction. Also slow kinetics of electron transfer leads to a requirement for overvoltage. 2. The Stripping Step: The sharp rise of a stripping peak is, to a rough approximation, explained by examination of the Nernst equation. The Nernst equation governs the shape of the peak's leading edge.

-356Figure V.1 Simplified plating circuitry. Key to Schematic Diagram: 1. Operational amplifier with infinite impedance and input terminals actively brought to ground. 2. Ag-AgCl reference electrode. 3. Test electrode (mercury on graphite). The potential at this electrode is -EBias with respect to EAgg which ~~~Bias -Ag-AgC1l is +0.222 volts on the electrochemical scale. Therefore a plating potential, E = EAgAgCl - EBias' is established. Electron transfer reactions occur at this potential. (For example, the trace metals are reduced and plated, e.g., 2+ - Cu + 2e + Cu.) These electron transfer reactions cause a current which flows from the counter electrode (see 4) to the test electrode. The current (base current) thus depends on the concentration of the reducible materials (e.g., trace metals, residual oxygen, and H+ ion). 4. Counter electrode (platinum wire). This is the site of the oxidation reaction (e.g., 2C1 + Cl2 + 2e ). The potential of the counter electrode floats and is determined by the current which it supplies in balancing reduction with oxidation. The reference and counter electrodes are isolated to a degree by Vycor* plugs with holes of diameter forty angstroms. These are penetrated only by diffusing ions. Therefore these electrodes are not affected rapidly by differing sample composition. As the mercury film of the test electrode becomes channeled and depleted, the associated double-layer shorting capacitance increases. This results in a higher base current. Trade name by Owens Corning.

-3574. E 3. 0 EBIAS. Figure V.1: Simplified plating circuitry.

-358For example, RT Pb E = Eo - 2.3 R In Pb, Pb where: Eo is the standard potential, the electromotive force for the cell in which the activities of reactants and products of the cell reaction are each equal to unity; n is the number of electrons transferred per molecule; F is the Faraday. Now 2.3 nF 30 mV. Suppose, at the start of the stripping Pb step, E - Eo = -90 mV. Then In Pb = 3. As stripping Pb ++ progresses, the concentration of Pb increases rapidly. That is to say, for Pb E - E = -30 mV, In Pb 1 Pb Pb E - Eo = 0, in P+- = 0, Pb E - Eo = +30 mV, in Pb = -1 Pb The trailing edge falls because the quantity of trace metal is finite. This edge is also influenced by diffusion of trace metal out of and away from the test electrode. V.1.3 Description of Physical Cell Design and Modifications Matson (1968) in 1968 brought to the University of Michigan Department of Meteorology and Oceanography his design of the mercury graphite composite electrode. Since this was a

-359laboratory version consisting of several pipe stands and many wires and tubes strung about, and since there was always the danger of dropping the vials from the test tube clamps mounted on the ring stands, it was desirable to redesign the cells into a smaller, more compact and modular configuration. From this initial laboratory design the cell has been further modified and reduced as was presented in Figures 2.4 and 2.5 in section 2 of the text. The cell modification consisted primarily of drilling a hole through the electrode to allow a small piece of plastic tubing to be passed into the electrode. The tip of the graphite electrode was pointed in order to improve the stirring configuration of the electrode and to facilitate the more uniform and repeatable dissemination of the nitrogen bubbles which are used as an oxygen purging agent and as a stirring agent. An improvement patent has been applied for. Figure V.2 is a cut-away drawing of the cell with both a holed and solid electrode and, in addition, a schematic of the equivalent electronic circuit of the cell itself. Holed electrodes were used throughout this experiment.

EQUIVALENT CIRCUIT CEIL CROSS SECTION REPRESENTATION -Ag Wire -Graphite -Wax(Hg) P Pt Wire 1 ^^ r~I ~Ag o^"^\\^^ ^ ~\ UHg 0 Vial- a ~~~~~~0 0 0 0o o0 0 Vycor Plug Polished 0 Sample Soln. Hg Surface 0l N2 Gas HOLED ELECTRODE SOLID ELECTRODE Figure V.2;.Celi cross section and equivalent electronic circuitry.

-361V.1.4 Comparison of Holed and Solid Electrodes Three solid electrodes were prepared for comparison. One was 1-1/8", one was 1", and one was 1" and pointed. The fourth one was of a modified design (holed) as shown in Figure V.2, and was 1" and pointed. Gas was provided to the first three electrodes by tubing in the solution as before. From Figure V.3 we see that there is little variation among the electrodes and that the charging is comparable. The advantage of the holed electrode is that the stirring configuration remained the same from sample to sample with less danger of contamination and of bumping the gas tube. The disadvantage is that they are more difficult to make. Sensitivity was checked by adding a lead standard and repeating the runs several times. The repeatability is good for both the charging and the spikes. The same spike was used in the repeat runs without changing the sample.

-362lOOng,Pb 10 Min. -o 0 -bl0 0 0 jL) II A A AI 60 o B _ L — A N z K Charging Voltage ^ 30- 04 0 z 3i * 0 0 w A A A X A] X X X AA AA - 0 |0 I TI X M 10 20 30 40 50 60 TIME — > MIN. Figure V.3: Comparison of holed versus solid electrode response.

-363V.2 OPERATION OF ASV APPARATUS V.2.1 Stripping Potentials The elements are stripped in the following order, beginning with the highest plating voltages; hydrogen, zinc, cadmium, indium, lead, copper, bismuth, and mercury. (In chloride, see Figure 2.6.) Of these zinc, cadmium, lead and copper are found in large enough quantities to be far above that of indium and bismuth. Thus, four peaks are usually observed before the mercury strips. (The location of each peak relative to the voltage is variable according to the reagent used, the acidity, and the characteristics of the cell.) Usually for the chlorides, a stripping voltage of 1.1 volts is almost into the zinc plating potential. If the acidity is high this voltage may be too large and hydrogen evolution is started. See diagnostics 6. It is suggested that one try a few quick plates of a few minutes to find the plating potentials of the metals starting at about 0.8 volts and increasing to the zinc peak. Do this with 100 nanogram spikes for best results. V.2.2 Preparation of Hg Use 0.4 g of reagent grade Hg. Measure into a 100 ml volumetric flask, and add 5 ml nitric acid. Heat in a hood and dissolve the Hg. Equilibrate to 100 ml. This results in 2 x 103 molar Hg. 200 X of this solution will result in a -6 2 2 coating of 0.5 x 10 6 M/-cm on a 4 cm surface if entirely plated onto the electrode surface.

-364V.2.3 Preparation of Spikes Spikes made from reagent grade materials are probably the easiest and least likely to be contaminated. The metal is weighed out in a reasonably precise manner, such as on a micro-balance, dissolved in a few milliliters of nitric acid and equilibrated in a volumetric flask with twice distilled water. For my experiments the following procedure was used: One gram to the nearest hundredth of a gram was weighed on a micro-balance. For the powdered metal the job was easy, but for the solid and pellets a file was used to subtract a little from the larger piece to get the right amount. The metal was dissolved in nitric acid and equilibrated to 100 ml in a volumetric flask. This was to be the standard. One milliliter was pipetted from the standard flask and equilibrated to 100 ml in a second flask, again with double distilled water. One milliliter of the second standard was taken and equilibrated in a third 100 ml volumetric flask. This was the final standard and contained one microgram per milliliter. Standards for all the metals were prepared in this way. The secondary standards were prepared from the first standards every two to four weeks. The third dilution was always prepared within 24 hours of the runs in which it was to be used. For this work, a combination standard was prepared containing 100 ng of lead and copper, and 10 ng of cadmium. The cadmium standard was less, due to the low signal to spike ratio of cadmium in the samples. See running procedure.

-365V.2.4 New Cells New cells are usually heavily contaminated and need to be cleaned. A good rinsing with distilled water and a little nitric acid is desirable for the cell electrodes. Be careful not to damage the silver wire and the solder on top of the cell head. Be sure to fill the glass electrode compartments 1/4 full with reagent before attempting to plate, and clear the gas from the bottom of the compartments frequently by gently flipping with fingernail with the wires partially removed. (See section V.2.9, diagnostic 6.) A syringe is probably the best way of getting the reagent into the glass, but the reagent may need to be jarred to the bottom. In some cases, the Vycor must be activated by blowing into the reagent charged tube and forcing the reagent through the Vycor plug. The cells should be almost filled with reagent and plated for a few hours, stripped, washed, and the reagent changed. One to two days is usually enough for most applications, but more time may be needed for extremely sensitive analysis. V.2.5 Plating of Mercury For optimum performance the concentration of mercury on the graphite electrode should be 106 M per square centimeter of exposed graphite surface (Matson, 1968). Theoretically, one should add enough mercury solution to the reagent and wait for an hour or so to get the desired concentration. However, it has been found that the mercury does not always plate on to the graphite surface as quickly as desired, especially if

-366the stirring rate is slow. For this reason, a visual means of inspection is desired for, at least, a good cell performance, if not an optimum performance. Irrespective of the plating times and concentration added to the reagent, the electrode should not have any shiny places on the exposed portion. The mercury should cause an obvious dull grey or "dirty" surface to appear, but not a much heavier whitish grey appearance. In most cases the latter problem of too much mercury is easily controlled by never adding more than two to three times the optimum amount to the reagent solution. The amount of mercury added initially is dependent on the original condition of the electrode surface and the time allowed for the plating to take place. If the cells have been plated before and have Hg on them, then only a little is needed. If they are new or have been refurbished or well wiped, the near optimum amount is needed. Also, the shorter the plating time the more Hg one should add to get the minimum coating. It should also be pointed out that the slower the Hg plate, the better the stability of the electrode surface. In addition, the bubbling can also cause some streaking on the electrode surface, and some bubbles tend to stick to the exposed graphite areas. For this reason, it is suggested that the following procedure be used. Aliquot the optimum amount of Hg solution into the reagent. Let the stirring continue for about 15 minutes. Turn off the gas and jar the bubbles from the electrode

-367surface. Allow to set over night at about 0.4 V, or just below the stripping potential for lead. Turn on the gas in the morning and allow the solution to equilibrate and mix for a few minutes. At the same time, turn the plating voltage to about 0.9 V and plate out contaminants for several minutes, then strip. You should be ready to run. The solution is usually contaminated and should be thrown away and the electrode washed with distilled water. If, upon inspection, you see a mottled surface (black and grey), or the surface is still shiny, more mercury is needed. A drop or two from a pipette plated for about an hour at 0.9 V with the bubbler on, is usually enough to coat the surface properly. You will find some electrodes, especially the older ones, do not seem to coat as well as the others. The solution to this problem is to keep adding Hg until the desired surface is obtained, or to change the electrode. V.2.6 Electrode Charging V.2.6.1 Rate of Change In order to determine the rate of change of the electrode charging, a series of runs with very short plating times was implemented. The results are shown in Figure V.4. It is obvious that the final current at the final potential (0.2 V — reference electrode) decreased with use. The plating times were 10 seconds in direct succession. A second study used a longer plating time and the results are also plotted in Figure V.4. The plating times in minutes are shown above the points in minutes. Again, the maximum

30 20 01 1^ ~~ re ~ F-. ~0 @ (9 o, 0 10 ~ I $<~~:1:~ ~Add I Hg 0 5 10 20 30 40 50 60 70 80 90 0010 120 TIME Figure V.4: The change of charging current at 0.2 volts with time.

-369charging current at the terminal voltage decreases with usage, and in a similar manner, irrespective of plating time. In both of the above cases it should be pointed out that the mercury layer was about ten times too little for optimum performance, and the decreasing tendency is observed consistently but at a slightly slower rate for a well coated electrode. V.2.6.2 Exposure To determine if the modified electrode was of the same characteristics as the solid electrode, a comparison study was tried. The exposed surfaces of the next four electrodes were 1-1/8 inches, 1 inch, 1/2 inch, and 1 inch, respectively. The surface preparations were to simply polish the exposed surface with crocus cloth and to plate with a weak solution of Hg for a few hours. The results, presented in Tables V.1 and V.2, show that the additional exposed surface increases the charging. In addition, exposure to the air of some of the exposed surfaces increases the charging rate markedly. Also, the gas flow rate effects the charging but not substantially if the solution is allowed to equilibrate for a few minutes after turning on the gas. Finally, newer electrodes have a lower charging rate as seen in the decrease in the maximum value upon replacing the old electrode in rig No. 4 with a new electrode. We should note two things at this point. One is that each electrode will usually not have the same charging characteristics even if the surfaces are the same area. This is

-370Table V.1, Charging current as a function of various conditions. All electrodes are 1" exposure and holed, except No. 1 which is 1 1/8" Peak heights of charging currents in mm. Cell Number 1 2 _3. 4 Electrode Conditions Short Plate (sec.) 57 45 24 18 Long Plate (hrs.) 58 45 28 22 Short Plates: 1/2 electrode exposed to air, no gas 85 All covered, no gas 49 All covered, with gas 64 All covered, with gas 64 All covered, with gas 64 1/2 covered, with gas 83 All covered, with gas 66 3 Min. plate 48 25 gas off 33 gas on 55 gas on 32 New Hg 46 42 27 22

-371TABLE. 2 FINAL CHARGING CURRENT AT O.2V, mm Cell No. 1 2 3 4 Exposed 1 1/8" 1" 1/2" 2 cm Length Conditions: 10 min. 44 29 18 26 24 hrs. 61 75 45 43 55 25 22 55 Wash 68 23 i8 55

-372probably due to the difference in preparation and polishing. They should not, however, be too different if the preparation was the same. Secondly, in the short run the decrease in charging also manifests itself by a decrease in sensitivity. The opposite is true for the long run of several weeks. An optimum compromise was not determined by experimentation as there is a compromise that will best determine the exposed area. If you desire a certain plating time, determine the sensitivity needed from estimation of the sample level and by spikes. The charging should not exceed one half the total scale. If the charging is high and the sensitivity is low, use less surface and longer plating times, assuming good electrodes. For 10 minute plates at a sensitivity level of 50 p a full scale, a surface length of 2 cm from the tip of the pointed electrode was satisfactory (- 3.5 cm2). V.2.7 Drawing of Base Lines For very small quantities of the metals the traces are usually not peaks but a hump with a base line. Sometimes this humped trace will have a flat top with no maximum. Until enough material is present, a maximum will not occur for a given scale setting. Even with the existence of a maximum for cadmium (and zinc), there is a transition from a fast initial charging to a region of less charging and a flatter base line curve. Figure V.5 depicts a classical example. Because of this change in charging rate, it is sometimes difficult to establish just when the inflection occurs and stripping is started. For a calculation of the amount stripped based on

-373cd T I MCE cu Pb Figure V.5: Drawing of base lines. A-B represents the slant line method and A'-B the horizontal method.

-374theoretical considerations, see Nicholson (1964), we would have to find the area or peak height from the beginning of the stripping to the end (line A-B). However, due to the linearity of the calibrations between peak heights and areas, and due to the fact that we are interested in differences and not absolute values of parameters, we can draw a base line horizontally from the left flat portion of the curve very accurately without estimating the initial inflection point (line A-B), if a real maximum has already been established. Table V.3 displays a real data sequence using both methods. The high base line on rig No. 2 best describes the advantage of the horizontal line method. The horizontal line method does not show a significant negative value, whereas the slant base line often does for small amounts of cadmium. A word of caution is in order; a maximum must be present for subtraction as a blank before a horizontal line can be used. Notice the increase from line 1 to line 2 and from line 2 to line 3. On line 1 there were no maxima present and part of the material went into the establishing of the initial maxima. This is another reason for the initial blank plus spike run with the sample added in the subsequent run. For large samples, as occurred with lead and copper, the horizontal line method was not used because of original advice, not because this method would not have worked. In subsequent work of this type, we plan to use the horizontal base line method.

-375TABLE V. SLANT VS. HORIZONTAL BASE LINE - Cd, Rig 1 Rig 2 Sample Horizontal Slant Horizontal Slant PH A PH A PH A PH A Blank 0 11 - 22 +lOng 16 16 45 34 17 17 109 87 +lOng 49 33 81 36 m m 151 42 Sample 59 10 79 -2 66 m 274 123 Blank 17 44 21 109 Sample 20 3 48 4 27 6 108 -1 Blank 18 47 24 106 Sample 25 7 50 3 33 9 103 -3 Rig3 Rig 4 Blank 0 7 - 22 +lOng 23 23 36 29 39 39 90 68 +l0ng 55 30 67 31 92 53 152 62 Sample 61 8 76 9 108 16 167 15 Repeat 61 0 75 -1 108 0 163 -4 Blank 20 34 35 93 Sample 22 2 35 1 39 4 80 -13 Blank 21 53 34 82 Sample 34 13 48 15 53 19 113 29

-376V.2.8 Flat Peaks On systems using the Heathkit recorder one will sometimes encounter a flat peak. This is sometimes due to an improper "Hum" adjustment. To correct, turn the damping off, adjust the hum to the minimum light on the indicator, and then restore the proper damping. If the phenomenon persists, check the reference battery, recorder sensitivity, and current amplifiers. V.2.9 Diagnostics from the Traces The following is a list of recurring problems and some suggested solutions. 1. Too little mercury: this situation leads to fast deterioration of the cell response and sometimes to double peaks. A semi-glossy surface is usually observed on the graphite electrode. 2. Uneven coating of mercury: this situation is similar to too little mercury, but the primary result is double peaks. The observed electrode surface is mottled and patchy. 3. Too much mercury: the result of too much mercury is broader peaks and slower response. This is due to the thickness of the mercury layer and the slower diffusion of the ions through the layer. 4. Large oscillations in the trace recorder: this is not to be confused with noise in the cell electronics. Usually this is caused by one of the electrodes not

-377being immersed in the reagent in the glass cell interior. Push the electrode down or add more reagent to the cell compartment. 5. Noisy signal: this problem is many faceted. For very sensitive work, turn the bubbler off just before stripping. Otherwise, you can position the bubbles so that they do not strike the glass and Vycor electrodes by turning the graphite electrode. Adjust the damping and hum adjustments, if present, on the recorder. Check wiring. 6. Lack of signal or sluggish response not associated with Hg coat: usually this is caused by bubbles forming in the counter or reference electrode. This is the first place to check for most troubles. Because of charging during the plating, some gas is evolved at the platinum electrode tip. Many times a gas bubble is formed at the porous Vycor and the current is diminished, thus the response is less. The reference electrode does not evolve gas but may have residual air in the porous Vycor that percolates slowly to the top of the Vycor, especially on new electrodes. These are common problems and cells should be inspected frequently for cell bubbles. Remove by flipping the glass gently but frequently with the fingernail with the wire partially removed from the cell. Check soldering and connections.

-3787. Fast deterioration of response: this is usually caused by two problems, lack of mercury and overvoltage on plating. See diagnostic 1. If numerous small bubbles form on the graphite electrode, hydrogen is being formed due to a plating voltage that is too high. For zinc, some of this is unavoidable but can be kept to a minimum by carefully calibrating the stripping potential for zinc and not exceeding it by more than 0.1 V. For the other metals, refurbish the electrodes by wiping and/or adding more mercury. The reason for this deterioration is that hydrogen forms at the electrode surface and alters the Hg coating to larger droplets and exposes graphite surfaces. This is not to be confused with larger bubbles from the stirring bubbler that stick to the electrode but cause little concern. 8. Reagent dries up: the stirring gas is usually very dry and will evaporate water from the cell over a prolonged plating. Pre-moisten by bubbling gas through distilled water and follow by a water trap. This is more than enough to moisturize the gas. To limit evaporation and to save nitrogen, turn the gas supply off overnight and for long periods of nonplating. Be sure to let the gas run for a few minutes before restarting the plating or stripping.

-379V.3 RUNNING PROCEDURES V.3.1 Procedure for Cutting Filters The Hi-Vol filter pads are usually folded along the longer axis and put into folders. This causes some settling into the fold from the rest of the filter surface if the folders are agitated too much. To attempt to gain a representative aliquot, a one inch square was cut through both sides of the filter close to the fold but not including the 2 fold. Thus, a two inch portion of the filter pad was obtained from different areas in the pad but near the center. A stainless steel scalpel was used to cut around a one square inch plastic template. The resulting sample was cut into small strips and put into the 25 ml volumetric flask using a plastic tweezers and a glass rod. All instruments were wiped after each use to minimize cross contamination. V.3.2 Procedure for Cleaning Flasks Several 25 ml volumetric flasks were washed in laboratory soap and tap water. They were rinsed twice in tap water and then in distilled water. They were then filled with tap water and HC1 and allowed to stand for a few hours. After one more rinse with distilled water, the stoppers were inserted until the filter pads were cut and the flasks labeled. V.3.3 Procedure for Digesting Samples Four milliliters of 70% perchloric acid were pipetted into the volumetric flask and the material was shaken to position the filter material in the acid and not on the sides

-380of the flask. A group of four to nine flasks were heated on a hot plate to 260~C for about one hour, or until all the black color disappeared from the filter strips. The flasks were removed from the heat, allowed to cool, and equilibrated to 25 ml with double quartz distilled water. Stoppers were inserted and the samples were allowed to set for at least 24 hours. With the acidity of the samples being so high, there was little absorption onto the glass sides of the flasks. However, there was a possibility of desorption from the glass. This is especially true for lead. V.3.4 Codes for Flasks The following code was used on the 25 ml sample flasks: S/sample no./month/day/year. For example, S806068 = sample 8, 6 June 1968. The blanks are designated by G B 1...N for the Gary area blanks, and C B 1...N for Chicago. The Gary blanks were processed and weighed while the Chicago blanks were new filter pads. V.3.5 Procedure for Transferring Samples to the ASV Rig Four 100 micropipettes were used to transfer the sample from the volumetric flask to the four quartz vials for ASV analysis. Each sample was drawn into the pipette and dumped into a waste beaker. A second sample was drawn and put into the quartz vial. The pipette was laid aside and a new pipette was used for the next sample. During the plating the pipettes were washed with distilled water, both inside and out, by squirting a generous supply of water from a squeeze bottle

-381onto and through the pipettes. The carry-over was measured and found to be minimal, if this procedure was properly followed. The quartz vials were cleaned by two rinsings with distilled water and subsequent shakings. A third rinse was left standing in the vials until they were needed in the next round of samples. Between the runs the vials were stored dry and inverted to minimize contamination. Due to the amount of material we were sampling, and to the relative predictability of this study, most incidents of contamination were easily observed and usually predictable. Any unusual values were rerun to verify that the signal was not that of procedural contamination. V.3.6 Running Procedure After the cells were properly conditioned with mercury, they were cleaned with double distilled water and a 10 minute reagent plate was tried. If the signal was high, the cells were cleaned again to check for carry-over of high reagent blanks. If the reagent was plating for more than three days and the reference electrode read above 1.1 volts on the reagent jug, the problem was usually carry-over. When a low reagent blank was read, no more attempts were made to clean the cell. (For more sensitive work, this would have to be monitored more carefully.) A filter blank aliquot was then added and run for 10 minutes. A combination spike of 100 ng lead and copper and 10 ng cadmium was added and plated for

-38210 minutes as before. A second spike was added to obtain a better peak and a more accurate standard. (See section V.2.7, Drawing of Base Lines.) During some runs additional spikes were made by doubling the previous spike to obtain a concentration versus peak height and/or area curve for subsequent calibrations of large quantities of the metals. (See section IV.4.1, Calibration.) After a standard run was completed, the process was repeated but a sample was added on top of the spike after it had been stripped and recorded. This sample was plated for 10 minutes, also, and then stripped. The reasoning behind this procedure was to eliminate the variable carry-over and to monitor the deterioration of the cell, if it existed. The carry-over was usually about 2-3%, but since the subsequent samples varied widely, the blanks would also vary even if the carry-over rate remained constant, which it probably did not. (See section V.3.7, Carry-over.) By subtracting the reagent blank, plus the filter blank, plus a spike, plus carry-over from the previous sample, a nearly true value of the sample is obtained, and the cell response is monitored in the long run. The filter blank spike was added to each spike run to ensure that the acid in the sample did not change the cell response between the spike and sample plus spike run. This was observed to happen on the pilot runs. The addition of more acid from the sample did not seem to change the calibration significantly as was expected.

-383V.3.7 Procedure for Minimizing Carry-over and Cross Contamination: Cleaning the Cells of the ASV Rig Ten milliliters of pre-purified reagent was pipetted into the clean quartz vials. 100 X of the blank solution and 100 X (100 ng - Pb, 100 ng - Cu, 10 ng - Cd) of spike solution was also pipetted into the vial, in that order. After completion of the last round of samples, the other set of vials was removed, one at a time. The electrodes were squirted with a generous supply of distilled water immediately after the removal of the original vial to prevent the mercury film from drying, cracking, and oxidizing, and thus deteriorating the sensitivity of the cell. When the water jet is removed, the excess is blown off and the newly prepared vials inserted as soon as possible. This process was completed one cell at a time. The mercury surface was never under a direct stream of water in order to minimize mechanical deformation and change of the cell response. V.4 REPRODUCIBILITY V.4.1 Static Reproducibility One probably would expect that cell deterioration would take place with the radical treatment of exposure to air and washing with a stream of distilled water; but, does the cell change significantly by simple repetition of the platingstripping procedure? The answer is not a simple one as there are several parameters to consider. Some of these are: slow contamination from the electrode compartment through the Vycor plugs, change in the valence due to reagent changes, plating

-384Table V,4: Carry-over using wash-bottle stream. Rig Number 100 ng spike after washing ratio 2 Areas under curves, (in. ). 1 9.6 0.23 42 2 10.7 0. 30 36 3 6.0 0.12 50 4 7.9 0.24 33 t The average carry-over is. 2.5%/ using area. Peak Heights (mm). 1 780 25 51 2 690 34 20 3 440 85 l4 54o 23 24', The average carry-over is 3.Co, using peak heights.

-385potential, pH, and others. If we assume that the cells are properly cleaned and the mercury has been plated properly, a repeatability test can be conducted, (see Table V.5). The reagent is 2.0 N NaCl + 1 N NaAc. The repeatability is good, and variations are probably due to timing (and measurement). Since we cannot always be assured that conditions are as good as those above, we should present a more realistic study, remembering that optimum performance can be achieved with enough patience and skill. Table V.6 and Figures V.6 - V.8 represent a sequence of eleven 10 minute plates of cell blanks. A significant deterioration does occur, but it is a fairly steady change. When using acetate buffer solutions, you must be careful that the lead does not precipitate out as acetate. This is accomplished by using acid solution of sufficient strength, and is another reason for adding the filter blank to the spike sample before getting the background and carry-over values in an initial run. An interesting phenomenon observed was that a dark spot appeared on the graphite electrode directly across from the charging electrode (current electrode). This spot grows with use and is usually about 2-3 mm in diameter, black at the center and diffusing gradually to the grey of the Hg coating. This is probably due to the electric or current field gradient in the vicinity of the current electrode. There does not seem to be any observable correlative effect, but it does show that the field is not uniform throughout the cell.

-386TABLE V.5: STATIC REPEATABILITY Run Cell 1 Cell 2 Cell 3 Peak ht. Peak ht. Peak ht. (mm) (mm) (mm) Cd Pb Cu Cd Pb Cu Cd Pb Cu 1 11 44 8 23 42 9 13 37 7 2 11 40 7 25 45 14 17 36 9 3 11 38 6 23 41 12 20 38 11 4r 0 2.5.8 1 1.7 2.1 2.9.8 1.6 Average of a Cd Pb Cu All 1.5 1.7 1.5 1.5

TABLE V.6: STATIC REPEATABILITY - 10 minute plating Rig 1 Rig 2 Rig 3 Rig 4 Run No. Pb Cu Cd Pb Cu Cd Pb Cu Cd Pb Cu Cd 1 20 70 45 17 55 35 7 32 21 6 32 10 2 18* 53* 46* 13 45 30 6 36 20 5 28 10 3 16 41 43 13 43 30 6 33 18 4 21 10 4 15 44 41 12 43 29 6 30 18 4 22 9 5 13 42 41 11 40 28 6 27 18 5 23 9 6 14.5 40 42 12 39 27.5 5.5 24.5 18 4 17 8 7 13.5 37 42 10.5 33 24 5.5 22.5 18.5 4.5 16 7.5 8 14 33.5 41.5 10 28.5 22.5 5.5 17 17.5 4.5 11 7 9 13.5 30.5 40 10 25 22 5.5 14.5 17.5 5 10 6.5 10 15 29 40 9 22.5 19 5 11.5 16.5 4 9.5 7.5 11 (75) 29 42 (54.5) 31 18.5 (85.5) 16 16 (60) 9 5 * 11 min; scale = 100( g; ( ) Spike 2x10-7 M1Pb

-38801 ~ 40- * 0 x2 30 x x x x x E x x 20 z3 A +- + + 3= 0 -+ + + + + + F I I2 3 4 5 6 7 8 9 10 II RUN NUMBER Figure V.6: Static reproducibility, Cd.

-38920 x E X ~ - X X E x 10- x X Ix x w _ a.J + A A A A 5- + + A + + + + + + + I I I I I I I.1 1, 1 2 3 4 5 6 7 8 9 10 II RUN NUMBER Figure V.7: Static reproducibility, Pb.

-390100 80 60 E x * E -'40 X 20 A + A I0 + i 2 3 4 5 6 7 8 9 10 11 RUN NUMBER Figure V.8: Static reproducibility, Cu.

-391Perhaps a future design improving the field characteristics would improve the cell performance. We should investigate further. V.4.2 Repeatability Within the Same Filter Pad Sample S106208 was sampled in three additional areas on a separate run. Each vial was treated as a regular run with the sample procedure as before. The standard deviation was 33% for Cd, 17% for Pb, and 3% for Cu within the four samples, resulting in an average of 18% reproducibility. The results are shown in Table V.7. V.5 CALIBRATIONS: CONCENTRATION CURVES, CONCENTRATION VS. PEAK AREA AND HEIGHT Preliminary investigations prior to the actual sample runs were made in order to determine representative relationships between concentrations and peak heights and areas. The results are tabulated in Table V.8 and plotted in Figures V.9 and V.10. As stated by Matson (1968), the area dependence is linear throughout the possible ranges. However, the peak heights start to roll off at about 2 micrograms absolute. That is to say, 2 micrograms within the sample vial for a 10 minute plating time. The standard amount of reagent was 10 ml in all of these studies. The following rule of thumb was observed: the peak height method is linear to 1-2 micrograms with a 30 to 40% error in the 10 to 20 microgram region. These graphs, or similar graphs, can be used to quickly estimate the concentrations of large samples with reasonable

-392Table V.7: Reproducibility within the same filter pad. Run Cd Pb Cu Number ng/m3 ng/m3 ng/m3 1 3 780 1500 2 4 900 1400 3 6 840 1400 4 8 1200 - Average 5.2 930 1430 <r~: 1.8 162 47 Percent o: 3550 17% 3%

Table V.8: Concentration vs. peak area and peak height. 10 minute plates ( in.2 x 100 and mm scaled to 100 4 ) Rig 1 2 3 4 Area Peak Area Peak Area Peak Area Peak Spike 200 ng 57 76 51 92 55 49 41 56 400 88 114 - - 80 101oi 95 135 600 140 177 - 218* 156 186 156 205 800 186 226 212 552 186 258 170 250 1000 244 278 - - 218 282 254 520 1200 284 334 - - 290 33550 272 590 1400 56 576 470 720 528 590 512 442 2400 500 515 570 460 555 525 685 5400 655 615 800 1070 685 695 695 845 13,400 22350X 1450 - 2570* 5190X 1540 2960x 2020 *: estimated by 2 x 1/2 width method. x: non-linear peaks

-3914* Rig. I x 2 A 3 3000 + 4 xl ( ) Estimated + 1000 cx + j I x ~ 0 w 300 U iI + A 100 30 I I I 0I. i.. 300 1000 3000 i,0O0 Pb AMOUNT, ng Figure V.9: Concentration versus peak height, Pb.

qcI ~aos Bad snsaJA uoTqo,-uaQuoo: OT'A ajnSTj Bu'lNnOIAiV qd 000'01 0002 0001 00~ I ~I I 1 01~~I 00~ V + 0 _1o m I i 0001:g > 0001 -96~I

-396accuracy. It is suggested that the aliquot be taken so that the concentrations are less than one microgram absolute, so that peak heights can be used. See the discussion concerning peak heights versus areas in section IV.5.4. Other graphs of this nature can be drawn from the runs of the area-wide samples. It should be noted that the roll off in peak height may be due more to the electronics and less to the cell characteristics. It is, therefore, necessary to calibrate for each change in the electronic components. I would suggest that more efficient current amplifiers would help to alleviate this nonlinearity, but it is not necessary for proper selection of aliquots when such is possible. In order to confirm the logarithmic dependence of the cell response on the plating time, a 200 ng spike was added to 10 ml of the reagent and the response recorded for several sequential plating intervals. Each interval was separated by 15 sec of stripping potential (0.2 V). This particular data set is presented in Table V.9 and graphically in Figure V.11. One cell was unique in that a fresh shot of mercury was added just prior to the study, while the other cells were several hours since their mercury plates and several plating periods had passed. It is interesting to note that the fresh mercury greatly improves the cell sensitivity. The half times of the cells (that time to plate half the material) is of the order of 10 minutes in general with more time needed for older cells and less for freshly prepared ones.

-397TABLE V.9: PLATING TIME CONSTANTS: 200 ng Pb spike Cell 1 Cell 2 Cell 3 Plating time* Height (mm) Height Height 5 72 (Hg) 55 10 85 121 72 15 96 139 86 20 104 151 92 30 114 173 107 60 134 207 138 120 146 238 170 15 97 133 73 * 15 seconds between runs

-398300 100 E 60 2 //, 30 - z I10- ~ 6 _ 3 L 60 80 100 120 140 PEAK HEIGHT, mm Figure V.1: Plating time constants versus response.

-399At the termination of the 120 minute run a repeat of the 15 minute interval was implemented to check on the repeatability or deterioration of the cell. From this data the reliability is better than 15% in all cases presented here. Other studies were processed and showed similar results.

APPENDIX VI DETAILS OF SAMPLING SITES -4~01

z _ -402F igure VI.1' PARTICULATE BLMONTOIG FULLETON -f Nwmz NO OSVE TI -- - _ - 54~ ~ ~~~ El~~~~~~~~~~~~~~~0 -SMONITORING nSCALE IN MILES NETWORK, 47TH Chicag~C, 1. iT I. ASTH ~J 1 iTH VT" 103110 IIJT~I*A CALLOC,-, I

TABLE VI. 1 STATION KEY FOR NORTHWEST INDIANA AIR SAMPLING NETWORK Area Name Address and Location 1 Hammond Water Works 110th and Lake Avenue 2 " " Goldblatt(NASN) Hohman and Sibley 3 t" " City Hall Highland and Calumet 4 Whiting Fire Station 119th and Schrage Avenue 5 t t South Side School 127th and Birch 6 East Chicago Marktown Brode and Pine 7 " "f Central Fire Station 450 E. Columbia Drive 8 " " Roxana Roxana Drive and S. Walsh Avenue 9 t" " Field School Block and James Place 10 " Franklin School 142nd and Alden 11 Gary Airport U.S. 12,West Gary o 12 " Ivanhoe 13th Avenue and Gerry 13 " " Fire Station 5th and Connecticut 13A " " " " (Directional) 14 "Williams School 19th and Indiana 15 " "Kuny School 51st and Kentucky 16 " Wirt School Birch and Gand 17 Lake County Highland 9135 Erie Street, Highland 18 " Hobart Forman School-S. Ind. Rt. 51, Hobart 19 " ". Crown Point Taft School, S. Main Street,Crown Point 20 " " Schneider Standard Oil Station, R.R. 51, Schneider 21 Porter County Ogden Dunes, Ind. 22 " " South Haven, Ind. 23 Chesterton, Ind. 24 " "Flint Lake N. Valparaiso, Ind.

TABLE VI.lcontinued: 25 Porter County Kouts, Ind. 26 Michigan City Central School 9th and Spring 27 it i Coolspring School Niemer Road 27A It Nieman School Tryon and Cook Rd. 28 LaPorte County LaPorte (proposed) 29 " 1 Hanna (proposed)

-405TABLE VI. 2 CITY OF CHICAGO, DEPARTMENT OF AIR POLLUTION CONTROL - TECHNICAL SERVICES DIVISION, SUSPENDED PARTICULATE, SULFUR DIOXIDE AND DUSTFALL MONITORING NETWORK, SAMPLING STATIONS A Taft High School 5625 N. Natoma Avenue B Lake View High School 4015 N. Ashland Avenue C Steinmetz High School 3030 N. Mobile Avenue D Cooley Voc. High School 1225 N. Sedgwick Street E South District Filtration Plant 3300 E. Cheltenham Place F G.S.A. Building 538 S. Clark Street G Crane High School 2245 W. Jackson Blvd. H Austin High School 231 N. Pine Street I Farr Dormitory 3300 S. Michigan Avenue J Kelly High School 4136 S. California Avenue K Lindbloom High School 6130 S. Wolcott Avenue L Hyde Park High School 6220 S. Stony Island Avenue M Stevenson Elementary 8010 S. Kostner Avenue N Calumet High School 8131 S. May Street 0 Chicago Voc. High School 2100 E. 87th Street P Fenger High School 11220 S. Wallace Street Q Carver High School 801 E. 133rd Place R Clay Elementary School 15251 S. Bursley Avenue S Argonne National Laboratory Argonne, Illinois T Sullivan High School 6631 N. Bosworth Avenue U Von Steuben High School 5059 N. Kimball Avenue V Logan Square Fullerton and Kedzie Avenues W Hale Elementary School 6140 S. Melvina Avenue

-4 06TABLE VI.3: METEOROLOGICAL STATIONS, NORTHWEST INDIANA I E. Chicago City Hall 4600 Indianapolis Blvd. II Kieser Corp., Gary 7501 W. 5th Ave. III Ogden Dunes, Ind. (Station 21) IV South Haven, Ind. (Station 22) V Chesterton, Ind. (Station 23) VI NIPSCO., Michigan City 1st and Wabash VII Gary Air Pollution Dept. 6300 W. 3rd Ave. VIII Gary Airport U.S. 12, West Gary IX Hammond City Hall Calumet Ave. and Highland

-4070 NBU TAM-5 0 \ 0'-> ~__TAM-2 TAM-7 0 TAM-3 __OMDW o TAM-5 TAM-4 OTAM-8 0 ARG ARG i 1TAM-6:, INDIANA ___ltI j, I, 1, -a i 10 km I Figure VI.2:Telemetered data stations, Chicago, IIll.

-4 08TABLE VI. 4 NORTHWEST INDIANA SAMPLING NETWORK RANDOM SAMPLING SCHEDULE, 1968 SAMPLING PERIOD (WEEK) Sampling day 1. Wed. Jan. 3* 40. Thurs. Oct. 3 2. Tues. Jan. 9 41. Tues. Oct. 8 3. Sat. Jan. 20* 42. Sun. Oct. 13* 4. Thurs. Jan. 25 43. Thurs. Oct. 24* 5. Mon. Jan. 29* 44. Thur. Oct. 31 6. Tues. Feb. 6 45. Sat. Nov. 9* 7. Fri. Feb. 16* 46. Wed. Nov. 13 8. Wed. Feb. 21 47. Tues. Nov. 19* 9. Tues. Feb. 27* 48. Tues. Nov. 26 10. Thurs. March 7 49. Fri. Dec. 6* 11. Tues. March 12 50. Thurs. Dec. 12 12. Sun. March 17* 51. Mon. Dec. 16* 13. Wed. March 27 52. Sat. Dec. 28 14. Thurs. April 4 15. Fri. April 12* 16. Wed. April 17 17. Thurs. April 25* VALPARAISO0 SAMPLING DAYS 18. Tues. April 30 June 6 August 4 19. Sat. May 11* 14 10 20. Thurs. May 16 20 19 21. Wed. May 22* 27 21 22. Mon. May 27 July 2 27 23. Thurs. June 6*x 9 24. Mon. JunelO 11 Sept. 1 25. Thurs. June 20X 19 14 26. Sun. June 23* 27 17 27. Mon. July 1* 25 28. Tue. July 9X 29. Tues. July 16* 30. Wed. July 24 31. Wed. July 31* 32. Thurs. Aug. 8X * NAS days 33. Sat. Aug. 17* x University of Michigan trace 34. Tues. Aug 20 metal studies (ASV) 35. Thurs. Aug. 29*x ~ Only Summer months are listed 36. Wed. Sept. 4 57. Fri. Sept. 135 38. Thurs. Sept. 19 39. Wed. Sept. 25*

-409TABLE VI. 5 NORTHWEST INDIANA SAMPLING NETWORK RANDOM SAMPLING SCHEDULE, 1969 SAMPLING PERIOD (WEEK) Sampling Day 1. Sat. Jan. 4* 40. Mon. Sept. 29 2. Tues. Jan. 7 41. Mon. Oct. 6* 5. Wed. Jan. 15* 42. Sun. Oct. 12 4. Thurs. Jan. 23 43. Thurs. Oct. 23* 5. Tues. Jan. 28* 44. Fri. Oct. 31 6. Sun. Feb. 2 45. Fri. Nov.7* 7. Thurs. Feb. 13* 46. Sat. Nov. 15 8. Wed. Feb. 19 47. Wed. Nov. 19* 9. Fri. Feb. 28* 48. Mon. Nov. 24 10. Thurs. March 6 49. Tues. Dec. 2* 11. Mon. March 10* 50. Wed. Dec. 10 12. Mon. March 17 51. Sun. Dec. 14* 15. Sun. March 23* 52. Sun. Dec. 21 14. Wed. April 2 15. Mon. April 7* 16. Sat. April 19 17. Fri. April 25* 18. Wed. April 30 19. Sun. May 4* 20. Fri. May 16 21. Tues. May 20* 22. Sat. May 31 * NAS days 23. Sat. June 7* x University of Michigan 25A. Wed. June 11x trace metal studies (NAA) 24. Fri. June 13 25. Wed. June 18* 26. Thurs. June 26 27. Wed. July 2* 28. Tues. July 8 29. Fri. July 18* 30. Thurs. July 24 31. Tues.July 29* 32. Mon. Aug. 4 33. Sat. Aug. 16* 34. Sat. Aug. 23 35. Thurs. Aug. 28* 36. Tues. Sept.2 37. Sun. Sept. 7* 58. Sun. Sept. 14 39. Mon. Sept. 22*

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— 415 - Winchester, J. W. and Nifong, G. D. "Water Pollution in Lake Michigan by Trace Elements from Pollution Aerosol Fallout." Paper WATR-34 presented at the American Chemical Society Meeting (April 1969). Winchester, J. W., Zoller, W. H., Duce, R. A. and Benson, C. S. "Lead and Halogens in Polluted Aerosols and Snow from Fairbanks, Alaska." Atmospheric Environment, Pergammon Press, Vol. 1, pp. 105 —119~-T967 ).

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