EPA-600/1-76-019
March 1976 Environmental Health Effects Research Series
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development,
U.S. Environmental Protection Agency, have been grouped into
five series. These five broad categories were established to
facilitate further development and application of environmental
technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in
related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL HEALTH EFFECTS
RESEARCH series. This series describes projects and studies re-
lating to the tolerances of man for unhealthful substances or
conditions. This work is generally assessed from a medical view-
point, including physiological or psychological studies. In add-
ition to toxicology and other medical specialities, study areas
include biomedical instrumentation and health research techniques
utilizing animals - but always with intended application to human
health measures.
This document is available to the public through the National
Technical Information Service, Springfield, Virginia 22161.
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EPA-600/1-76-019
March 1976
BASELINE LEVELS OF PLATINUM AND PALLADIUM
IN HUMAN TISSUE
By
Donald E. Johnson, R. John Prevost, John B. Tillery,
David E. Camann and John M. Hosenfeld
Southwest nesearch Institute
8500 Culebra Road
San Antonio, Texas 78284
Contract No. 68-02-1274
Project Officer
Dr. Robert ?1. Bruce
Clinical Studies Division
Health Effects Research Laboratory
Research Triangle Park, N.C. 27711
t , ! ,
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
HEALTH EFFECTS RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, N.C. 27711
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DISCLAIMER
Th\s report has been reviewed by the Health Effects Research
Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection
Agency, nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.
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ABSTRACT
This report presents the results of an epidemiological study of
populations living near a freeway in Los Angeles, California, and in the
high desert region of Lancaster, California, for concentrations of platinum,
palladium, and lead in blood, urine, hair, feces, autopsy tissues, ambient
air, surface water and soil. Platinum and palladium are determined in
samples from miners in Sudbury, Ontario, Canada, and metal refinery
workers in New Jersey.
Analytical methods are developed for platinum, palladium and lead
using atomic absorption spectrophotometry.
The objective is to determine baseline levels of platinum and
palladium in the population and environment prior to wide-spread use of
catalyst-equipped vehicles. Lead is determined to ascertain the future
epidemiological effect of non-leaded gasoline.
Platinum and palladium concentrations were below the detection
limit for Los Angeles, Lancaster, and Sudbury samples. Refinery workers'
urine and refinery air samples had detectable concentrations of both metals.
Higher lead values were observed in Los Angeles samples taken
near the San Diego Freeway than in samples taken in the high desert area
of Lancaster, California.
This report was submitted in fulfillment of Project No. 01-3881-003
and Contract No. 68-02-1Z74 by Southwest Research Institute under the
sponsorship of the Environmental Protection Agency. Work was completed
as of August, 1975.
m
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TABLE OF CONTENTS
Page
Abstract ill
Table of Contents iv
List of Figures x
List of Tables xi
Acknowledgments X1V
I. CONCLUSIONS 1
II. RECOMMENDATIONS 4
III. INTRODUCTION 6
IV. EXPERIMENTAL 10
A. Selection of Study Sites 10
1. Baseline 10
2. Mining 11
3. Refineries 12
B. Recruitment of Study Participants 12
1. General Approach 12
2. Questionnaire Development 15
3. Backup Materials 18
4. Recruitment Activities 20
a. Southern California 20
b. Ontario 25
c. New Jersey 26
5. Participant Selection 27
6. Description of Study Participants 29
C. Collection of Samples 30
1. Environment 30
a. Baseline 30
b. Mining 37
c. Refineries 38
IV
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Table of Contents (cont'd.)
1).
2).
3).
4).
5).
Blood
Urine
Hair
Feces
Tissues
2. Study Pargicipants
a. General Procedure 39
b. Informed Consent 43
c. Information Sheets 44
D. Analytical Methods 51
1. Literature Review 51
2. Instrumentation 53
3. Reagents 53
4. Selection of Analytical Methodology 54
5 . Platinum and Palladium Methodology 54
a. Extraction Procedure 54
b. Biological Samples 64
64
65
67
67
68
c. Environmental Samples 69
1). Air Samples 69
2). Soil Samples 69
3). Water Samples 71
6. Lead Methodology 71
a. Biological Samples 71
1). Blood 71
2). Urine 72
3). Hair 72
4). Feces 73
5). Tissues 74
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Table of Contents (cont'd.)
Page
b. Environmental Seimples 74
1). Air 74
2). Soil 75
3). Water 77
7. Calculations and Analytical Data 77
a. Instrument Parameters 77
b. Standard Solutions 80
1). Platinum and Palladium 80
2). Lead 80
c. Analytical Data 82
1). Limits of Detection 82
2). Precision 82
3). Accuracy 82
8. Special Analysis 84
a. Paint Analysis for Pb Content 84
1). Analytical Procedure 84
2) Results 84
b. Neutron Activation Analysis (NAA) 85
1). Blood 85
2). Analytical Procedure 85
3). Results 86
c. Dilution Tunnel Sweeping 86
1). Analytical Procedure 86
2). Results 87
d. Vacutainer Contamination Study 88
1). Introduction 88
2). Experimental 88
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Table of Contents (cont'd.)
Page
a) Selection of
Vacutainers 88
b) Analytical Procedure 89
(i) Lead Analysis 91
(ii) Platinum and
Palladium Analysis 91
3). Discussion 92
4). Calculations 93
a) Regression Analysis 93
b) Statistical Analysis 93
5). Results 96
a) Lead 96
(i) Blood 96
(ii) Water and Acid 98
b) Platinum and Palladium 98
6). Conclusion 98
a) Lead 98
b) Platinum and Palladium 100
c) Contamination 100
e. Lead-210 Study 100
1). Selection of Subcontractor 100
2). Method of Analysis 101
a) Sample Preparation 101
b) Sample Dissolution 102
c) Decontamination 102
d) Counting 102
e) Calculations 103
Vl l
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Table of Contents (cont'd.)
Page
3). Limit of Detection in
Blood and Feces 104
a) Blood 104
b) Feces 104
9. Discussion and Conclusions 104
a. Platinum and Palladium 104
b. Lead 106
E. Data Processing 109
F. Statistical Methods 112
1. Baseline 112
a. Environment 112
b. Human Subjects 114
2. Refineries 118
a. Environmant 118
b. Study Participants 119
V. RESULTS 122
A. Baseline 122
1. Platinum and Palladium 122
2. Lead 126
a. Environment 126
b. Study Participants 133
c. Autopsy - Los Angeles 152
d. Sources of Variation in Human
Lead Determinations 152
e. 210Pb Analysis 163
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Table of Contents (cont'd.)
Mining
1. Environment
Z. Study Participants
3. Autopsy Cases
Refineries
1. Environment
Z. Study Participants
Page
166
166
168
168
168
168
17Z
References
Appendix A
Appendix B
Appendix C
Appendix D
Appendix E
Appendix F
Individual Information on Participants
from Los Angeles and Lancaster
Determination of Sample Size to
Analyze Vacutainer Contamination Study
Individual Lead Values for Participants
from Los Angeles and Lancaster
The Labeling Code
Analysis Variables in Lead
Effect of Additional Factors on Lead
Concentration
179
18Z
185
187
ZZO
ZZ4
230
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LIST OF FIGURES
Figure Number Page
1. Platinum, Palladium and Lead Questionnaire 16
2. Pertinent Socioeconomic and Demographic
Characteristics of Volunteer Participants 32
3. Volunteer's Informed Consent 45
f
4. Effect of Acid Concentration Upon HMWA
Extraction of Pt and Pd 58
5. Extraction of Pt (25 ng) from 3M HC1 Using
Various Concentrations of SnCl_, Solution (3MHC1) 60
6. Extraction of Pd (12.5 ng) from 3M HC1 Using
Various Concentrations of SnCl., Solution (3M HC1) 61
7. Regression Analysis of Blood-Pb Spikes 90
8. Baseline Soil Lead Sample Data 129
9. Soil Lead Concentration with Distance from
the San Diego Freeway 130
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LIST OF TABLES
Table Number Page
1. Numerical Coding of Responses to Questions
8 and 10 19
2. Pertinent Socioeconomic and Demographic
Characteristics of Volunteer Participants 31
3. Analysis of Occupations of Volunteer Participants 33
4. Effect of Elements Upon Extraction of Pt and Pd
from 3M HC1 59
5. Limits of Detection of Pt and Pd in Biological
Samples 63
6. Pt and Pd Spike Levels of Composite Samples 66
7. Limits of Detection of Pt and Pd in Environmental
Samples 70
8. Comparison of 6M HC1 "Leach" with Aqua Regia
"Digest" of Glass-Fiber Air Filter for Pb 76
9. Instrument Parameters for Lead Determination
by Air/Acetylene Flame 78
10. Instrument Parameters for the HGA-2000
Determination of Pt, Pd and Pb 79
11. Pb Spike Levels Used to Calculate Analytical Curves 81
12. Precision for Pb Analysis 83
13. Vacutainer Study Data 94
14. Results of Vacutainer Study -- Comparison of
Controls and Vacutainer Blood Lead 97
15. Vacutainer Study Pt and Pd Results 99
16. Platinum and Palladium Levels in Southern
California 123
Xl
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List of Tables (corit'd)
Table Number Page
17. Autopsy Cases - Los Angeles 1Z4
18. Platinum and Palladium in Autopsy Samples-
Los Angeles 1Z5
1 n
19. Baseline Air Lead Sample Data 127
ZO. Comparative Analysis of Baseline Air Lead Data 1Z8
21. Outlier Analysis of Baseline Soil Lead Data 13Z
ZZ. Comparative Analysis of Baseline Tap Water
Lead Data 134
Z3. Skewness Test of Normal Distribution Under
Various Transformations of the Baseline Human
Subject Lead Determinations 135
Z4. F Test of Various Equality Unde:r Various Trans-
formations of the Baseline Human Subject Lead
Determinations 137
Z5A. Baseline Lead Concentration Data Summary (Blood) 139
Z5B. Baseline Lead Concentration Data Summary
(Long Hair) 140
Z5C. Baseline Lead Concentration Data Summary
(Short Hair) 141
Z5D. Baseline Lead Concentration Data Summary (Urine) 14Z
25E. Baseline Lead Concentration Data Summary (Feces) 143
Z6 . t Test of Significant Mean Lead Concentration
Differences between Los Angeles and Lancaster
Participants 145
Z7. Sampling of High Blood Lead Concentrations in
Baseline Participants 148
Z8. Significance of Additional Factor Relationships 150
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List of Tables (cont'd)
Table Number Page
29. Autopsy Tissues (Los Angeles) 153
30. Variance in Participant Groups 154
31. Blood Lead Determinations from Sampling
Experiment 157
32. Analysis of Variance of Natural Log Blood Lead
Determinations 158
33. Sources of Blood Lead Variability 159
34. Platinum and Palladium Concentrations in Air
Samples at the Sudbury Mine 167
35. Autopsy Cases - Sudbury 169
36. Platinum and Palladium Concentrations in Air
Samples at the New Jersey Precious Metals
Refinery 171
37. Platinum Concentrations in Urine Samples from
the Six New Jersey Refinery Workers with
Detectable Platinum Levels 173
38. New Jersey Refinery Wroker Urine Palladium
Concentrations Classification by Refinery Work
Section 174
39. The One-Way Analysis of Variance of Logarithmically
Transformed Urine Palladium Concentrations by
Refinery Work Section 176
40. Correlation of Log-Transformed Urine Lead
Concentrations of Refinery Worker s with Various
Occupational and Social Factors 178
XTM
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ACKNOWLEDGMENTS
The work accomplished in this study was materially assisted
by the interest, experience, and unstinting cooperation of personnel
of the Catalyst Research Program, EPA, Research Triangle Park,
and particularly that of Mr. John Moran, Dr. Robert Bruce, Ms. Vandy
Duffield, and Dr. Doug Worf of that facility. The thanks of our entire
study team is offered to these individuals for the help they provided.
This study was performed on locations in California, Pennsylvania,
New Jersey, Ontario and Texas; without the significant cooperative
efforts of a large number of diverse organizations at these locations,
accomplishment of the study objectives would have not been possible.
: I
Organizations to which particular acknowledgment is due include:
The School of Public Health and
The Office of Married Student Housing
UCLA
Mira Loma Hospital
Lancaster, California
Wadsworth Veterans Administration Hospital
Los Angeles, California
Internation Nickel Company
New York, New York - Toronto, Ontario -
Cop'per Cliff, Ontario
Matthey Bishop, Inc.
Malvern, Pennsylvania & Winslow, New Jersey
Because epidemiological studies of this nature cannot be performed
without the cooperation and aid of individual volunteers who give of their
XIV
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time and efforts and, literally, blood, the authors wish to extend
their personal thanks to the participants in California, Ontario, and
New Jersey who made this study possible.
XV
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I. CONCLUSIONS
1) Baseline levels of platinum and palladium in the
environment (ambient air, surface soil and tap water) and in urban
populations (children, young adults, elderly - male and female - blood,
urine, hair, feces and autopsy samples - liver, kidney, spleen, muscle
and fat) of Southern California (Los Angeles and Lancaster) are
extremely low. The levels in nearly all samples were below the
detectable limits of the analytical methods. These samples were
collected in September 1974 prior to the introduction of the 1975 automo-
biles which were equipped for the first time with the catalytic muffler.
Z) The design of the environmental epidemiology study of
baseline levels of platinum and palladium was such that, if needed, a
future survey could be conducted to determine whether or not the
operation of the catalyst-equipped vehicles has altered these baseline
levels.
3) The levels of lead in ambient air and surface soil were
substantially higher in the study areas of Los Angeles than in Lancaster.
There were no differences in lead content of tap water collected from
residences in these study areas. Examination of exterior paint on the
surfaces of residences in Los Angeles indicated a low level of lead.
4) Lead in blood, urine, long hair and short hair was
significantly higher in study participants in Los Angeles than in those
1
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in Lancaster. Feces lead (a good indicator of orally ingested lead)
was slightly higher in Lancaster residents than those studied in Los
Angeles. The residents studied in Los: Angeles were selected from
those living very close (within two blocks) and on the downwind side
(prevailing winds) of a major expressway (approximately 225,000 cars/day.
Surface soil lead values showed very high levels close to the freeway
with decreasing values with distance away from the expressway. Thus,
given the known high lead values in air and soil from the expressway
source and the elimination of the other common sources of lead ingestion
(food, water, paint), it appears highly likely that automotive lead
emissions were responsible for the observed lead levels in blood, hair
and urine of the Los Angeles study participants.
5) The examination of ambient air and miners for levels of
platinum and palladium in the Sudbury area of Canada did not provide
definitive data on the relationship of ambient air levels of platinum and
palladium. This was because air levels (except for one part of the
plant) were below detectable levels.
6) Data from platinum and palladium refineries indicate that
measureable levels of platinum (0.5-2,,6 |ag/liter) and palladium
(0.3-6.3 fig/liter) are found in urine of workers exposed to air containing
3 3
0.02-0.2 |o.g/m platinum and .001-0.36 |J.g/m of palladium.
Measureable levels were not found in blood from these workers.
2
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7) The information from the refineries indicates that it is
likely that measureable levels of platinum and palladium would be seen
in the general population when ambient levels of these two metals
3
approach 0.1 |jg/m . The metals would appear initially in urine rather
than blood. The data do not provide any inferences with regard to the
absorption of soluble or insoluble forms of the metals. It is probable
that metal particles emitted from the catalytic muffler would have to be
in the respirable range for inhalation and absorption. Reports from
Dr. Moore (EPA, Cincinnati) indicated that both soluble and insoluble
forms of respirable platinum and palladium were absorbed in animal
expe r im ent s.
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II. RECOMMENDATIONS
1) The original plan was to examine blood, urine, hair and
feces in refinery workers and to collect autopsy samples from former
refinery employees. The refineries agreed to blood and urine
collections only. Arrangements to collect autopsy samples from
pathologists in the area of the refinery were unsuccessful. Additional
data are needed on the distribution of platinum and palladium in human
tissue other than blood and urine following exposure to air containing
the two metals at the 0.01-0.1 fj.g/m levels. It is likely that autopsy
samples could be collected if additional effort were expended and if
the sampling period covered at least two years.
2) Additional data to define the relationships between air levels
of platinum and palladium, and tissue levels in the general population
(different age groups, both sexes) are needed, but it is recommended
that the collection of these data be deferred until there is more
information available on quantities and types (respirable-nonrespirable,
solubility, chemical form) of the two metals emitted from the catalytic
mufflers. Data are available which indicate that particles of these
two metals are emitted, but the physical and chemical characteristics
of these particles have not yet been established.
3) It appears that the placement of priorities for evaluation of
the potential health effects of the catalytic mufflers should emphasize
the production of sulfuric acid and sulfates . Additional effort should
4
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the production of sulfuric acid and sulfates. Additional effort should
be directed at characterizing the emissions from these muffler
systems. It is strongly recommended that research be initiated to
evaluate the health impact of the catalytic muffler on populations living
in the immediate vicinity of major expressways with regard to
evaluated levels of sulfuric acid and sulfates from automotive emissions.
It is recognized that the muffler has been in use for only one year on new
automobiles (1975), so the impact will not be significant for perhaps
one or two more years, but efforts need to be initiated so that the
necessary techniques for ambient air measurements and measurement
of proper health effects indices can be perfected.
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III. INTRODUCTION
Catalytic converters were introduced (late September 1974) on
many of the 1975 model automobiles in the United States to reduce
emissions of carbon monoxide and unburned hydrocarbons. The catalysts
used small quantities of platinum and palladium, and there have been
some indications of emissions ofparticles of these metals. Health effects frc
exposure to platinum and palladium reviewed in a previous part of
(1)
this study indicated that soluble forms of platinum can create allergic
responses in sensitive individuals. Hov/ever, little information is
available concerning long-term chronic exposure of humans to low levels
of platinum or palladium, in particular for groups that may be at greater
risk such as the young or aged and for individuals with some type of
medical impairment. There are also some indications that platinum can
be methylated, thus possibly producing a more toxic component.
The EPA has placed additional emphasis on the collection of
biological data on platinum (Pt) and palladium (Pd); since there is limited
biological experience with them, they are likely to be persistent, they
may be metabolized to more toxic products, and exposures will involve
the general population. Emissions from vehicles equipped with the
oxidation catalysts contain components other than Pt and Pd which may
create health effects. The production of sulfates and sulfuric acid by the
catalyst is particularly important. This project has been directed at the
possible introduction of Pt and Pd as particulates and with the reduction
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of lead emissions to the environment, as the catalyst equipped vehicles
require non-leaded gasoline.
Several papers were presented at a symposium, entitled "Health
Consequences of Environmental Controls: Impact of Mobile Emissions
Controls", relative to the problems of trace metals involved in the usage
of the oxidative catalyst equipped vehicles. The subjects of these papers
included examination of emission data, toxicological investigations of
the two metals, development of analytical assay methods, review of
relevant health effects information, effects of the usage of the catalyst
on world markets of Pt and Pd and the design of an environmental
epidemiology study to collect health effects data on Pt and Pd. Many of the
papers discussed plans for conduct of their studies. The overall intent
of the symposium was to review the available data and to make
recommendations as to the additional information needed to make decisions
regarding the safety of the catalytic muffler. Specifically, these
investigations were to provide data to assist both EPA and affected
industries in solutions to this and future problems which impact on public
health.
(i)
The design of this program was presented at this symposium;
thus, its contents were reviewed by academic, government, nonprofit
and industrial organizations. The project has included two types of
environmental epidemiology studies: one directed at determining baseline
levels of platinum, palladium, and lead in the general population prior
to the introduction of the catalysts equipped vehicles, and the second
7
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aimed at determining platinum and palladium residues in occupationally
exposed individuals with the intent to define the relationship between
airborne levels and tissue levels of the two metals.
The baseline study was to be conducted in Southern California
with the selection of a population with relatively heavy exposure to
automobile emissions and also in a second population with low exposure
to vehicular emissions. Three age groups of both sexes were to be
examined; children, young adults and elderly. The demographic make-ups
of the two populations were to be as similar as possible. Tissue samples
were also to be collected at autopsy from individuals from the study area
to determine levels of the three metals in different tissues.
The location of the survey of a population with high exposure to
vehicular emissions was selected so that it would be able to utilize
ambient air data from the L.A.C.S. located along the San Diego Ereeway in
Los Angeles. The design of this baseline study was such that it would
provide an accurate estimation of levels of Pt, Pd and lead just prior to
the introduction of the catalytic mufflers. These data could then be used
for comparison with similarly collected data for subsequent years,
assuming continued usage of the catalyst. The baseline data would serve
a very useful purpose for determining the impact of this new technology
on the environment and on tissue levels.
The occupationally exposed populations were to be drawn from
platinum and palladium refineries located in New Jersey and from the
mining and processing of ore containing Pt and Pd located in the
8
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Sudbury, Canada area. The reasons for including mining and refinery
workers is that the mining was likely to involve exposure to insoluble
forms of the two metals, while the refineries will involve at least a
portion of the metals in the soluble form. These surveys were also to
include examination of autopsy tissue from deceased employees at these
sites.
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IV. EXPERIMENTAL
A. Selection of Study Sites
1. Baseline
The Los Angeles area was selected for the high exposure
to vehicular emissions because it has a very large population and a high
percentage of new automobiles projected for the new car year (1975)
equipped with the catalyst, emissions from heavy industry can be
minimized by selection of areas within the city, and the EPA study (LACS)
was located in the area. After an on-site inspection of the area, it was
decided to conduct the study on the east side of the San Diego Freeway
(within 2 blocks) bounded on the north by Sunset Boulevard and on the
south by National Boulevard. The San Diego Freeway has a traffic
density of 225,000 - 250,000 cars per day in this area. The prevailing
winds in this area are from the west and southwest; thus, the study area
is downwind of the freeway much of the time. Much of the residential area
within the above boundaries was at the same level as the freeway, and
the residents were primarily middle class residing in single and multiple
dwellings.
The low exposure area selected for the baseline study was in
Lancaster, California. This city is located 70 miles northeast of Los
Angeles in the high desert. The city is not affected by smog from the Los
Angeles basin. The city has a population of 30, 948 and has light industry
with no known point sources of lead, platinum or palladium. The
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surrounding area is very sparsely inhabited. The population from this
area was drawn from various areas of the city with the predominate
workplace (of those studied) being a county hospital located in the fringe
of the city.
2. Mining
There are only very small quantities of Ft and Pd mined
in the United States, principally as a residue of other metal mining.
The Sudbury area of Canada is the largest producer of these two metals
in North America. The ore in this area contains very low levels of Pt
and Pd as compared with South African ore which is 10-20 times higher.
The primary metals produced in Sudbury are copper and nickel, with
smaller quantities of iron. Gold, silver, tellurium, osmium, rhodium,
i
selenium, cobalt, platinum and palladium are produced from the ore
residue. Platinum and palladium are processed to a concentrate and then
sent to refineries for further processing.
The largest mining company in the Sudbury area is the
International Nickel and Copper Ontario (INCO). Contacts were made
with this company through offices in New York and Toronto. This
organization gave their approval for the conduct of the survey at their
plant in Sudbury contingent upon approval of the unions prior to contacts
with union employees. INCO was very cooperative and provided
considerable assistance in the conduct of the survey at their plant.
11
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3. Refineries
There are two primary platinum and palladium refineries
located in the United States. Each of these companies was approached
for their cooperation and participation in the study. Both companies
had considerable reservations about the study. After numerous
discussions, each agreed to participate for a portion of the planned survey.
Both of the refineries studied are located in New Jersey.
One of the companies agreed to collect samples of blood
and urine from employees within the refinery and to collect air particulate
samples within the work environment of these employees. The company
performed analysis on the collected samples for platinum and palladium
and submitted the results to SwRI.
The second company (Matthey Bishop, Inc., Malvern, Pa.)
collected blood and urine samples from their refinery employees, along
with pertinent information on each employee sampled such as age, sex,
length of time with company, duties within plant, smoking history, and
ethnic origin. The company also collected air particulate samples in the
plant during the week that the employees were sampled. All collected
samples were divided, with a portion to the company laboratories and
the balance to SwRI.
B. Recruitment of Study Participants
1. General Approach
The general approach taken in this study to solicit and
recruit volunteer participants has been to work through organizations.
12
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The organizations worked with directly have been employers of volunteer
participants and a university attended by other volunteer participants.
Another method used successfully by this study team
utilizes house-to-house surveys to recruit volunteer participants.
House-to-house surveys were considered and ruled out as unnecessary
in this study due to the degree of precision needed in positioning of the
place of residence of the volunteers. In this study, it is sufficient that
the volunteers live within a specific region or work for a specific
employer. The precision required for this study can be well achieved by
working through organizations. Working through organizations provided
the study team with a number of advantages over house-to-house surveys.
Principal personnel in the organizations served as points of initial
contact, liaison during planning recruitment activities, and provided aid
during recruitment, selection, and sample gathering activities.
Volunteers feel more comfortable in familiar surroundings during
recruitment and sample gathering activities.
The first step taken in the recruitment activities, when
working through organizations, is initial telephone contact with a potential
participant organization. In many cases, preliminary telephone calls
are required to appropriate state, federal, or local government agencies
or to local universities and industries to determine the background of
circumstances in the particular area which might affect successful
recruitment and use of human volunteers. In this study, preliminary
phone calls were made to each of the types of institutions listed above.
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The initial telephone contact is used to briefly describe the study and
the need for human volunteers. A minimum of information regarding the
study is provided at this point, as the primary goal of the initial phone
call (or calls, as usually occurs) is to establish a person in the
organization who will serve as the initial contact and to establish a time
and place for meeting in person with representatives of the organizations
to discuss in detail the specific proposal of study. Arrangements are
usually made at this point to forward to the initial contact person a set
of written materials explaining in detail the background of the study and
the specific requirements needed from the participating organization.
These are forwarded for review before the initial meeting in order that
the potential participating organization can better prepare for the meeting.
At the initial meeting, the potential organization is briefed
regarding study requirements. The principal objective of the meeting is to
obtain permission for performing the study. Other objectives include
establishment of a principal person for contact, a time and place for
meeting with potential volunteers, and establishments of the methods to
be used in recruitment acitivities. The initial meeting is followed by
advertisement of the study which specifies the place and time for the
meeting with potential volunteers, and, finally, the recruitment meeting
where materials explaining the purpose and requirements of the study are
provided and questionnaire forms are completed by volunteers.
14
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2. Questionnaire Development
In order to recruit and select volunteer participants, a
questionnaire form, shown in Figure 1, was developed. The form was
designed to be self-administered with a minimum of instructions. A record
of the racial/ethnic background of each potential participant is included
in the form design. This portion of the questionnaire is coded for
completion by the person administering the data collection. Coded
instructions for keypunching the results of completed forms are included
on the form itself. A three-step procedure was designed to obtain and
process information regarding potential participants with use of the
questionnaire form. Step 1 is administration of the questionnaire to
potential participants including brief explanation as to study background,
necessity of volunteer participants, and types of information required for
proper participant selection. The questionnaire is filled out by potential
participants and racial/ethnic background is recorded by the person
administering the data collection.
Step 2 involves preparation of the completed forms for
keypunching. An identification number is assigned to each completed
questionnaire form and coded in the appropriate boxes on the form. Most
of the information on the form is numerically coded in the form design so
that this preparation mainly involves inscription of the numerical
information in an appropriate box. However, Question 8 "What is the
nature of the company for which you work?" and Question 10, "What is
your job title?" are not directly encodable. Answers recorded for these
15
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Figure 1. Platinum, Palladium and Lead Questionnaire
OMB 158 S 74010
Approval expires September 3, 1975
ENVIRONMENTAL QUESTIONNAIRE
STAFF USE ONLY
Cols 1-4
ID#
1 Name (In Full).
? Address Street.
City
Postal Code.
Telephone
Cols 5-30
Cols 31-50
Cols 51-65
Cols 66-70
Cols 71 77
Col 80
Years
3 How many years have you lived in your present city or town'
4 Is your residence located
1-ln the central portion of a city 3—In a rural town or community
2-ln a suburban community or residential area 4—In a rural setting some distance from any town.
5 How far is your residence from the nearest
a Freeway, expressway or turnpike
b Other major multilane traffic artery
c Large industrial or mining operation
6. Do you have air conditioning in your living quarters? 1—No
2—Yes, window only
3—Yes, central
7 Which of these best describes your present occupational status.
Col 6
less than
2 blocks
1
1
1
less than
1 mile
2
2
2
1 mile or
more
3
3
3
Col 7
Col 11
1—Employed fulltime (including self-employed)
2—Employed part-time
3-Unemployed
4—Housewife
5—Student
6-Play/Nursery School
7-Pre-School
3-Retired
IF YOU ARE EMPLOYED, PLEASE CONTINUE. OTHERWISE, SKIP THE NEXT FIVE QUESTIONS AND BEGIN AGAIN WITH QUESTION 13.
8 What is the nature of the company for which you work'
1—Mining and smelting 3—Finished metal products
2-Oil or chemical industry 4—Jewelry
5-Other (Please Specify)
Cols 1213
9 How long have you worked for your present employer?.
10. What is your job title? ,
11. Your work is primarily
1—Office work
2—Production or manufacturing
3-Other (Please specify)
You perform your work primarily 1 -Inside
2 Outside
12 If you work in production or manufacturing, does your work involve1
Col 19
1-Assembly 3-Chemical Processing 5-Ore Concentration 7-Other (Please Specify)
2—Machining 4—Smelting 6—Mining
13 Have you ever smoked as many as five packs of cigarettes, that is, as many as 100 cigarettes during your entire life' 1 -Yes
2-No
Col 20
14 Do you now smoke cigarettes'
1-Yes
2-No
Col 21
16
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Figure 1 (continuation) Platinum, Palladium and Lead Questionnaire
15 II you are a current or >in ex cigarette smoker:
er day
1 - Less than 112 pack per day (1-5 cigarettes per day)
2-About 1/2 pack per day (614 cigarettes per day)
3-About 1 pack per day (15 25 cigarettes per day)
4-About 1-1/2 packs per day (26-34) cigarettes per day)
5-About 2 packs per day (35 or more cigarettes per day)
b How old were you when you first started smoking?-
_Years
r How old wrro you when you last gave up smoking, if you no longer smoke?_ Years
Hi Wh.il is yout mm it.il st.itus7
1--Single
2 -Married
3 -Separated
4-Divorced
5-Widowed
17 How many times have you and your family changed living quarters during the last five years?
0- None 2-Two times 4-Four times
1-One time 3-Three times 5-Five times or more
18 What educational level has been completed by the head of your household:
I - Less thnn 8th qrade
2 8th grade
j High School - Incomplete
4- High School -Completed
19 What was your age in years on your last birthday?_
20 What is the natural color of your hair'
21 What is your sex?
1-Male
22 Females Only.
a What is your hormonal status?
h Do you use oral contraceptives'
1—Brown
2-Black
3-Red
2—Female
1—Pre puberty
2-Menstrual
3—Menopause
1-Yes
2-No
5—College—Incomplete
6-College-Completed
7-Graduate School
.Years
4-Blond
5—Gray
23 Have you ever experienced any of the lung related 0—None
problems listed here: 1—Asthma
2—Emphysema
3—Tuberculosis
4-Histoplasmosis
5—Bronchiectasis
6—Bronchiohtis
7—Bronchitis
8—Tumor or Cancer
9-Other (Please Specify)
2t Aio you presently being treated for any of the illnesses listed here. 0-None 3-Sickle-cell
1-Diabetes 4-Kidney disease (Please Specify)
2-Thyroid ___
25 Are you presently taking prescription medication on a regular, daily basis? 0-None 2-Stimulant 4-Cortisone Type
1-Tranquilizer 3-Pam 5-Other (Please Specify)
Suppressant
YOU HAVE COMPLETED THE QUESTIONNAIRE
THANK YOU FOR YOUR COOPERATION
STAFF USE ONLY
IMNOWO 1 23456
Col 22
Cols 23 24
Col 28
n
Col 29
Cols 30 31
Col 32
Col 33
Col 34
Col 35
Col 36
n
Col 37
Col 38
Col 39
r
Col 80
17
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questions have been reduced to the numerical codes shown in Table 1
and encoded in the appropriate boxes on the forms. The third and final
step in preparation and processing of the questionnaire data is keypunching
the data onto two keypunch cards. Card 1 contains name, address, and
telephone number, and card 2 contains covariate data used to select
participants and, ultimately,to correlate with the results of analysis of
the samples obtained from human volunteers.
3. Backup Materials
/
A set of backup materials was developed for use in
recruiting organizations and in recruiting volunteer participants at each
organization. The materials included a narrative summary describing the
study and requirements of participating organizations and volunteer
participants, a one-page summary of sample collection criteria and
procedures for each of the four distinct areas in which organizations and
participants were recruited, and a one-page summary of study background
and specific requirements for volunteer participants for each separate
organization from which volunteers were obtained. In addition, a one-
page brief summary of requirements for autopsy samples in the two areas
of Southern California was generated for use in soliciting help in the
matter of collecting and providing to this study such samples by appropriate
agencies.
18
-------
Table 1
Numerical Coding of Responses
to Questions 8 and 10
Question 8 : Code 1 - 4 as indicated on form.
Code 5 in following manner:
5 other, (inappropriately answered)
6 medicine (dentistry)
7 public assistance (fire, police, ambulance)
8 law
9 education
10 business (commercial activity)
11 industry
12 recreation
13 media
14 government (civil service, military)
15 construction
16 research
Question 10: Job Title
0 (inappropriately answered)
1 professional
2 administrative
3 technical
4 clerical (secretary, file clerk, cashier)
5 sales
6 foreman and craftsmen
7 laborer (kitchen, custodial, maintenance, news carrier)
8 assistant (attendant)
9 volunteer worker
10 waiter, waitress
11 teacher
12 librarian
13 heavy motorized equipment operator
14 mining
15 refining
16 electrowinmng
19
-------
4. Recruitment Activities
a. Southern California
The study design incorporated use of volunteer
participants living near a freeway in Los Angeles and a second set of
volunteer participants living in an area with less exposure to automotive
emissions near the Los Angeles area. The design was to match the
socioeconomic characteristics of the more and less exposed groups as
much as is practical and reasonable so as to minimize spurious effects
due to socioeconomic parameters. A number of public organizations in
the Los Angeles region were contacted to obtain advice regarding specific
areas appropriate for the study design. Principal organizations and
persons contacted are the following:
Person
Dr. Fred Ottoboni
Dr. Norm Perkins
Jim Heacock
Dr. Oscar Balchum
Jack Rogers
Dallas Candy
Dr. Stanley Rocow
Dr. Thomas T. Noguchi,
Medical Examiner
Organization
State Dept. of Health
Berkeley, Calif
State Dept. of Health
L.A. Branch Office
Occupational Health Unit
USC Medical School
Dept. of Chest Medicine
L.A. County Dept. of Health
Occupational & Radiological
Health
Acting L.A. County Health Officer
L.A. County Dept. of Health
L.A. County Lung Association
Los Angeles County
20
-------
Person
Don Madden
J. A. Stuart,
County Air Pollution
Control Officer
Howard Lange
Dr. Ray Thompson
Wesley Sholts, Dir.
Ron Huber, Asst. Dir.
Dr. Picken, Staff Phys.
Robert M. Young,
Personnel Officer
Dr. Wright, Chief of
Staff
Henry Ford, Office of
Director
Dr. Fishken, Chief of
Clinical Lab. Sciences
Cordell R . Welcome,
Office of the Director
John Valance, Director
of Brentwood
Dr. Jeremiah Thompson, UCLA
Pharmacology Dept.
Dr. David Porter, Pathology Dept.
Dr. Jane L. Valentine,
School of Public Health
Dr. John F. Schacher, Professor of
Infectious & Tropical Diseases,
Div. of Epidemiology, School of
Public Health (also chairman of
human subjects)
Organization
Public Info. Assistant
Air Pollution Control
District
Los Angeles, Calif.
District 7
California Highway Dept.
Los Angeles, Calif.
Dept. of Health
Riverside County
U. C. Riverside
Mira Loma Hospital
L. A. County Health
Wads worth VA Hospital
Los Angeles, Calif.
21
-------
Areas along the San Bernadino Freeway in the vicinity of Pomona,
San Bernadino and Riverside and areas along the San Diego Freeway in
Los Angeles and in the vicinity of Santa Monica were found to be the best
candidates for the study sites with higher exposure. Recruitment through
churches, apartment complexes, hospitals, and universities was con-
sidered. An area in Los Angeles along the San Diego Freeway in the
vicinity of Santa Monica was ultimately chosen for the higher exposure
site. The specific area lies immediately west of the San Diego Freeway,
in Los Angeles, between National Boulevard and Sunset Boulevard.
Selection of this site was principally for the following four reasons:
1) EPA operates an air monitoring station in the vicinity of the site chosen
which is planned for long-term monitoring of the San Diego Freeway.
2) The prevailing wind is from the direction of the ocean, four or five
miles away to the west, with little or no industry between the freeway
and the ocean. Therefore, heavy metal pollutants found in the air can be
related to automotive traffic. This condition is not true for the second
major area considered for study, the San Bernadino Freeway. Pollutant
levels are generally higher on the San Bernadino Freeway, but some of
the pollutants result from industrial, rather than automotive, sources.
3) A UCLA student residential area is located immediately adjacent to
the San Diego Freeway, downwind, and UCLA provided approval for
volunteer student participation. 4) A large VA hospital, the Wadsworth
Veterans Administration Hospital, is located near the freeway with a
22
-------
staff of several thousand, some of whom reside in the primary area of
study, downwind of the vicinity of the freeway. Conversations with
VA hospital staff indicated necessary cooperation could be expected to
recruit volunteer participants among hospital staff and staff families.
Conversations with L.A. County Department of Health officials
yielded consideration of a remote county hospital in Lancaster, California,
as the best candidate for volunteers from a less exposed area. The area
is in Los Angeles County, approximately 40 miles north of Los Angeles
metropolitan area, 70 miles out of downtown Los Angeles. The population
makeup of the area of Lancaster was estimated to be similar to that
found in Los Angeles regarding socioeconomic parameters. Subsequent
conversations with administrative staff at the hospital, Mira Loma
Hospital, Lancaster, California, indicated that the necessary cooperation
could be expected to enable SwRI to recruit volunteer participants among
hospital staff and staff families.
Preliminary meetings were held with staffs at UCLA, the Wadsworth
Veterans Administration Hospital, and the Mira Loma Hospital. A person
responsible for contact was established at each of the organizations:
UCLA - Dr. Jane L. Valentine
Wadsworth - Cordell R. Welcome
Mira Loma - Robert M. Young
For each organization, a specific date, time, and place was
established for meeting with potential volunteers, and the meeting was
advertised. At UCLA, an article was written and submitted to a campus
newspaper, and notices were posted at appropriate bulletin boards in the
23
-------
residential area, a married student housing area where students and
student families were located. Some notes were provided directly to
residents of the campus housing selected for study. On the appointed
day, a meeting was held with prospective volunteers to obtain completed
questionnaire forms from all volunteers, both students and student
families.
At Wadsworth, an article was placed in the hospital newsletter,
and advertisements were posted on appropriate bulletin boards advertising
the recruitment meeting. Prospective volunteers completed questionnaire
forms and turned them in to the survey team.
At Mira Loma, the recruitment meeting was advertised by
placement of notices on appropriate bulletin boards. On the appointed day,
SwRI staff first met with principal members of the hospital administrative
and medical staff. A certain number of the supervisors then briefed their
people regarding the study requirements for volunteers. A subsequent
meeting with prospective volunteers was held to obtain completed questionnain
forms from all who volunteered for the study.
The final set of completed questionnaire forms were then prepared
for keypunch and the results were sorted and listed for use in selecting
specific volunteers. Volunteers selected from the UCLA married student
housing area tended to be children and young adults, with some older people.
Volunteers selected from Wadsworth tended to be middle and older aged
adults, with some younger adults. Volunteers selected from Mira
24
-------
L/oma staff and families were from all three age groups: children, young
adults, and older adults.
b. Ontario
The study design incorporated use of volunteer
participants occupationally exposed to platinum or palladium. Persons
in the mining of precious metal refining industries were considered as
the primary candidates to fulfill this study requirement. To the purpose
of securing cooperation and participation in the study, the following
representatives of International Nickel Company were contacted in New
York, Toronto, and Copper Cliff, Ontario:
Person
Louis S. Renzoni,
Vice President Operations
Norman Hillier, Mgr.
Safety & Plant Protection
Hank Berks, Safety & Plant
Protection
Keith Segsworth,
Air Management
Bill Brown, Assistant Mgr.
Prit Scott. Employ eo
R ela lions
Organization t ,
Location
J. C. Parlee, Vice Chairman INCO
of the Board
INCO of Canada
New York
Toronto
INCO, Ontario Div. Copper Cliff
INCO, Ontario Div. Copper Cliff
INCO, Ontario Div. Copper Cliff
INCO Copper
Refi no ry
Copper Cliff
iNC.O South Mine Copper Cliff
-------
The offices in Toronto and Copper Cliff were visited
to brief appropriate officials regarding the proposed study and to
determine an appropriate site for study,, if INCO should choose to
participate. INCO officials chose to participate in the study and selected
a portion of the Copper Cliff which deals with precious metals and a
mine area where catalytic converters employing platinum and palladium
are used to a great extent.
Questionnaire forms were left with the assistant
manager of the Copper Refinery and with the employee relations depart-
ment at the South Mine at Copper Cliff. Volunteers were recruited by
company officials, and forms were completed and returned to SwRI
personnel at an appointed date. All volunteers meeting the study
requirements of working in an area with exposure to platinum or
palladium were selected as participants.
The cooperation and aid supplied to this study by INCO
should be especially noted. This company provided in excess of two man
weeks of senior level people, free of charge, to aid the initiation of study
activities and followed this up by arranging for a barber, two laboratory
technicians, and performing air samplings at a number of stations,
again without compensation. INCO is due our sincere thanks and
compliments and that of the Environmental Protection Agency.
c . New Jersey
Two companies dealing in precious metals refining in
New Jersey were selected for study. Persons working in precious metals
26
-------
refining processes where some potential of exposure to platinum or
palladium exists were sought as study participants. Officials of each of
the two firms were met with to secure cooperation and participation in
the study.
One of the firms conducted a study in their refinery
and reported the results to Southwest Research Institute.
Matthey Bishop, Inc. collected environmental and
human samples at their refinery located in Winslow, New Jersey.
These samples were analyzed at Southwest Research Institute. The
primary individuals involved with the study at Matthey Bishop were:
Mr. V. W. Makin, President and Mr. Orin G. DeLa , Manager of
Industrial Relations.
5. Participant Selection
a. Selection Criteria
For each of the four areas studied, distinct selection
criteria were developed for recruiting and selecting volunteer
participants. In general, the selection criteria can be described with
two categories: 1) non-occupationally exposed participants and,
2) occupationally exposed participants.
Selection criteria for the two groups of non-occupationally
exposed participants are principally involved with location of residence,
age, and sex of the participant. For participants from the area of high
exposure near the San Diego Freeway in Los Angeles, the selection
criteria included four parameters: 1) normal occupation away from high
27
-------
potential of exposure to lead and precious metals, 2) location of
residence, 3) age, and 4) sex. All persons selected as participants
lived in the vicinity of the San Diego Freeway downwind of the prevailing
wind pattern (east of the freeway). The objective was to recruit three separat
age groips witii equal numbers of males and females in each age group.
The age groups are: 1-16 years, 17-34 years, and 35 years and over
(Groups I, II, and III, respectively).
For the second group of non-occupationally exposed
participants, those from the area of lower exposure in the vicinity of
Lancaster, California, the selection criteria included the same four
parameters as for the higher exposed group. However, the residence
requirement was much less strict than that for the higher exposed group.
It was sufficient that potential participants reside in the general area of
Lancaster or Palmdale and that they had no occupation which normally
took them into Los Angeles.
The selection criteria for the occupationally exposed
participants were limited to two principe>l requirements: 1) occupation in
a job which potentially exposed the participant to significant levels of
platinum and/or palladium, and 2) a minimum of six months at the
particular occupation. Information regarding age and sex of the
participants was obtained, but no specific requirement was enforced
regarding these parameters. Using the occupation criteria, participants
were recruited in Ontario, Canada in the precious metals mining and refining
industry and in New Jersey in the precious metals refining industry.
28
-------
For each participant, a complete questionnaire form
was obtained with the exception of the refiners in New Jersey where
only a part of the questionnaire form was used: questions 1, 9, 10, 14,
19, and 21 as presented in Figure 1. In addition to the principal
parameters used as selction criteria, data regarding a number of
supplementary parameters were also obtained in order to identify certain
important socioeconomic and health related data for each individual.
These data can be used to establish the gross characteristics of the
participants when statistical data are being used in comparisons between
different groups of participants. Most important among the supplementary
parameters are: years of residence in the city, frequency of change of
living quarters, education level of the head of household, and smoking
history.
6. Description of Study Participants
A total of 141 participants were recruited and selected in
Los Angeles, 142 in Lancaster, California, and 49 in Ontario through use
of the recruitment methods documented here. An additional 61 volunteer
participants were obtained in New Jersey by recruitment by company
officials in the particular organization chosen for study. For the New
Jersey participants, information regarding age, occupation, sex, and
smoking history was collected with the partial questionnaire form. The
ethnic composition of these 393 volunteer participants is as follows:
Los Angeles: 60% white, 40% non-white; Lancaster: 80% white,
20% non-white; Ontario: 100% white; New Jersey: 90% white, 10% non-white.
29
-------
Pertinent socioeconomic and demographic characteristics for the volunteer
participants used in this study are presented in Table 2 and shown in
Figure 2. Analysis of the occupations of the participants is provided in
Table 3. Separate information is provided for the non-occupationally and
the occupationally exposed groups. A complete listing of information on
all participants from Los Angeles and Lancaster is given in Appendix A.
To utilize the coded information, refer to Figure 1.
C. Collection of Samples
1. Environment
a. Baseline
The baseline study for environmental characterization
of platinum, palladium and lead in air, water and soil was performed in
Lancaster and Los Angeles. In Los Angeles, the reference point for
sample collection was the San Diego Freeway and the sites designated
as "A,B,C,&D" in the Los Angeles Catalytic Study (L.A.C.S.) and
operated by the E.P.A. These sites are upwind and downwind and
straddle the freeway between Sunset and Wilshire Boulevards.
After approval was obtained and access granted for
use of the "C" site, two hi-volume air samplers (Staplex) were set up
adjacent to the samplers maintained by E.P.A. The SwRI samplers were
placed so that, relative to the freeway, they were downwind and in the
same plane as the surface of the freeway. Samples were collected on
Type A glass fiber filters without organic binders. Continuous collection
took place until the rotameter on the saimpler approached 40 cfrn.
30
-------
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When this value was reached, a new, clean filter was then exchanged
for the old filter with the particulate matter collected on it. The used
filter was then folded in half with the sa.mple on the inside. This
previously numbered filter was then returned to its original plastic bag
and sealed. A computer-printed label was then affixed to the bag and
the identification number recorded in the log book on the data sheet.
Each sample recorded had accompanying data that included initial and
final times, rotameter readings and site location. Notation on wind
direction was also made. Sample collection continued for
14 days. These samples were used for ambient air measurements of
platinum and palladium. The objective was to collect particulate matter
from as much air as possible (two samplers for 14 days) to insure that the
maximum sensitivity could be achieved,, The intent of the study was to
report the limits of sensitivity as "less than" values if no platinum or
palladium was detected.
In addition to the air sampling at site "C" of L.A.C.S.,
air samples were taken also at the UCLA Married Student Housing (MSH)
on Sepulveda Blvd. The samplers were placed in the playground area
next to MSH Community Center. This site was chosen because, as with
the "C" site previously mentioned, it was also in the same plane as the
freeway surface and more importantly v/as in the area where a large percent*
of the study participants resided. The fenced-in playground area
provided a secure spot for uninterrupted and undisturbed sample
collection. Air collection times and procedures were the same as
34
-------
performed at the "C" site. These filters were used for ambient air
lead measurements. Ambient air lead data from the LACS was to be
used for most of the study area; however, it was decided that additional
lead data would be needed for the UCLA MSH area, as this is some two
miles from the LACS site.
During the Los Angeles air collection period, samples
were also taken in Lancaster, California. Air samplers were placed
in the backyards of homes within the community. Samples were collected
continuously and until the pressure drop registered 40 cfm on the rotameter,
at which time the filter was changed. These samples were used for Pt
and Pd measurements. An additional air sampler was run to determine
ambient air lead levels, and its filter was changed every 24 hours. Both
types of samples, continuous and 24-hour, were collected over 14 days
and ran concurrently with the Los Angeles samplers. Data reflecting
sampling times and flow rates were noted and recorded in the log book.
Calculation of the true and total air flow was performed using calibration
sheets previously constructed for each air sampling unit.
During this 14-day air monitoring period, one day was
set aside for soil sampling. Acid washed polyethylene containers were
used for this purpose, and duplicate samples were taken at each site.
Soil was sampled adjacent to sites "A" & "D". Surface soil samples were
collected. Also, on opposite sides of (upwind and downwind) and within
ten feet of the freeway, duplicate samples were taken. These sampling
points were between sites "B" and "C"; however, they were much closer to
the freeway than were the air sampling sites.
35
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Soil samples were also taken at the UCLA MSH complex,
Soil collected approximately 100 feet west of the freeway served as the
control, as this point was upwind from the freeway. On the downwind side,
duplicate samples were taken at 20, 100 and 300 feet from the freeway.
The latter two distances, 100' and 300', are both within the confines of
the MSH complex and approximate the boundaries of the complex
perpendicular to the freeway. (Figure 8)
Samples in Lancaster were taken on a random basis
within residential areas and near the hospital where many of the volunteers
were employed. Each of the soil samples from Los Angeles and Lancaster
had a computerized label placed on the container after collection which
described the location and sampling point.
Water samples were collected in one liter acid-
washed polyethylene containers. Samples were taken from tap water at
the MSH complex, the Veterans Hospital (Wadsworth), and from various
homes in the study areas both in Los Angeles and Lancaster. Again, each
container had its own individual label affixed for easy referral at data
analysis time .
Paint samples were collected from exterior surfaces
of the MSH. Suitable samples were obtained by scraping the paint down
to the surface using a knife. The paint chips were placed into polyethylene
bags.
36
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b. Mining
Environmental sampling was also performed at a
mining and smelting complex in Sudbury, Ontario, Canada. The
International Nickel Company (INGO ) was most cooperative in allowing
SwRI to conduct the survey at their facilities and fully assisted the survey
team.
Air samples were collected at various points at the
INCO facilities. The points were chosen based on discussions with the
engineering personnel in order that probable sources of Pt and Pd could
be ascertained before sample collection began.
Ambient air samples describing the background levels
were collected outside near the INCO engineering building. Samplers were
started and ran until the rotameter fell to approximately 40 cfm at which
time a new filter was exchanged for the soiled filter. During the seven-day
collection period, fog and misty conditions were present on three days and,
consequently, the samplers were checked more often than usual.
Two samplers were operated in the precious metals
building where the various metals are removed from the crushed ore
slurry. This removal process is one of concentration in which some
metals, especially Pt and Pd, are shipped in a residue form for
processing at a subsequent facility. The air samplers were placed near
probable sources of Pt and Pd in the room air during the concentrating of
these metals. Particulate matter was collected on each of the filters
until such time as the rotameter approached 40 cfm, and the filter was
then changed.
37
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Underground mining operations provided another
air sampling point for Pt and Pd. The rationale for sampling air in
the mines was to determine if the workers were inhaling these metals
in the dust formed as a result of mining Pt and Pd ore and from the use
of diesel engines operated with catalytic: mufflers. The Institute survey
team went down into the mines on a tour to observe mining operations
and, more importantly, visit the sites where the air samplers were
placed. The samplers were positioned near the various drilling, hauling
and ore crushing processes and were in operation only during the hours
of greatest activity which was during the day shift.
An air sampler was set up in the area where
regeneration of the diesel muffler catalytic pellets was accomplished.
The used pellets are screened to remove chaff and then are roasted in a
regeneration unit at a temperature of 650°C to remove tar. During this
roasting period, the air samples were taken.
Water and soil samples were taken during the same
seven-day interval as were the air samples. A representative from INCO
collected these samples.
c. Refineries
Sampling of the environment within a refinery in New
Jersey was performed to characterize the particulate matter with reference
to Pt and Pd. Two refineries of these precious metals were contacted to
participate in the research study. One refinery performed their own
38
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sampling and analyses. The other refinery also collected samples,
but the analyses were performed at the SwRI laboratories in San Antonio.
The air in two areas of the second refinery complex was sampled.
Staplex air samplers were suspended six feet from the floor near the
return air flows in the salts recovery and refinery areas. The collection
of the sample on preweighed 8" x 10" glass fiber filters took place for
five consecutive work days. The filters were changed every 24 hours,
and the total volume of air sampled was computed for each of the calibrated
samplers. Each filter was subsequently vacuum-dried to achieve a
constant weight before the weight of the particulate matter was determined.
Before the filters were prepared for analysis, a section (15%) of each
filter was quantitatively removed and set aside. This portion was sent
to the refinery for their analysis. In addition to these sections of collected
filters, an additional air sampler was also run by the company next to one
of the SwRI samplers. Air sampling was performed concurrently with the
biological collection from the human volunteers.
Environmental sampling other than air was not performed
due to prior agreement with this company and concurrence of the Project
Officer.
Z. Study Participants
a. General Procedure
The conduct of a survey of this magnitude requires
considerable advance planning.
39
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Because of the variety and number of specimens
required, an efficient labeling system was needed to ensure that all
the samples were properly collected and processed. A computerized
labeling system was used to preprint all labels necessary for sample
collection and processing at a particular site. As an example, each
participant had his own shopping bag labelled with his name and
identification number. Inside the bag were the sample collection containers
which had the participant's name, location (Los Angeles, Sudbury, etc.)
identification number, sample type (urine, feces) and sample number
(first or second sample). Prior to the first meeting with the participants,
the collection kits were put together. These kits included two feces
bottles and two urine bottles prelabelled with the above described label.
The sample container kit was then handed out at the first meeting with
the study participants.
Hair samples were collected from each participant in
fulfillment of the sampling protocol. The accomplishment of this task was
performed at the meetings when the volunteers came for blood collection.
Professional barbers were used. Two types of hair samples were taken:
long hair and short hair. The long hair was taken from the top and sides
of the head using thinning shears. The short hair sample was taken from
the nape of the neck where hair growth was most recent. Electric clippers
were used to collect this sample, and a minimum of 1 gram of hair was
required for each type of sample. It is obvious that the continued
participation of the volunteer could easily be ended if the hair was cut
40
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improperly so as to alter the cosmetic appearance of the participant's
hair. Therefore, before any hair was collected, each of the barbers
was given verbal instructions on the type and amount of hair required
and that the appearance of the participant's hair style must not be
changed.
Blood collection was carried out by a qualified
medical technologist under the supervision of a physician. While it was
assumed that the medical technologist was familiar with blood collection
procedures, a strong emphasis was made to preclude faulty technique.
The technologist was advised as to the sources of contamination in the
collection procedure.
Blood samples were collected by the vacutainer
system using two 10-ml low lead, heparinized tubes as supplied by
Becton and Dickinson. A suitable vein in the antecubital region was
chosen, and the area was cleansed using a brisk mechanical scrubbing
action with the alcohol prep. If the cleansed area came into contact with
anything else before the sampling, the entire procedure was repeated.
Similarly, sampling equipment was discarded if contaminated before use.
Experience in previous surveys indicated that a
continuing effort was needed to alleviate any fears or hesitancy on the
part of adults and especially the children in collection of blood samples.
All procedures were thoroughly explained and questions answered before
blood collection commenced. A concerted effort was made to insure
that no trauma, either physical or emotional, was experienced by the
41
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volunteers. Although every effort was made to collect 10 ml of blood
from young children, in some instances this was not possible. Some
young children were quite small, and their veins were difficult to collect
blood from even using specially designed syringes. As this study was on a
voluntary basis, no undue chances were taken with these children, even
if the primary difficulty was the child's noncooperation.
After the blood was drawn, the volunteer was
instructed to place his thumb behind the elbow and with the remaining
fingers wrap around the arm and hold the sterile gauze in place. The
participant was then walked to the waiting area and observed for a few
minutes. A tape strip bandage was then applied to prevent the puncture
site from becoming infected. For the children, a special effort was made
to compliment their behavior and to provide rewards of candy or balloons.
The blood collected in the vacutainers was immediately
rotated for a few minutes to ensure that the heparin in the tubes would
prevent coagulation from occurring. The blood sample was then poured
into an acid-washed, 30-cc polyethylene bottle with the corresponding
label attached and then immediately frozen. The urine samples were
weighed and the specific gravity factor a,pplied to yield the total volume.
The bottle was then shaken to ensure a homogeneous sample and an aliquot
poured into a 175-ml polyethylene bottle and made to 1% acetic acid. The
corresponding label was placed on the bottle which was then put into an
ice chest with dry ice. The feces sample was placed on dry ice as soon as
it was handed to the survey personnel. Hair samples were kept at ambient
42
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temperature. All samples were held in their respective environments
during shipment to, and storage at, the San Antonio laboratories.
b. Informed Consent
The volunteers selected for study were told about the
project, its purpose, goals and possible connection to their way of life.
The informed consent was presented to them, and it was explained that
this form is a requirement of the U.S. Public Health Service whenever
human subjects are employed in research. Emphasis was placed on the
fact that the signing of this form in no way affected their right to
withdraw from the program at any time. Each volunteer was verbally
instructed as follows:
"The informed consent form before you is a requirement
of the U.S. Public Health Service regulations concerning
use of human subjects. This form is for your protection.
When it is completed by your signature and my signature,
it will serve as a record that I, as a Project Director, have
been present to answer any of your questions regarding the
project that I have described, the purposes and intent of the
program, as well as a description! of any inconveniences,
discomforts, and potential risks that may be involved, and
I have provided you with a description of the benefits
expected. I have also assured you that you are free to
withdraw your consent and discontinue your participation in
43
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the project or activity at any time you wish. I also
wish to assure you that your identity in this survey
will not be disclosed. If you feel that I have
accomplished these to your satisfaction and that you are
willing to participate in the survey, please sign the
informed consent."
The volunteers were then asked to sign the consent form if they
felt that the goals of the project, any possible discomfort to them and
non-disclosure aspects had been explained to their satisfaction. The
consent form thus signed by the volunteer was then countersigned by the
project director as the person who informed them. Another participant
in the survey acted as a witness to the above signatures. At present,
these signed informed consents are on file at SwRI in the office of the
principal investigator. Access to the names of these volunteers has been
limited to the principal investigator and his project staff. A copy of the
form used for informed consent is shown in Figure 3.
c. Information Sheets
After the informed consents were completed, the
participants in the study were given a detailed explanation of the schedule
for collection of samples. Sample containers for urine and feces collections
were then handed out. Usually, a small group (5-10 people) had the
collection procedures explained to them, and in this way the time spent
44
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Figure 3. VOLUNTEER'S INFORMED CONSENT
SOUTHWEST RESEARCH INSTITUTE
8500 CULEBRA ROAD • POST OFFICE DRAWER 28510 • SAN ANTONIO. TEXAS 78284
I.
residing at (street address, city, zip code)
hereby acknowledge and certify to the following:
i. That I hereby volunteer and consent to participate as a human test subject in
an experiment designed to determine exposure to environmental pollutants entitled,
"Determination of Baseline Requirements for Platinum and Palladium in Human Tissue".
2. That I have been given, in my opinion, an adequate explanation of the nature,
duration and purpose of the experiment, the means by which the experiment will be
conducted and any possible inconveniences, hazards, discomforts, risks, and adverse
effects on my health which could result from my participation therein;
3. That I have been informed of all appropriate alternative procedures, if any
exist, that might be advantageous to me;
4. That I understand my questions concerning procedures which affect me will
be answered fully and promptly;
5. That I understand that I have the right to withdraw my consent and to discontinue
participation in this experiment at any time without prejudice regardless of the status of
the experiment and regardless of the effect of such withdrawal on the objectives and
results which the experiment is designed to achieve; and I also understand that my
participation in the experiment may be terminated at any time by the investigator in charge
of the project or the physician supervising the project regardless of my wishes in the
matter;
6. That I hereby understand and agree that the samples collected from me will be
analyzed for their content of trace metals (platinum, palladium and lead), and that these
are the only tests that will be made on these samples and that no medicinal compounds
will be analyzed.
7. That I attained the age of years on my last birthday which was
, and that I am executing this Volunteer's Informed Consent as
my free act and deed.
Executed this day of , 19
Executed in my presence and in
the presence of each other.
Witness
Volunteer
Person informing volunteer and obtaining
volunteer's consent
SAN ANTONIO. HOUSTON, CORPUS CHRIST). TEXAS. AND WASHINGTON, D.C.
45
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VOLUNTEER'S INFORMED CONSENT
(page 2 )
If subject is a minor, complete the following,
Subject is a minor (age ).
Father
Mother
Guardian
Other person and relationship
46
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at this meeting could be kept to a minimum. It was emphasized to
each volunteer that accurate information could only be obtained if
directions were followed completely. Incomplete sampling would
produce incomplete information, and therefore the success of the research
project depended on their complete cooperation.
The urine collection began in the evening after supper,
generally between 6 and 8 PM. Prelabeled, 2-liter wide-mouth poly-
ethylene bottles were given to each participant for the urine collection.
These containers had been cleaned in an acid bath containing 4N HC1 and
3N HNC>3 for eight hours, then rinsed at least six times with deionized
water and finally dried in a laboratory oven. The subjects were told to
collect urine through the next morning. The sample was then brought to
the place designated for blood collection or dropped off at a collection
point. The second sample collection began that evening after supper and
continued until the following morning.
Instructions for fecal specimens were also given.
Again, the volunteers were cautioned against putting anything into these
specially cleaned containers other than their own feces. Toilet paper or
urine were to be avoided. During the same period as the urine collection,
the volunteers were told to collect all of their fecal specimens. No
restriction was placed on the volunteer's diet. Verbal instructions for
the proper collection for each of the samples was supplemented by a
printed instruction sheet included in the bag with the containers given to
each individual.
47
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When each subject had completed the sample
collections, he was paid for his participation. Each volunteer was told
that he would receive a summary of the results. Individual values were
not to be given.
The procedure used at the refineries for collection of
samples differed somewhat from those of the baseline and mining areas.
At both refineries, blood and urine samples were collected in conjunction
with an annual physical examination of the employees. Collections were
carried out by the companies. At one of the refineries, an information form
was filled out by each employee listing name, age, sex, job title, length
of employment with the company, shift worked, and smoking habits. An
identification number was assigned to each employee and this number
incorporated on each of the samples collected.
The procedures used at this refinery were as follows:
Acid-washed urine collection containers showing participants' names were
handed out to each volunteer. They were given verbal and written
instructions on the proper collection of samples. Shift workers from the
three shifts at the plant volunteered; thus, the collection period varied
according to shift. For the day shift, they were told to begin collection
of their samples in the evening (generally between 6:00-9:00 PM).
Collection continued through the night and included the first sample upon
arising in the morning. The second shift (4:00 P.M. to 12:00 Midnight)
began their collection after work and continued until the first specimen
after arising was collected. For the personnel of the third shift
48
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(11:00 P.M. to 7:00 A.M.), the first specimen after rising was collected.
In each case, the workers were asked to bring the urine samples to the
nurse's station after collection was completed. Each specimen was
subsequently weighed, and an aliquot (maximum of 175 ml) was acidified
to 1% acetic acid. These aliquots were then immediately frozen. An
additional aliquot of each sample was also prepared for the company in
the manner prescribed above.
Collection of blood was performed by medical technologists
employed at a local hospital.
Blood collection took place at the plant and during
working hours with the employees being scheduled at the convenience of
the plant's production schedule. For the day-shift personnel, appointments
were made for every 10 minutes, and this schedule was posted as a
reminder to each participant. Blood sampling was begun at 1 P.M. and
continued until all volunteers from the day shift had their blood drawn.
However, before blood collection began, each employee was instructed to
wash his arms thoroughly with soap and water lest any trace amount of
Pt and Pd contaminate his blood sample. If the arm was still dirty after
the medical technologist had washed the antecubital area with an alcohol
swab, the arm was rewashed with additional soap and water. Standard
blood drawing techniques were used with the vacutainer system
employing two 10-ml heparinized, low-lead vacutainers. The blood in
each of the two low-lead vacutainers was poured into acid-washed 30-cc
polyethylene bottles as soon as practical after collection. One blood
49
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sample was frozen and the other retained by the refinery. The SwRI
samples were shipped frozen in dry ice to San Antonio and kept frozen
until analysis.
Autopsy samples were collected in Los Angeles and
in Sudbury. Twenty-five gram samples of muscle, liver, kidney, spleen,
lung and fat were collected by a pathologist in a hospital in the area.
Unsuccessful attempts were made to secure autopsy samples from
accidental deaths through Medical Examiner's offices. Each pathologist
was given sample containers with a label that was to be filled in for
information such as age, sex, ethnic origin, cause of death and smoking
history if known. The pathologists were advised as to the intended
purpose of these samples, and each was instructed on the precautions to
follow to prevent contamination. All samples were frozen as soon as
possible following collection and kept frozen until analyzed.
Ten autopsy cases (5 male - 5 female) were collected
in Los Angeles, and ten were collected in Sudbury (all male). The autopsy
cases in Los Angeles were from persons of different ages (young to elderly)
that resided in Los Angeles prior to death. The autopsy cases from
Sudbury were restricted to individuals that had been employed as miners,
ore processors, etc. in the mining operations in Sudbury.
50
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D. Analytical Methods
1. Literature Review
Review of the literature prior to 1974 revealed very few
references to Pt or Pd concentrations in biological samples. Generally,
where references were made to Pt or Pd, neutron activation analysis
(2)
was the only method able to estimate the concentration present.
There are a number of references in the literature for
Pt and Pd analysis on metallurgical, geological and other types of
samples using atomic absorption spectrophotometry; however, the levels
of the two metals are much higher in these samples than in biological
samples.
Increased interest in Pt and Pd over the last two years
has produced several recent papers dealing specifically with Pt and Pd
(3)
in biological samples. A paper by Yoakum, Stewart and Sterrett
gave an emission spectrochemical method to determine Pt, Pb and Mn
in rat tissues. These investigators stated that the emission spectrochemical
method and flameless atomic absorption methods could not reach a level
of sensitivity sufficient to quantitate residual concentrations of Pt in
tissues without preconcentration treatment.
(4)
LeRoy stated that, to determine Pt in one gram of wet
tissue by the graphite analyzer, there would have to be a minimum
concentration of 0.25 ppm for reproducible results. This was based
upon direct injection of the digested tissue into the graphite analyzer.
LeRoy also mentioned the use of aliphatic secondary amines (in xylene) as
51
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extractants for preconcentrating Pt and Pd prior to analysis. He stated
that methyl isobutyl ketone (MIBK) could be used to extract Pt but did not
recommend it.
An excellent review of analytical methods for determining
(5)
Pt and Pd in biological tissue by Bumgarner and Yoakum summarized
the situation regarding "flameless" atomic absorption analysis by
saying a preconcentration scheme would still be necessary.
Analysis of Pt and Pd using the graphite analyzer ("flameless'
and atomic absorption spectrophotometry (AAS) has been reported on
(6-8)
aqueous solutions both directly and by extract. Adriaenssens and
(9)
Knoop have reported the optimal conditions for analysis of three noble
metals (including Pt) in the graphite analyzer. The reported sensitivity
and detection limit for Pt were 1 ng and 1. 1 ng , respectively.
(10)
Guerin reported some interferences that can affect the
analysis of Pt and Pd in the graphite analyzer. He also mentioned the
extraction of Pt and Pd using Aliquat 336 in MIBK from HC1 solution.
Guerin said there was no solvent enhancement effect as there is with
flame analysis using organic solvents. The reported absolute detection
limit using a 10(j.l injection of the extract was 0.005 ng Pd and 0.05 ng Pt.
„ - (11)
Janouskova, Nehasilova and Sychra examined the effect
of 19 elements and 6 acids on the graphite furnace determination of Pt.
They found that only ruthenium, strontium and nitric acid interfere.
The reported sensitivity was 0.8 ng for 1% absorption.
52
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2. Instrumentation
All analyses are performed on a Perkin-Elmer Model 306
Atomic Absorption Spectrophotometer modified (Perkin-Elmer Optical
Modification Kit No. 040-0286) to reduce the "light scattering" effect
caused by the graphite furnace. A Deuterium arc background corrector
is routinely used to compensate for non-specific background absorption.
Absorption peaks are recorded with a Perkin-Elmer Recorder Model 056
with a 10 mv range.
Flameless analyses are done with a Perkin-Elmer HGA-2000
Graphite Furnace. Flame analyses are by aspiration of the sample into
an air-acetylene flame using a 3-slot burner head.
Calculation of analytical curves (method of additions) and
determination of unknown sample concentrations are done on a
Hewlett-Packard Programmable Calculator Model 9810A.
Ashing of tissue samples for Pb determination is performed
on a LTA505 low temperature asher manufactured by LFE Corporation,
Waltham, Massachusetts.
Evaporation of urine and water samples is carried out with
a Rotavapor-RE/A, Brinkmann Instruments, Inc., Westbury, New York.
3. Reagents
All reagents are analytical grade unless otherwise indicated.
Atomic absorption standard solutions (1,000 ppm) for Pt
and Pd are the K^Ptd/ and PdCl?, respectively, from Ventron Corp. ,
53
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Alfa Products, Danvers, Massachusetts. Atomic absorption standard
for Pb (1,000 ppm) is from Fisher Scientific Co. , Pittsburgh, Pennsylvania.
4. Selection of Analytical Methodology
Several important criteria were considered in the development
of methodologies for Pt, Pd and Pb analyses of biological material.
(a) Since the expected concentration of Pt and Pd in the
samples would be very low, some preconcentration procedure
would be needed.
(b) The methods developed had to be adaptable to large
numbers of samples.
(c) The method must be fast, simple, and accurate.
(d) If possible, the sample workup would be for all three
elements to avoid duplication of effort.
(e) The time available for methodology development would
be limited.
The final criterion, being the most severe, limited the
development to selecting procedures from the literature and adapting
them to biological samples and atomic absorption analysis.
5. Platinum and Palladium Methodology
a. Extraction Procedure
The above restrictions placed on the analytical methods
development of Pt, Pd and Pb directed the main emphasis to finding
a suitable extraction procedure which would quantitatively remove Pt,
Pd and Pb from the sample matrix.
54
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Ammonium pyrrolidine dithiocarbamate (APDC)
chelation with subsequent extraction of the metal complexes into methyl
isobutyl ketone (MIBK) was tried on aqueous spike solutions. Very erratic
results were obtained with Pt, but Pb and Pd extracted very well at pH 5. 0.
Recoveries of Pd ranged from 68 to 87%.
Extraction of the stannous-chloro complexes of Pt with
MIBK or ethyl acetate gave recoveries of 80 to 120% at spike concentration
of 0. 8 ppm but only 40-50% at 0. 1 ppm. Pd and Pb were not extracted under
these conditions.
The extraction of Pt and Pd stannous-chloro complexes
with high molecular weight amines (HMWA) appeared to fulfill most of the
requirements listed earlier for an acceptable extraction procedure. Lead,
however, did not extract under the conditions used for Pt and Pd. Our
method was patterned after those of Khattak and Magee.
Biological samples have to be digested or ashed prior
to determining the analyte metal(s), and this provides a convenient means
of extracting with a HMWA. The digest or ash is either in, or solubilized in, an
acid, solution, therefore time-consuming pH adjustments are unnecessary, since
the amine functions in an acidic environment. The overall reaction for
this type of extraction is:
n[RNH3V] + [MX]"' ==: ([RNH3+] [MXJn") + nA~ (2)
(°rg) (Aq) n (org) (Aq)
where H A" is HC1 and MX represents the stannous-chloro
(Aq) (Aq)
(14)
complex of Pt(IV) or Pd (II).
55
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The procedure for extraction is essentially the same
for all types of samples. The sample is either digested with acids or ashed
in a muffle furnace. Samples digested with acid are evaporated to 1 to 2 ml
on a hot plate under N? and then reconstituted and evaporated three times
with 5 ml of concentrated HC1. Following the last evaporation, the sample
is cooled and transferred to an extraction vessel using 3N HC1.
Ashed samples are solubilized with aqua regia, evaporate*
to 1-2 ml on a hot plate under N? and then carried through the evaporation-
reconstitution procedure described above.
Once the sample has been transferred to an extraction
vessel (15-20 ml screw-cap Pyrex centrifuge tube), the sample is adjusted
to approximately 10 ml with deionized water or 3 N HC1. The solution
should be approximately 3 N HC1 for extraction.
One milliliter of 25% SnCl^ solution (in 3NHC1) is then
added, and the sample is vigorously shaken for 30 seconds. A 1-ml aliquot
of 0. 02M tri-n-octylamine (xylene solution) is added, and the sample is
shaken for 30 minutes followed by centrifuging for 15 minutes at
3,000 RPM. The octylamine layer (top) is removed with an Eppendorf
pipet and placed in a 4-ml screw-cap vial.
A quick second extraction of the sample is carried out
with 0. 5 ml of xylene, and this is added to the original extract.
The extract is evaporated to dryness under N-, on a
hot plate using low heat. Once the extra.ct is dry, it is capped and
stored until ready for analysis. Just prior to analysis, the sample is
reconstituted with 0. 1 ml (100 41!) xylene and mixed well. A 5-|xl
56
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or 10-jjtl aliquot of the extract is injected into the graphite analyzer
(HGA-2000) for determination of Pt and Pd.
The acid concentration of the extract solution effects
recovery of both Pt and Pd. Figure 4 illustrates that increasing the
acid concentration above 0.5N causes a decrease in recovery of Pd,
while an increase above 8N causes a marked decrease in recovery of Pt.
An approximately 3N HC1 extract was decided upon, since it provided
good recovery of both Pt and Pd and was convenient to use for extracting
a large quantity of samples.
Some other elements were investigated as to their
effect upon the extraction of Pt and Pd. Table 4 shows that only Cu at
2, 000 ppm proivded a significant effect upon a 50 ng Pt ( 1 ppm) extract
signal.
Pd (37.5ng) (0.075 ppm) was seriously affected by
Fe (2,000 ppm) and Cu (2,000 ppm) as illustrated by Table 4. Mn also
enhanced the Pd signal.
Another source of interference with the Pt and Pd
extraction is the concentration of the SnCl? solution used to form the
anionic species prior to extraction. Figures 5 and 6 illustrate the
effect upon Pt and Pd in a 3N HC1 solution. There is a marked decrease
in the response obtained from 50 ng of Pt extract and 37.5 ng of Pd
extract as the concentration of the SnCl solution is increased. This
effect was not observed until late in the study, and, therefore, the 25%
SnCl concentration was used.
57
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(SJ
58
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TABLE 4. EFFECT OF ELEMENTS UPON EXTRACTION
OF Pt and Pd FROM 3 N HC1
Concentration
Element
Fe 2000 0 ++
Mn 500 0 +
Cu 2000 + ++
Pb 1000 0 0
Cd 500 0 0
Zn 2000 0 0
(1) Concentration In 3M HC1 solution Pt and Pd extracted from.
(2) Concentration of Pt = 1 ppm (50 ng of extract analyzed).
(3) Concentration of Pd = 0.075 ppm (37. 5 ng of extract analyzed).
(4) + = enhancement of signal
0 = no effect.
59
-------
100
90
80
70
60
JS
•jf 50-
ffi
rt
-------
150
135
120
105
E
c
• *+
4-»
00
• H
ffi
90
75
60
45
30
15
0.05 Abs
•4-
4-
%SnCl2
6'0
FIGURE 6. EXTRACTION OF Pd (12. 5 ng) FROM 3N HC1 USING VARIOUS
CONCENTRATIONS OF SnCL SOLUTION (3N HC1)
L.I
61
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Shaking times were examined for the Pt and Pd extraction
procedure. Little or no effect was observed on Pt extraction when the
solution was shaken from 5-60 minutes. An increase in the Pd
extraction was observed with shaking times greater than 5 minutes.
The maximum was reached in 15 minutes.
(12,13)
The procedure of Khaittak and Magee was followed
closely during the earlier part of the program, but as improvements
upon the extraction procedure were made, they were incorporated into
the analysis of the samples. Therefore, improved limits of detection
of Pt and Pd for a sample matrix from different locations (see Table 5)
were realized as the program progressed.
The extraction procedure for Pt and Pd is limited by the
fact that the anionic exchange liquid tri-n-octylamine (TOA), creates
an excessive amount of "smoke" during the atomization step in the HGA-2000
This restricts the total amount of extract that can be analyzed and thereby
limits the sensitivity of the method.
Reducing the concentration of the anionic liquid is a
method of reducing the excessive "smoke". The original procedure of
Khattak and Magee called for a 0.2M TOA (in benzene). Below a
0.02M TOA (in xylene), the extraction of Pd became very erratic.
(15,16)
According to Davidson and Jameson, this would be expected since
the concentrations of other anions present will limit the extraction of the
desired anions. Reducing the concentration of the anionic liquid would, in effect,
present fewer available exchange sites for which the analyte anionic
species could compete.
62
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TABLE 5. LIMITS OF DETECTION OF Pt and PD
IN BIOLOGICAL SAMPLES(1>
Sample
Type
Blood
Urine
Hair
Feces
Liver
Kidney
Spleen
Lung
Muscle
Fat
Study
Area
Baseline
Mining
Refinery
Baseline
Mining
Refining
Baseline
Mining
Baseline
Mining
Baseline 1
Mining )
Baseline )
Mining ?
Baseline )
Mining J
Baseline )
Mining /
Baseline )
Mining )
Baseline )
Mining /
Pt
ppm
0. 031
0. 0014
0.0014
0. 006
2 x 10~5
0. 0001
0. 05
0. 0019
0. 002
7 x ID'5
0.00024
0.0026
0.0013
0. 0013
0. 0009
0.0013
Pd
ppm
0. 009
0. 0004
0. 0004
0. 003
7 x ID'6
0. 0002
0. 02
0. 0006
0. 001
2 x ID"5
0. 0006
0. 0067
0.0033
0. 0033
0. 0022
0.0016
Sample Size
10 ml
15 ml
15 ml
1000 ml composite
1000 ml composite
150 ml
11.5 grams composite
11.5 grams composite
300 grams composite
300 grams composite
55 grams wet tissue
5 grams wet tissue
10 grams wet tissue
10 grams wet tissue
15 grams wet tissue
10 grams wet tissue
(1) 2X background noise = limit of detection.
63
-------
The absolute amounts of Pt and Pd, which may be
quantitated on the Perkin-Elmer Model 306, are 1. 07 ng and 0. 33 ng,
respectively. Improvement in the limit of detection therefore necessitated
using larger sample quantities. This was achieved by compositing a large
number of small samples to get one larger sample. Compositing of
samples was done for hair, urine, feces, and air. Table 5 gives the
limit of detection of Pt and Pd for each sample matrix and location.
The limit of detection for the composite samples is based on the absolute
amounts of Pt and Pd detectable with the P-E 306 and the size of the
composite used.
b. Biological Samples
(1) Blood
Whole blood samples were digested with HNC^
(70: 30) in a Vycor beaker on a hot plate (150°C) with a flow of N^.
Table 5 gives the volume of blood analyzed from each sampling site.
The blood was evaporated to 1-2 ml and reconstituted 3X with 5 ml of
concentrated HC1. Following the last evaporation, the samples were
removed from the hot plate and allowed to cool before rinsing into an
extraction vessel with 3N HC1. The extraction procedure outlined
earlier for Pt and Pd was followed to remove these elements from the
digested matrix.
The blood digests from the baseline study were
extracted with 0.2M TOA (in benzene). Only 3/5 of the extract solution
64
-------
could be recovered for evaporation-reconstitution because of the
solubility of benzene in the aqueous phase. The mining (Sudbury) and
refinery blood digests were extracted •with 0.02M TOA (in xylene).
All of the organic extract was recovered for subsequent evaporation-
reconstitution as outlined in the extraction procedure.
Recovering all of the TOA extract, a substantial
improvement in the limit of detection was realized (Table 5). Precision
also improved for Pt and Pd analysis.
(2) Urine
Composites of urine from each sampling site
(except the refinery) were made from the individual overnight samples.
Composites were approximately 1 liter in volume.
A rotary evaporator was used to reduce the composite
urine samples to dryness. The urine residue was solubilized with aqua
regia (50 ml) and rinsed into a Vycor beaker. The sample was evaporated
to dryness on a hot plate (150°C) under N2. The dried residue was then
ashed in a muffle furnace at 500°C using Mg(NO ) as an ashing aid.
The ash was then solubilized with aqua regia and again evaporated to near
dryness on a hot plate (150 C) under N . The sample was reconstituted-
LJ
evaporated with 5 ml of concentrated HC1. Following the last evaporation,
the sample was transferred to an extraction vessel with 3N HCl and
extracted according to the procedure outlined earlier for Pt and Pd.
Table 6 gives the spike levels used with the
composite samples.
65
-------
TABLE 6. Pt and Pd SPIKE LEVELS OF
COMPOSITE SAMPLES
Quantity
of Sample Microliters of Spike Concentration
Sample Analyzed Solution Used' Pt
Urine 1 liter
Feces 300 grams
Hair 11.5 grams
500
100
500
100
50
100
200
0.
0.
0.
0.
0.
0.
0.
0010
0002
0033
0007
0087
0174
0348
0.
0.
0.
0.
0.
0.
0.
in ppm
Pd
0005
0001
0017
0003
0043
0087
0174
Spike solution: 2 jig/ml Pt and 1 jig/ml Pd.
66
-------
(3) Hair
Composites of hair were made from the "long hair"
samples collected at each sampling site. The composite samples consisted
of about 12 grams of hair (see Table 6).
The hair was washed with 0. 12M sodium lauryl
sulfate solution and rinsed 3X with deionized water, followed by an isopropyl
alcohol wash and by three rinsings with deionized water. The washed hair
was then transferred to a polyethylene beaker and placed in an oven
at 60 C to dry.
The dry hair sample was weighed into a Vycor
beaker, and 30 ml of HC1O.: HNO3 (1: 1) was added. The sample was
allowed to stand at room temperature 1-2 hours before placing on a hot
plate (150 C) for evaporation-digestion. The volume of sample digest
was reduced to 1-2 ml and reconstituted-evaporated 3X with concentrated
HC1. Following the last evaporation, the sample was rinsed into an
extraction vessel with 3N HC1 and extracted by the previously outlined
procedure for Pt and Pd.
(4) Feces
Fecal samples were composited for the baseline study
and the mining study. The composites ranged from 300g to 500g (Table 6).
The samples were partially digested with concentrated HNOo overnight in
polyethylene jars. Following this partial digestion, the samples were
further digested by adding small aliquots to a 400-ml Teflon beaker on
67
-------
a hot plate (125-150 C) and digesting-evaporating until all of the sample
had been completely digested. The digestion was continued by adding
until a clear amber solution remained. The solution was then
o
evaporated down until solids were observed forming in the digest. Then
10 ml HC1O4 was carefully added and the digestion continued until 2-3 ml
remained. The sample was then filtered through a glass -fiber filter
with rinsing of 6N HC1. The filtrate was evaporated to near dryness on
a hot plate and reconstituted-evaporated 3X with concentrated HC1.
Following the last evaporation, the sample was transferred to an
extraction vessel and extracted by the procedure given for Pt and Pd.
(5) Tissues
Tissue samples from the baseline and mining studies
were homogenized using a VirTis "45" Homogenizer with stainless steel
blades. Approximately 5-55 grams of tissue (wet) were homogenized,
depending upon the type (see Table 5).
The tissue homogenates were weighed into a Vycor
beaker and placed in a vacuum oven at 40-50 C overnight. The dry
samples were then mixed with Mg(NO,)-, ashing aid and placed in a muffle
furnace at 500 C. The samples were a.shed until a -white ash remained.
The ash was solubilized with aqua regia and evaporated-reconstituted 3X
with concentrated HC1. Following the last evaporation, the sample was
transferred to an extraction vessel with 3N HC1. Extraction followed
the procedure outlined earlier for Pt and Pd.
68
-------
c. Environmental Samples
(1) Air Samples
Air samples from the baseline, mining and refinery
studies were each composited (Table 7). The composited glass-fiber filters
(20. 3 x 25.4 centimeters) were cut into approximately 1-cm squares,
added to a 2-liter boiling flask, and 100-250 ml of aqua regia was added.
The amount of acid added depended upon the number of filters composited.
Samples were refluxed for 24 hours, filtered through glass-fiber filters,
and the filtrates were evaporated to several milliliters on a hot plate
(150-200°C) under N£. The remaining sample was then reconstituted-
evaporated 3X with concentrated HC1. Following the last evaporation,
the sample was transferred to an extraction vessel with 3N" HC1. Extraction
of Pt and Pd followed the procedure given earlier.
(2) Soil Samples
Soil samples were dried in an oven (60 C) for
48 hours before being ground with a mortar and pestle. Five grams of
the dried, ground soil was weighed into a 250-ml Vycor beaker and digested
with 50 to 150 ml of aqua regia on a hot plate (200°C) with constant stirring.
The samples were removed from the hot plate, cooled, and filtered with
a glass-fiber filter. The filtrate was collected in a Vycor beaker, evaporated
under N£ to 1-2 ml and reconstitute-evaporated 3X with 5 ml of concentrated
HC1. Following the last evaporation, the sample was rinsed into an
extraction vessel with 3N HC1 and extracted by the procedure given earlier
for Pt and Pd.
69
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TABLE 7. LIMITS OF DETECTION OF Pt and Pd
IN ENVIRONMENTAL SAMPLES
Sample
Type
Water
Soil
Study Area
Baseline
Mining
Baseline
Mining
8
5
0
Pt
x 10"
x 10"
.0008
Pd
c Pprn
pprn
ppm
2.
1.
0.
4 x
5 x
10-5
lO"5
ppm
ppm
0007 ppm
Sample
250
400
10 g
ml
ml
Size
sample
sample
dry sample
Air
Baseline exposed 0.05 pg/m3 0.062 pg/m3
Baseline control 0.11 pg/m3 0.033 pg/m3
Mining
Refinery
0.003(j.g/m3 0.003(j.g/m3
3 0.003jjig/m3
47424 m compos
9988 m3 composi
2111 m composi
2111 m3 composi
70
-------
(3) Water Samples
Up to 400 ml of water was used in the determination
for Pt and Pd. The sample volume was reduced to less than 10 ml in a
rotary evaporator under reduced pressure and 70 C heat. Using
approximately 25 ml of aqua regia, the sample Was rinsed into a Vycor
beaker and digested-evaporated to 1-2 ml, under N->, on a hot-plate
(150 C). The sample was reconstituted-evaporated 3X with 5 ml
concentrated HC1 and transferred to an extraction vessel with 3N HC1.
Extraction of Pt and Pd followed the procedure given earlier.
6. Lead Methodology
a. Biological Samples
(1) Blood
The procedure of Hwang, Ullucci and Mokeler
(18)
using modifications from the method of Mitchell, Ryan and Aldous
was used to determine the Pb concentration in whole blood samples.
Using an Eppendorf pipet, a 1. 0-ml aliquot of whole
blood was transferred into a 5-ml centrifuge tube. One milliliter of
a hemolyzing-chelating solution consisting of a 5% Triton X-100
(octylphenoxypolyethoxyethanol, Rohm and Haas, Philadelphia, Pa. )
solution containing 2% ammonium pyrrolidine dithiocarbamate (APDC)
was added, and the sample was mixed vigorously for 5 minutes and
allowed to stand 10 to 15 minutes to ensure complete hemolysis of the
71
-------
blood; this was followed by the addition of 1.0 ml of water-saturated
MIBK. The sample was then shaken for 3 minutes and centrifuged
for 5 minutes at 3,000 RPM. The organic layer was then analyzed
for Pb by injecting 10-|al aliquots into the HGA-2000 graphite furnace.
(2) Urine
The procedure used for urinary Pb determinations
(19)
was based upon that of Kubasik and Volosin .
A 10-ml aliquot of acidified urine (1% acetic acid
added as a preservative) was pipetted into a 25-ml centrifuge tube.
Using NaOH, the pH was adjusted to 7.0, and 5 ml of tris(hydroxymethyl)-
aminomethane buffer (pH 7.0) was added. One milliliter of a 1% APDC
solution was added along with 1.0 ml of water-saturated MIBK. The
sample was mixed for 10 minutes and then centrifuged for 10 minutes
at 3,000 RPM, and the organic layer was removed for Pb analysis
by injecting aliquots into the HGA-2000 graphite furnace.
(3) Hair
Hair samples were washed by a modification of
(20)
Hammer, et al. method.
All of the hair sample collected (usually 1 to 4 grams)
was cut into approximately 1-cm lengths with stainless steel scissors.
The hair was placed in a 250-ml Erlenmeyer flask, and a sufficient
amount of 0. 12% sodium lauryl sulfate solution was added to completely
72
-------
cover the hair. The flask was then placed on a mechanical shaker for
1 hour; then the solution was decanted off, and the hair was rinsed
with deionized water until no trace of the surfactant remained. The
hair was then washed 2X with isopropyl alcohol and rinsed 3X with
deionized water. The washed hair was placed in a polyethylene beaker,
covered with thin paper to keep contamination out, and placed in an
oven (60 C) until dry.
A 1-g sample of the washed and dried hair was
weighed into a Vycor beaker and digested on a hot plate with
HNC^: HCIO^ (50: 50). The digest was evaporated until dense fumes
of perchlorate were given off and was then allowed to cool. The digest
was filtered with a glass-fiber filter using 0. IN HNOo as rinse. The
filtrate was collected in a 10-ml volumetric flask and made to volume
with 0. IN HNO3- This sample was analyzed for Pb by aspirating
into an air/acetylene flame.
(4) Feces
A 1. 5-g aliquot of homogenized feces was digested
with concentrated HNO^ in a Teflon bomb designed by Rantala and
Loring. ' The bomb was placed on a hot plate at 1 50 C for 1 hour,
removed and allowed to cool to room temperature before attempting
to open. T'~>e digest was quantitatively rinsed through a glass-fiber
filter, and the filtrate was collected in a 10-ml volumetric flask.
Deionized water was used to make the volume to 10-ml. This solution
73
-------
•was analyzed for Pb by injecting 10-jj.l aliquots into the HGA-2000
graphite furnace.
(5) Tissues
Tissue samples collected in the baseline study
were analyzed for Pb. A 10-15-g portion of the tissue •was homogenized
with a VirTis "45" homogenizer using stainless steel blades. An
aliquot of the homogenate (usually l-2g) was weighed into a Pyrex
o
ashing boat, placed in a vacuum oven (60 C) overnight, and finally
placed in a low temperature asher. The tissue samples were ashed
under reduced pressure at 400 watts forward power for 4-8 hours.
The remaining ash was then solubilized with IN HNC>3 and rinsed into
a 10-ml volumetric flask. This final 10-ml solution was then used to
determine the Pb content of the tissues by aspirating into an air/acetylene
flame or injecting aliquots into the graphite furnace.
b. Environmental Samples
(1) Air
Air samples, collected on 20. 3- x 25. 4-cm
glass-fiber filters during the baseline study, were analyzed for Pb
(Table 8). A 2. 54- x 20. 3-cm strip of the filter was cut with stainless
steel scissors. The strip was cut into approximately i-cm squares
and placed into a 250-ml Erlenmeyer flask. Two hundred milliliters
of 6 NHC1 was added, and the sample was shaken for 18-20 hours on
a mechanical shaker. The sample was then filtered using a glass-fiber
74
-------
filter that had been prewashed with dilute HC1. The filtrate was
collected in a 250-ml volumetric flask and filled to the mark with
deionized water. This solution was aspirated into an air-acetylene
flame using spiked working standard, made up in the same acid
concentration, to quantitate the Pb concentration of the baseline
samples.
Verification of this leach method was done by
performing a "total digest" of selected air samples and comparing
with the results obtained with the leach procedure. The total digest
consisted of cutting 2. 54- x 20. 3-cm strips of the glass-fiber filter
and placing into a 500-ml boiling flask, adding 150-200 ml of aqua regia,
and refluxing for 16-18 hours. The sample was then filtered and made
to 250-ml with deionized water. Analysis of this solution was by
aspiration into an air-acetylene flame using spiked working standards,
made up at the same acid strength to quantitate the unknown samples.
Table 8 shows there is little difference between "leaching" the filters
with 6N HC1 and "digesting" with aqua regia.
(2) Soil
Soil samples from the baseline study were analyzed
(22)
for Pb by a leaching procedure. A 15-20g soil sample was dried
in a low (60 C) temperature oven for 48 hours. Then a 5-g sample
of the dried soil was weighed into a 125-ml Erlenmeyer flask, and 50 ml
75
-------
TABLE 8. COMPARISON OF 6 N HC1 "LEACH" WITH AQUA
REGIA "DIGEST" OF GLASS-FIBER AIR FILTER FOR Pb
6N HCL Aqua Regia %
Sample "Leach" "Digest" Difference
Al 7.16 7.23 1.0
A2 6.52 7.69 15.2
Bl 6.01 6.25 3.8
B2 5.65 5.99 5.7
76
-------
of leaching solution (3: 7 mix of 25% hydroxylamine hydrochloride
and 35% acetic acid) was added. The sample was sealed and shaken on
a mechanical shaker for 15 hours. The leach solution was filtered
through a glass-fiber filter directly into a 2-oz polyethylene sample
bottle. Aliquots of the solution were then diluted by an appropriate
factor to maintain the Pb concentration within the linear range of the
instrument.
(3) Water
Water samples from the baseline study were ,
analyzed for Pb by extracting the ammonium 1-pyrrolidine dithiocarbamate
complex of Pb into methyl isobutyl ketone (MIBK).
A 2-ml aliquot of the water was neutralized (pH 7)
with NaOH and then buffered with Trisma buffer (pH 7). A 0. 1-ml aliquot
of 1% APDC solution was added and the sample shaken for 1 minute.
Then, 1 ml of MIBK was added and the sample shaken again for 5 minutes.
The organic layer was removed and analyzed by injecting 10-|j.l aliquots
into the graphite furnace.
7. Calculations and Analytical Data
a. Instrument Parameters
Table 9 lists the instrument parameters used for
analysis of Pb by the flame method.
Table 10 gives the parameters for Pt, Pd and Pb analyses
on the HGA-2000 graphite furnace.
77
-------
TABLE 9. INSTRUMENT PARAMETERS FOR LEAD
DETERMINATION BY AIR/ACETYLENE FLAME
Lead Analysis
Spectrophotometer: Flame:
Wavelength 283. 3 nm Air 30 psi/No. 60
Source 9 mA Acetylene 8 psi/No. 40
Slit No. 4 (1.0 mm) Aspiration rate. .2.5 ml/min.
Damping No. 1
D2 Arc ON
Recorder 20 mm/min.
Scale Expand. . . Auto Cone, with 5 ppm
Pb at full scale
also 2. 5 ppm full scale
78
-------
TABLE 10. INSTRUMENT PARAMETERS FOR THE HGA-ZOOO
DETERMINATION OF Pt, Pd and Pb
Lead Analysis
Spectrophotometer:
Wavelength 283 . 3 nm
Source 9 mA
Slit No. 4 (1.0mm)
Damping No . 1
Graphite Furnace:
Dry 25 sec at 100°C
D-> Arc
ON
Recorder 10 mm/min
Scale Expand ... .IX
.1 ». *-» J.J. «•••*••
Atomize . . .
Tube
Gas
7 sec at 2100°C
grooved
f^ •*• ^* *•' '•'
N-, at 20 psi, No. 4
(flow meter), auto
interrupt
Platinum Analysis
Spectrophotometer:
Wavelength 265. 9 nm
Source 18 mA
Slit No. 4 (1.0mm)
Damping No. 1
D2 Arc ON
Recorder 10 mm/min
Scale Expand. .. 3X
Graphite Furnace:
sec at 200°C
sec at 1500°C
C
Dry 15
Ash 30
Atomize. . . 15 sec at 2700 '
Tube Regular
Gas N2 at 20 psi, No.4
(flow meter),
manual interrupt
Palladium Analysis
Spectrophotometer:
Wavelength 247. 6 nm
Source 23 mA
Slit No. 3 (0.3 mm)
Damping No . 1
Recorder 10 mm/min
Scale Expand. ... 10X
Graphite Furnace:
Dry. . . . ,
Ash . . . .
Atomize
. 30
.30
.15
sec at 150°C
sec at 1500°C
sec at 2700°C
Tube Regular
Gas N at 20 psi, No.4
(flow meter),
manual interrupt
79
-------
b. Standard Solutions
(1) Platinum and Palladium
Quantitation of blood samples for Pt and Pd
was accomplished by spiking 15-ml aliquots of whole blood prior to
digestion with 50(il and 100[j.l of a combined aqueous standard containing
1.2 p.g/ml Pt and 0.2 (ig/ml Pd. These spiked samples represented
blood concentrations of: Pt 0.004 |ag/ml and 0.008 |j.g/ml, Pd 0.00067 p.g/rr
and 0. 0013 (o.g/ml.
Composite samples -were spiked according to
Table 6, using an aqueous standard containing 2 pprn Pt and 1 ppm Pd.
These spiked samples (blood and composites)
were used to quantitate the Pt and Pd concentrations of the unknown
samples.
(2) Lead
Pb spikes were added to each type of sample
matrix according to Table 11. These spike samples were used to
establish an analytical working curve to determine the analyte
concentration in the unknown samples.
A series of spike samples were analyzed before
and after every 10-20 unknown samples. Both sets of data from the
spiked samples were used to construct the analytical working curve
used to quantitate the bracketted unknown samples.
80
-------
TABLE FT. Pb SPIKE LEVELS USED TO
CALCULATE ANALYTICAL CURVES
Quantity Microliter Volume
of Sample Spike Solution of Spike Solution
Sample Analyzed ug/ml Used
Concentration
of Pb
in Samples
Blood 1 ml 10 0
5
10
20
30
Urine 10 ml 10 0
10
20
40
Hair 1 gram 1000 0
5
10
25
Feces 1. 5 grarn 100 0
5
15
30
60
natural cone.
5 p.g/100 ml
10 (j.g/100 ml
20 [jLg/100 ml
30 jj.g/100 ml
natural cone.
10 jig/1
20 jj.g/1
40 ug/1
natural cone.
5 Hg/g
10 ug/g
25 [jLg/g
natural cone.
0.33 !_Lg/g
1.00 ug/g
2.00 ng/g
4.00 jig/g
81
-------
c. Analytical Data
(1) Limits of Detection
The limits of detection for Pt, Pd and Pb in
the different sample matrices are given in Tables 5 and 7. The
limit of detection represents the concentration of analyte which will
give a signal-to-noise ratio of 2.
(2) Precision
Ten determinations made on a spiked blood
sample gave a Pt concentration of 0.012 |j.g/ml with a standard
deviation of 0. 0004 |ag/ml (C. V = 3. 3%) and a Pd concentration of
0.003 |j.g/ml with a standard deviation of 0. 00012 fxg/ml (C. V. = 4.0%).
Lead precision data are listed in Table 12.
(3) Accuracy
Interlaboratory istudies are being planned to ascertain
the accuracy of these methods by techniques involving analytical methods
other than atomic absorption spectrophotometry.
Recovery of added spikes range from 97-101% for
Pt and Pd in blood at 0.012 ppm and 0.003 ppm levels, respectively.
Lead recovery of spiked blood (0.2 ppm) range
from 96 to 106%, while the recovery range for urine (0.002 ppm) is
89 to 97%. Recoveries of spiked lead in hair (10 ppm) and feces
(1 ppm) range from 95 to 103%.
82
-------
TABLE 12. PRECISION FOR Pb ANALYSIS
Pb Concentration
Sample n ppm
Blood 10 0. 178
Urine 12 0.01854
Hair 12 26.21
Feces 8 0.265
S. D. ppm
0.012
0.00292
1.799
0. 184
C.V.
%
6. 74
15.75
6.86
69.43
83
-------
8. Special Analysis
a. Paint Analysis for Pb Content
An exterior paint sample from the housing complex,
where a majority of the children volunteers in the baseline study lived,
was analyzed for Pb.
(1) Analytical Procedure
A weighed amount (0. 673 grams) of the paint chips
was dissolved in 20 ml of methyl isobutyl ketone. The solvent was then
evaporated off using low heat and a flow of N-,. The dried residue was
digested with a 1: 1 mixture of cone. HNO^:H2SO4 on a hot plate (100°C). The
sample was digested for 24 hours, filtered through a glass-fiber
filter and the filtrate collected in a 100-ml volumetric flask. Deionized
water was used to fill the flask to the mark. A 1: 50 dilution of this
solution was made prior to aspirating the sample into an air-acetylene flame.
(2) Results
The Pb concentration was 2.4 mg/gram of dried
paint. The solubility of the sample in MIBK and the low lead content
suggest a latex-type paint.
Ingestion of this type of paint would not be suspected
in high blood-Pb levels in children living in the housing complex.
84
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b. Neutron Activation Analysis (NAA)
(1) Blood
The 0.2M TOA (in benzene) extracts from 128 blood
samples in the baseline study were composited to make one sample.
The 0. 02M TOA (in xylene) extracts from 49 blood samples in the
mining study were composited to make another sample. These two
samples were evaporated to dryness and reconstituted with a known
volume of benzene or xylene.
General Activation Analysis, Inc. , San Diego,
California, did the neutron activation analysis of these sample
composites.
(2) Analytical Procedure
The samples plus comparator standards were
irradiated for 30 minutes in the TRIGA Mark I Nuclear Reactor at a
flux of 1. 8 x 10 n/cm /sec. After a decay of 24 hours, the samples
were wet-ashed under reflux in the presence of palladium and gold
carriers. Palladium and gold were then precipitated from the resulting
solution, dissolved in aqua regia and counted on a Ge(Li) detector
coupled to a multichannel gamma-ray spectrometer. Palladium
forms Palladium-109 with a half-life of 13. 5 hours, while platinum
produces Gold-199 with a half-life fo 3. 15 days.
85
-------
(3) Results
Accounting for the volume of the extracts used
for atomic absorption analysis and the volume of TOA recovered
from each extract, the Pt and Pd concentration in blood is;
baseline: 4. 9 ppb Pt < 0. 1 ppb Pd
mining: < 2. 8 ppb Pt < 0. 38 ppb Pd
The (< ) indicated that no analyte was detected, and the upper limits
are based on three standard deviations from the counting statistics.
c. Dilution Tunnel Sweepings
A sample of material collected in the air dilution
tunnel of EPA's catalyst dynamometer testing facility was sent to
General Activation Analysis, Inc. , San Diego, California, for Pt
determination by NAA.
(1) Analytical Procedure
The sample was removed from its shipping container
and sealed in a tared polyethylene vial. The weight of the sample was
1.0154 grams. A platinum standard wets sealed in a similar vial.
Both the sample and standard were irradiated
simultaneously for 30 minutes in a TRIGA Mark I Nuclear Reactor
at a flux of 1. 8 x 10 n/cm /sec. After a twenty-hour decay, the
sample vial was opened and the sample placed in a 250 -milliliter
Erlenmeyer flask. Ten milliliters of gold was added to the sample,
and, using the same pipet, 10 milliliters of gold were placed into a third
polyethylene vial. This third vial was then heat-sealed.
86
-------
The sample was wet-ashed with nitric, hydrochloric
and sulfuric acids until clear. Gold was precipitated using sulfur
dioxide. The metal was -washed, dissolved in aqua regia, and the solution
placed into a fourth polyethylene vial. This fourth polyethylene vial
was then counted for 12 hours on a Ge(Li) detector coupled to a 4096
channel gamma-ray spectrometer. The platinum standard was similarly
counted. Platinum produces Gold-199 via the following reactions:
Pt-198 (n,v) Pt-199
Pt-199 P > Au-199
Only platinum produces this Gold-199 radioisotope. Gold-199 was
detected in the separated sample. It was then quantitated by comparison
with the unopened platinum standard.
After the above quantitation, the sealed vial plus
the vial containing the 10 ml of gold was placed back in the TRIGA MarkI
Nuclear Reactor. After the second irradiation, the two vials were counted
as above, and the amount of gold in the sample vial -was determined.
This procedure determined the recovery factor which, in this case, was
83. 6%. The platinum value was corrected for this recovery value.
(2) Results
Sample Ft (ppm)
Dilution tunnel sweepings
CPL, EPA, NERC,
RTP4/75 2.44
87
-------
d. Vacutainer Contamination Study
(1) Introduction
(23)
There has been some evidence that so-called
"low-lead" blood collection tubes may actually be contaminated with
significant levels of lead. This contamination may be introduced from
the manufacturing process, or it maybe incorporated into the glass
matrix of the tube itself. The evidence from leaching experiments and
(23)
from microprobe analysis indicates that it is possible both these
sources of contamination are responsible for the lead contamination
present.
This investigation proposed to look at the lead
contamination by a leaching procedure using whole blood, deionized water
and a dilute acid (0. IN HC1) as the leaching solutions.
(2) Experimental
(a) Selection of Vacutainers
From previous investigations of lead concentratio
in whole blood, the relative standard deviation of the analytical method
was known. This allowed the determination of the number of vacutainers
that would have to be analyzed to have a preselected confidence interval
at the 95% level (see AppendixB). Setting the length of the confidence
interval at 0.008 (j.g/ml would require 40 vacutainers to be analyzed to
achieve this interval.
88
-------
A Hewlett-Packard Model 9810A calculator
was used to generate a list of random numbers (random number program).
Forty of these random numbers were used to select the vacutainers.
Each vacutainer in a case (1,000 vacutainers) was numbered in a
systematic fashion, and those vacutainers whose numbers corresponded
with the random numbers were taken for analysis.
(b) Analytical Procedure
Instrumental parameters are listed in Table 10.
Lead was selected as the analyte to represent
the heavy metal contamination. The lead analysis was based upon the
natural level of lead found in whole blood (BOOcc) purchased from a
local blood bank. The method of additions and regression analysis was
used to determine the lead concentration in the blood (Figure 7).
Since the program requires data on platinum
and palladium concentrations in blood, it was decided that these two
metals would also be included in this investigation.
Levels of platinum and palladium in normal
(unexposed) human blood have not been determined, but they are so low
that to get valid data on these metals from this study it would be
necessary to spike the blood (1 ng/ml). Any platinum or palladium
contamination from the vacutainers could then be determined by the
increased absorption signal. From the design of this investigation,
any loss of these metals to the vacutainer surfaces could also be
89
-------
10(1
•ILL
i'U
1
•a
• H
0)
rt i )
0) 4
10
8.47 pg/ldOT ml
± 0.62 v«g/100 ml
C. V. = 7.3%
in
00 in] 10
-'O
FIGURE 7. REGRESSION ANALYSIS OF BLOOD-Pb SPIKES
90
-------
determined, provided it was great enough to be above the detection
limit of the atomic absorption instrument.
(i) Lead Analysis
The procedure used for lead analysis of
(18)
whole blood is based upon that of Mi-tchell, Ryan and Aldous. One
milliliter of whole blood is treated with 1.0 ml of a hemolyzing-chelating
solution consisting of a non-ionic surfactant (Triton X-100, 5% by
volume) and sodium diethyldithiocarbamate (2% by weight). The sample
is vigorously shaken and then allowed to stand for 10 to 15 minutes to
insure complete hemolysis. One milliliter of methyl isobutyl ketone
(MIBK) is added, and the sample is thoroughly mixed and then centrifuged
at 3,000 RPM for 5 minutes. The organic layer is removed for lead
analysis.
Lead analysis of the water samples
followed the same procedure used for blood, but the dilute acid samples
were neutralized (pH 7) with 0. IN NaOH prior to extraction.
(ii) Platinum and Palladium Analysis
The extraction of platinum and palladium
from whole blood is based upon the methods of Khattak and Magee.
Five milliliters of whole blood is digested in a Vycor beaker with HNO3
(70: 30) on a. hot plate at 200 C. A flow of N? is used to evaporate the digest
solution to approximately 1 or 2 ml. The remaining digest is reconstituted
and evaporated to near dryness twice with concentrated HC1. It is finally
91
-------
reconstituted with 5 ml of 0. 1M HC1 and quantitatively transferred to a
10-ml volumetric flask. Deionized water is used to fill the flask to
the mark. The diluted solution is then placed in an extraction vessel,
1 ml of 25% SnCl2 solution (in 3 N HC1) is added, and the solution is
shaken for 30 seconds. Then 0. 5 ml (BOOfol) of a 0.2M tri-n-octylamine
solution (in benzene) is added to the extraction vessel and shaken for
1 minute. The organic phase is removed from the vessel and analyzed
for platinum and palladium.
(3) Discussion
Whole blood and deionized water were added to the
vacutainers by the route commonly used, i. e. with a needle using the
vacuum in the tube. The acid leach solution was added by removing the
rubber stopper. This prevented the acid solution from being contaminated
by the metal needle. Twenty-five of the vacutainers were used for whole
blood and the remainder for the deionized water and dilute acid leaches.
All the vacutainerg; were filled at the same time.
Then, at 1-, 3-, 6-, 24- and 30-hour intervals, the blood tubes were
analyzed for lead. Vacutainers with deionized water were analyzed for
lead at 6-, 24- and 30-hour intervals, and those with dilute acid were
analyzed at 6 and 30 hours. Only one analysis was made for platinum
and .palladium, and that was at 40 hours.
All the vacutainers were maintained at room temperatur
throughout the study.
92
-------
At each of the specified time intervals, blood
lead analysis was performed on 5 of the blood-containing vacutainers
and on 3 control blood aliquots (i. e. blood not exposed to a vacutainer).
This gave a direct comparison of the blood-lead levels in the vacutainers,
at the specified contact times, with the control bloods, thereby preventing
any instrument-parameter variation from affecting the analytical results.
Each vacutainer was sampled for lead only once
during the course of this study.
Three deionized water and three dilute acid-containing
vacutainers were analyzed at the specified time intervals along with 2
controls (i. e. leaching solution not in a vacutainer) for each.
(4) Calculations
(a) Regression Analysis
Control blood spiked at four different levels
was analyzed in duplicate by the extraction method given for lead analysis.
Regression analysis was performed on a Hewlett-Packard Model 9810A
calculator on the absorption peak heights vs the lead concentrations.
The results were that the blood used for this study contained a lead level
of 8.47 ng/100 ml + 0. 62 |j.g/100 ml with a coefficient of variation of
7. 3% (see Figure 7).
(b) Statistical Analysis
The data were examined by two different methods
(see Table 13). First, the results were calculated on the basis of the
93
-------
TABLE 13. VACUTAINER STUDY DATA
Time
Hours
1
3
6
24
30
dif.,mm
t
\s^
a<.
df
iif.,mm
t
i^
<£*.
df
3if,,mm
t
\s^
ex.
df
dif0mm
t
v^—
G<
df
BLOOD
Indiv
13
1.46
0.64
_..
10
Mean
mple)
•nple )
1.61
0.52
-_.(c>
3
2.11
0.90
___(c)
j
ACID
Indiv
( no s
( no s
4.80
3.%
<0.01
10
( no sa
-4.67
-0.76
_->>
8
Mean
imple )
umple )
mple)
(a) calculations based on number of individual injections of sample aliquot into graphite fun-Bee
(b) calculations based on mean value of each sample analyzed.
(c) ~^£E- very large
94
-------
individual sample aliquot injected into the furnace (individual data points).
Secondly, the results were calculated on the basis of the mean value of
the data points for each sample (mean of data points).
The test to show whether or not there is lead
contamination from the vacutainers is a test for the difference between
means of independent groups using Student's t distribution. The control
bloods (or deionized water or dilute acid leach solutions controls) are
labeled group 1, and those from the vacutainers are labeled group 2.
We test the hypothesis:
Ho :
vs Ha :
or whether the mean lead level of the blood in the vacutainers
is greater than that in the control blood
If we let
X: = the mean of group i
N.
,, ., ; .th ,
= size of the i sample
= variance of the i sample
= 1,2
the test statistic, tc> is defined as
\l
(NJ - i)
NI
Sj2 +
+ N2
(N2 - DS22
- 2
i 1
_N! N2 _
with (N^ -f N-, - 2) degrees of freedom (df).
95
-------
The significance level, oC , is the probability
of obtaining by chance a value as large as tc from a Student's t distribution
with (N< + N7 - 2) degrees of freedom, when the null hypothesis, H ,
i ^ o
is true. Symbolically,
P [t(Ni + N2 - 2) > tc] = S.
/~s
If oc is less than the chosen significance
level (0.05, 0.10, 0.01), then we reject H in favor of H . If it is
O cl
greater, we accept HQ as no change in the lead levels.
(5) Results
(a) Lead
(i) Blood
At the 0.05 level, there is no significant
difference between the control blood and the vacutainer blood after 1 hour
contact time for both the individual peak and mean peak calculations
(see Tables 13 and 14). After 6 hours Ln the vacutainer, the individual
peak calculations showed a significant difference between the control
blood and the vacutainer blood, but the mean peak calculations for this
time interval indicated no significant difference. Since each vacutainer
may contain varying amounts of lead but still remain below the limits
specified by the manufacturer, and also since the instrument response
may not be exactly the same for each individual injection (pipet
error, slight variation in graphite tube, etc.), the mean peak calculations
96
-------
TABLE 14. RESULTS OF VACUTAINER STUDY -- COMPARISON
OF CONTROLS AND VACUTAINER BLOOD LEAD
Time
Control Blood
fxg/100 ml
Vacutainer Blood
IJig/100 ml
Significant
Difference at
the 0.05 Level
lours
1
3
6
24
30
Mean
8.47
8.47
8.47
8.47
8.47
Std. Dev.
0.28
0. 41
1. 43
0.66
1.20
Mean
9.65
10.25
9.76
9.51
9.75
Std. Dev.
1.01
0.85
1.58
1.22
0. 73
(Table 13)
no
yes
9
?
yes
97
-------
may be a more meaningful indication of the actual lead contamination
present. At the 24-hour interval, based upon the mean peak calculations,
the difference between control blood and vacutainer blood may or may
not be significant. The difference is significant after 30 hours contact
time between the blood and the vacutainers.
(ii) Water and Acid
Both the deionized water and dilute acid
leaches showed a significant difference between the control leach solution
and that in the vacutainers after 6 hours (see Table 13). At the 24- and
30-hour intervals, there were no, significant differences between the
controls and the vacutainers for each the dionized water or dilute acid
leaches.
(b) Platinum and Palladium
There was no indication of contamination of the
vacutainers with these metals. After 40 hours, there was a significant
difference between the spiked controls and the vacutainers spiked blood
levels (see Table 15), but this difference indicated a "loss" of the
platinum and palladium spike to the container.
(6) Conclusion
(a) Lead
The lead contamination found in this particular
case of B-D vacutainer 10-ml tubes is approximately 0. 13 |ag per tube
(see Table 14). This is within the 0. 1 |j.g per tube level specified by
the manufacturer's certification.
98
-------
TABLE 15. VACUTAINER STUDY Pt and Pd RESULTS
Mean
Std. Dev.
t (0.05)
df
Significant
% diff (means)
Platinum
Control
mjT)
13
8
8
11
5
11
3. 1
Vacutainer
jnm
12
7
8
5
11
8.6
2. 9
2. 53
8
yes
2.2.
Palladium
Control
mm
62
54
67
69
63
6. 7
Vacutainer
mm
56
56
53
55
1. 7
3. 39
5
yes
13
99
-------
The fact that the lead level remains relatively
constant with regard to exposure time would indicate that it is not tightly
bound to the glass matrix of the vacutainer. Also, the lead contamination
does appear to be uniformly constant throughout a given lot of vacutainers
but within the stated limit.
(b) Platinum and Palladium
There was no evidence that the vacutainers
contained detectable amounts of either platinum or palladium. The data
do indicate that after exposing spiked blood to the vacutainers for 40
hours there is a 22% "loss" of the platinum spike and 13% "loss" of the
palladium spike.
(c) Contamination
There should be no problem with contamination
when using these vacutainers for peidemiological investigations. The
only precuation that should be followed is to remove the blood from the
vacutainer and place it in a linear polyethylene container (acid washed)
within a few hours after it has been drawn. This would prevent "loss"
of the analyte metals to the walls of the vacutainers.
e. Lead-210 Study
(1) Selection of Subcontractor
Five firms were contacted to see if they were
210
interested in performing Pb analysis on a limited number of biological
and environmental samples. Two of the companies were not set up to
210
perform Pb determinations on a routine basis and were not interested
100
-------
in doing the limited number of samples. Another company was
interested but did not have the necessary standards available. A
fourth company said they could find no reasonable method to determine
210
Pb utilizing either fast or thermal neutron activation analysis. The
LFE Environmental Analysis Laboratories, Richmond, California, was
interested and sent a price quote for Pb analysis . This company was
selected to perform the analysis.
(2) Method of Analysis
(a) Sample Preparation
(i) Blood and feces samples from the base-
line survey were removed from the freezer and packed in a styrofoam
mailing carton with enough dry ice to last 72 hours. The blood samples
were sealed in a polyethylene bag to protect them from the feces samples.
A total of 30 blood samples (in 30-ml polyethylene bottles) and 30 feces
samples (in 60-oz polyethylene jars) were shipped by air express for
21°™. , -
Pb analysis.
Three glass-fiber air filters used to
collect particulate matter in the baseline survey were sealed in individual
polyethylene bags. The bags were then sealed in an insulated envelope
for air shipment with the other environmental samples.
Eight soil samples (16-oz polyethylene
jars) were packed in an insulated mailing carton with enough dry ice to
210
last 72 hours. This carton was shipped by air express far Pb analysis.
101
-------
(ii) The soil and feces samples were dried
at 110°C to constant weight and the dry weight of the sample recorded.
The samples were then ashed at 450°C to remove any carbonaceous
and/or organic materials.
(b) Sample Dissolution
The air filters and ashed feces and soil
samples were dissolved with successive HNO-j-HF treatments to achieve
complete dissoltuion. The dissolved sample was equilibrated with
standardized Pb carrier. The total blood sample was wet ashed with
HNOo in the presence of standardized Pb carrier.
(c) Decontamination
The equilibrated samples were purified radio-
chemically by precipitating a lead carbonate, lead iodide, and a lead
nitrate. For the soil samples with high concentrations of Fe, the Fe was
210
removed with a Hexone extraction. The purified Pb was mounted as
lead sulfate, and the radiochemical yield was determined by weighing the
lead sulfate and by correcting for the macro Pb in the sample. The time
of the lead sulfate precipitation is recorded as the final separation time
, 210 210
of Pb- Bi.
(d) Counting
The lead sulfate contained in a Mylar sandwich
on a plastic planchet is counted on a CE-14 low background beta counter
as soon as possible after the Pb- Bi separation time. The sample
210
is counted five times within a period of two weeks to observe the Bi
ingrowth.
102
-------
(e) Calculations
210
The standard method for Pb analysis at
Z10
LFE involves a separation of the daughter Bi and multiple beta counts
210
of the sample as the Bi grows back into equilibrium. The counting is
done on a CE-14 low background beta counter. Sixteen of these counters
are on-line at LFE with backgrounds of 0.4 to 0.5 cpm. The sample is
counted through a thin aluminum absorber (4.75 mg Al/cm ) to screen
out any Po alpha particles. The Pb beta particles (0.061 MeV
maximum) do not register on the counters. All counts are assumed due to
7 \ n
Bi (1.160 MeV maximum).
Punched data cards are produced for each
measurement on the sample by the computer. All sample information is
available in disk files, and on a routine basis, no keypunching is required.
The calculation is done by computer. A
weighted linear least squares analysis is performed on the growth data
210
resolving an equilibrium Bi value and an assumed long-lived component.
All data points are corrected for growth during counting and are weighted
as the inverse variance of the net cpm as derived from counting statistics.
After an initial fit, points that are more than 2 6 (counting statistics)
away from the fitted value are rejected and a second fit is done. Errors
are computed by propagating errors due to counting statistics through the
least squares formula. If the data points do not fit the determined line as
well as would be expected from the counting statistics, a larger error,
based on the goodness of fit, is used.
103
-------
(3) Limit of Detection in Blood and Feces
(a) Blood - On a 10ml blood sample, the limit
Z10
of detection for Pb is 0.045p Ci/total sample.
(b) Feces
A 10-g (dry wt.) sample has a detection
limit of 0.05 1 Ci/gram for 21°Pb.
9. Discussion and Conclusions
a. Platinum and Palladium
An extraction system designed to handle a large
number of samples on a routine basis must keep procedural steps to a
minimum.
The HMWA extraction system described here is a
relatively simple means to extend the limit of detection of the atomic
absorption analysis of Pt and Pd.
Further improvements in this HMWA extraction
system could improve the abosolute amount of Pt and Pd which may be
determined. The excessive amount of "smoke" during the atomization
of the extract limits the volume of TOA. which may be injected into the
graphite furnace. Decreasing the concentration of TOA has been only
partially successful in eliminating this problem. Increasing the ashing
temperature has not helped either. There are losses of analyte at the
temperature needed to remove the excess matrix.
This excessive "smoke" during atomization necessitates
that the hollow cathode lamp and the deuterium arc lamp (background
104
-------
corrector) be alined very carefully, or incorrect absorption readings
will result. Pd is affected more by incorrect alinement than is Pt.
Composite samples were another means of increasing
the limit of detection for Pt and Pd. Experience in this laboratory has
shown that wet ashing large quantities of solid material requires an
excessive amount of time. Digestion of spiked composite hair and feces
samples gave very erratic results. Recoveries were in the range
30-70% for Pt and Pd in feces and hair.
Spiked urine composite recoveries for Pd ranged from
0-60%, and for Pt the range was 0-100%. More work needs to be invested
in this area to make it a reliable method for increasing the sensitivity
of Pt and Pd determinations.
The limits of detection given in Table 5 for urine,
hair and feces are calculated on the basis of complete ( > 90%) recovery
using the extraction procedure outlined. The limit of detection for blood
is calculated on the basis that the absolute limit of detection for our
instrument is Pt = l.OTng and Pd = 0.33ng.
Analysis of particulate matter collected on glass-fiber
filters for Pt and Pd is limited by the total amount of material on the
filter. Samples collected in the mining study contained such large
amounts of particulate matter that large volumes of acid were needed to
solubilize all the analytes present. Removal of this acid required an
excessive amount of time .
Extracts of the air samples collected in the mining study
contained an interference which prevented their analysis. This interference
was thought to be very fine particulate matter which was not digested
105
-------
or removed by filtering and was subsequently trapped in the TOA
extract. Background correction could not compensate for this interference,
Another set of air samples collected at the mining study
site contained less particulate matter. Analysis of these filters by the
method described was possible.
The extraction of Pt and Pd in a single extract using
a liquid anion exhcnager (tri-n-octylamine) from an approximately 3N HC1
solution provides a means of concentra.ting these elements so they
will be within the detection limit of AAS using the flameless graphite
furnace. The procedure improves the limit of detection for Pt and Pd
in biological samples and also provides a means of improving the
sensitivity of AAS analysis for Pt and Pd.
b. Lead
The extraction procedure for blood Pb provides a
simple and fast means of analyzing a large number of samples. Table 12
shows that the method has good precision.
Table 11 gives the quantity of spike solution added to
1 ml of blood to determine the analytical regression curve (Figure 7}
used to calculate the unknown blood samples. Attempts at spiking a
large quantity of blood at different levels of Pb concentration and then
using an aliquot for analysis have produced erratic results in our
laboratory. The spike is added directly to the sample prior to extraction.
106
-------
The limit of detection for Pb in blood is restricted
more by the reagent blank signal than by the background noise level of
the instrument. Attempts to remove Pb from the reagents has been
only partly successful.
Extraction of urine Pb by this procedure gives a rather
high C.V. (Table 12). One reason for this is the low concentration of
Pb normally found in urine. Another reason may be that the 1% acetic
acid used in this laboratory to preserve the urine samples is not
sufficient to maintain all the urine components in solution.
Like blood, the limit of detection of Pb in urine is a
function of the reagent blank's Pb concentration. High reagent blank
absorption increases the limit of detection. Urine samples are spiked
similarly to the method given for blood (Table 11) and for the same
reason.
Hair analysis for Pb by the air-acetylene flame provides
good precision (Table 12). The most common reason for coefficients
of variation greater than 7% is improperly washed hair.
The limit of detection for Pb in hair by the flame
method is limited by the instrument noise level rather than reagent blank
interference. Spikes are added to the hair samples right after the
digestion acid has been added.
Feces analysis for Pb varies (Table 12) because it
is difficult to obtain a completely homogeneous sample. Even though the
107
-------
samples are homogenized prior to analysis, the relatively small sample
analyzed (1.5 grams) makes it difficult to imrpove upon the analytical
variation.
Digestion of the feces in the Teflon bombs is a fast
and easy method to analyze for Pb. The limit of detection is restricted
by the Pb concentration in the reagent blank and the size of sample
which may be used. Use of suprapure acids has decreased the reagent
blank absorption but has not completely eliminated it.
Determination of Pb in fecal samples by "closed"
digestion is considerably faster than "open" digestion methods, but
precision suffers because of the nonhomogenity of the sample.
The procedures for Pb analysis in blood, urine,
and hair provide fast and reliable methods of determining Pb in these
commonly used epidemiological monitors of environmental health.
Leaching of air filters and soil samples with acids
is a better method to determine Pb in these sample matrices rather
than lengthy "total" digestion procedures commonly used. Care must
be taken to verify that all the analyte is being removed using the leach
procedure.
108
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E. Data Processing
Two types of data forms were processed on this project. A
questionnaire form providing personal information pertinent to this
study was completed by each person volunteering as a human subject
participant for the human subject sampling. A metal analysis form
for coding chemical analysis results was completed for each sample
analyzed in the laboratory.
The questionnaire was filled out by prospective study partici-
pants. The Los Angeles, Lancaster, and Ontario participants
completed the Platinum, Palladium and Lead Questionnaire,
OMB-158-S-74010, while the New Jersey participants completed a
brief Information Form. Upon their receipt, the questionnaires for a
study site were coded, assigned an ID number, keypunched, and
listed in name, sex, and age sequences for selection of the most
appropriate participants. The Principal Investigator and the
Project Officer selected the study participants to meet the planned
age and sex distributions at each baseline site.
109
-------
To insure accurate reporting, transmission, and interpretation
of the analytical determinations on each collected sample, a fifteen-
character label code was devised for this project and similar epidemiologica
studies. The code consisted of four characters identifying the project,
two characters identifying the site, three characters for the sampling
period and subperiod or sample number, one character specifying the
sample medium, and one character for the analysis to be performed, and
four characters giving the ID number for a human subject or the location
identification for an environmental sample. Documentation of the label
code is shown in Appendix D.
A label generation computer program was developed to print
up the required number and types of sa.mple labels for each container
into which the human subject and environmental samples were to be
placed during sample collection and processing. The fifteen-character
label code, the sample medium (blood, feces, air, water, etc.),
and the sampling period or sample number were printed on each sample
label. On the human subject sample la.bels, the participant's name
was printed on the labels to be used for sample collection, but it was
deleted from the processing sample labels. Two samples of the sample
labels are shown below.
URINE
2222UMLA1133881 FIRST SAMPLE
BLOOD
a2?8BMLA1233881 SECOND SAMPLE
110
-------
When the study participants at a site had been selected, their
keypunched questionnaire cards and instructions regarding the type
and number of labels were input into the label generation computer
program. All of the sample labels needed for collection and processing
of the site's samples were printed by the program in a sequence
that would facilitate their use.
Later, when the chemical analysis of a set of samples from a
site was completed, the results were reported for data processing and
statistical evaluation on the Metal Analysis Coding Form. This form
was specifically designed for transmitting the chemical determinations
obtained on this project and related epidemiological studies. For each
sample analyzed, the fifteen-character sample label code, the sample
medium, and each of the analytical determinations (metal, concentration,
and units) were recorded on the Metal Analysis Coding Form. A reduced
copy of the form is presented in Appendix D. The information on each
set of Metal Analysis Coding Forms was checked and then keypunched.
After all the human subject sample determinations were
received and keypunched, the questionnaire data cards and the metal
analysis determination cards for each type of sample were merged into
a single file that was sorted by ID number and card type. A computer
program was written to abstract the necessary questionnaire and sample
determination information from the file in a form suitable for statistical
analysis.
Ill
-------
The data processing of the environmental samples was done
manually. This was because there were few air, soil, and water
samples with positive chemical determination, and because various
sampling configurations were used.
F. Statistical Methods
1. Baseline
a. Environment
The statistical methodology was to characterize and
compare the environments of the Los Angeles and Lancaster human
subject participants. Because there were no detectable levels of platinum
or palladium in any of the individual baseline environmental samples, only
the detected lead concentrations were statistically analyzed.
Two air samples were obtained at the Los Angeles
participants' residence, the U. C.L.A. married student apartment,
for lead analysis. Thirteen air samples were obtained from the backyards
of some of the Lancaster participants. The lead concentration determinatior
of these Los Angeles and Lancaster air samples were compared. The
standard t test of two independent samples was used to detect any significant
difference in the mean air lead concentration. The t test assumes both
sampled populations are normally distributed with equal variances. The
equality of variance assumption for the two independent comparable
groups was tested by the standard F-test. The validity of these assumptions
was examined for each set of tissue data without transformation, under
112
-------
logarithmic transformation, and under square root transformation.
The square root transformation yielded acceptable variance equality
between the two air quality populations, whereas the logarithmic
and untransformed data did not. Hence, a two-sided t test was applied
to the square root transformed lead determinations for each air sample.
The soil lead analysis focused on characterizing
the relationship between the surface soil lead concentration and the
distance upwind or downwind from the freeway in Los Angeles.
Graphical techniques were used to present the soil lead results from two
Los Angeles locations adjacent to the San Diego Freeway as a function of
the upwind and downwind distance. The configuration of the Los Angeles
soil sampling permitted only one soil lead sample to be taken at the
Los Angeles participant's residence. Seven soil samples were obtained
from the backyards of Lancaster participants and analyzed for their
(24)
lead concentration. Dixon's gap test for outliers was used to
determine whether the Los Angeles residence soil sample could be
considered a member of the Lancaster soil population. Inspection
indicated that the logarithmically transformed Lancaster soil data
appeared more normally distributed data than either the untransformed or
square root transformed data. In addition, use of logarithmically
transformed data would yield the most conservative Dixon test (i. e. ,
considering the Los Angeles sample as an outlier only when it certainly
must be an outlier). For these reasons, the Dixon gap test was applied
to the logarithmically transformed soil lead data.
113
-------
Five samples of tap water were obtained from the
homes of Los Angeles and Lancaster participants and analyzed for their
lead concentrations. The two-sample t test was used to test the null
hypothesis of no difference in the mean lead concentration of the Los Angeles
and Lancaster water supplies. Since square root transformed data yielded
acceptable equality of variance, the two-sided t test was conducted on
the square root transformed data.
b. Human Subjects
The statistical analysis methodology was to compare the
mean platinum, palladium, and lead concentrations in the blood, long
and short hair, urine, and feces samples from corresponding groups
of 137 participants from the Los Angeles site and 125 participants from
the Lancaster area. Because none of the participant samples had
detectable platinum or palladium concentrations, the statistical analysis
was restricted to the lead concentration data. The two blood, urine,
and feces samples obtained during the week from each participant were
considered replicates; their mean was utilized as the observed participant
value. When a reported lead concentration was below the analytical
method's detection limit, the detection limit was substituted as the
concentration in the statistical analysis.
Three Lancaster participants had extremely high
outlier hair lead values. A retired man had a lead concentration of 4,700 (j.g,
in his long hair sample. An elderly lady's hair samples showed lead levels
of 3,800 (JLg/g in the long hair and 760i (j.g/g in the short hair. A preschool
114
-------
girl who lived with the elderly lady had hair lead levels of 130 ^g/g in
her long hair and 940 |j,g/g in her short hair. Since the three were
neighbors in an isolated area who all spent the entire day at home and
who all had normal blood and urine lead levels, a non-vehicular lead
source was hypothesized. Thus, the hair lead data on these three
participants was excluded from the statistical analysis.
The standard t test of two independent samples
was utilized to compare corresponding participant groups from the
two sites with respect to significant differences in population means.
Site comparisons were conducted for each tissue on the total participant
groups and on subgroups stratified by sex and age. The t test assumes
both sampled populations are normally distributed with equal variances.
The normality assumption was examined by testing the skewness' of the
(25)
group observations. The equality of variance assumption for the
two independent comparable groups was tested by the standard F-test.
The validity of these assumptions was examined for each set of tissue data
without transformation, under logarithmic transformation, and under
square root transformation for the total group and the male and female
subgroup comparisons across site. In every case, the logarithmic
transformation yielded the more valid t tests. Thus, logarithmically
transformed lead concentration data was utilized. Each t statistic
tested the null hypothesis of equal population or stratum means across
site against the two-sided alternative of unequal means.
115
-------
The lead concentrations of the blood, hair, urine,
and feces samples from the participants at the two sites were also
related to various potentially pertinent factors in addition to sex and age.
These additional factors were preschool-nursery vs children in school,
length of residence in the city, distance from the expressway, distance
from other highways, types of air conditioning, level of cigarette smoking,
ethnic grouping, and occupation. Because these additional factors were
not considered in the participant selection process, most of these factors
were highly correlated with the site. For example, 85% of the Los Angeles
participants had no air conditioning, while 55% of the Lancaster participants
had central air conditioning and another 18% had window units. Because
of the design interactions of these additional factors with the site, each
factor was analyzed both as a main effect and within site in relation to
the lead concentration data for each tissue. The effects of each factor
were inspected using both the original and logarithmically transformed
data. All the detected main effects proved to be spurious; actual
site and/or age effects, masquerading through the design interaction as
the effect of an additional factor, were responsible for the apparent
factor effect. Only when an additional factor showed a consistent
relationship to the lead determinations for two or more tissues at the
same site was the apparent factor effect subjected to a formal t test
of significance. When the factor had more than two levels, the nature of
the relationship of the factor to the lead mean determined the definition
of the two groups submitted to the t test. When the factor possessed
116
-------
level ordering and the lead mean varied according to this ordering,
the lowest and highest levels of the factor were taken as the compared
groups. Otherwise, all the levels of the factor were compressed into
the two best comparison groups. The null hypothesis of equal lead
concentration means was compared against the alternative of an elevated
mean for the logically affected group using a one-sided t test. The data
were logarithmically transformed prior to each t test to better satisfy
the equality of variance assumption.
Two blood, urine, and feces samples were obtained on
consecutive days from most of the Los Angeles and Lancaster participants.
For all the lead determinations made on a given tissue from a given
site-sex-age group, the between participant variation was compared
against the within participant variation. The between participant variance
measures the amount of lead determination variability from one participant
to another in the given tissue and site-sex-age group. The within
participant variance measures the lead determination variability between
the two samples from each participant in the group. The null hypothesis
that the between participant variance equals the within participant variance
was tested against the alternative that it exceeds the within participant
variance using a variance ratio F test.
In many cases, the F test accepted the null hypothesis.
The implication in such cases is that the two samples obtained on
consecutive days from a single person have as much lead variability
117
-------
as two samples taken from different people in the same site-sex-age
group. To further examine this sampling variability and to determine
whether the analytical method was the responsible factor, an
additional blood sampling experiment was performed. Sixteen blood
samples were taken from an adult male at the same time. Each sample
was separated into two aliquots. Each aliquot was processed, frozen,
and analyzed for lead using the same procedures employed with the
Lancaster and Los Angeles participant blood samples. An analysis of
variance was conducted using the logarithmically transformed lead
determinations to examine the variation between samples and between
aliquots within a sample. The interaction term was used to estimate
the precision variance of the combined processing/analytical procedure.
The variance components estimated from this sampling experiment
were compared against the participant and sampling variability obtained
with the comparable group of Lancaster and Los Angeles participants
(males aged 17-34) to evaluate the sources of variation.
2. Refineries
a. Environment
The environment of New Jersey refinery workers was
examined through 24-hour ambient air samples obtained for five
consecutive work days in both the refinery and salts sections of
the refinery. The platinum and palladium concentrations of each sample
were determined. The statistical methodology was to characterize the
118
-------
distribution of platinum and palladium in the air in the refinery
and salts sections. Characterization consisted of tabulating the
concentration determinations by work section and calculating the mean
and standard deviation of each set of data.
A relatively high palladium determination was obtained
on the Monday air sample in the refinery section. Since even with dilution
this sample was above the linear calibration range for palladium, its
3
value was estimated as 0. 356 ug/m . It is uncertain whether this sample
represents a valid palladium concentration resulting from an operational
malfunction in the refinery section or whether the sample was contaminated.
For this reason, the palladium characterization of the refinery section
air was presented both including and excluding the Monday sample. It
should be noted that the workers urine specimens were collected Monday
night and Tuesday morning and that the blood samples were taken on Tuesday.
Hence, if there was a very high palladium air concentration in the refinery
section on Monday, it could have had an effect on the palladium results
from the New Jersey participants.
b. Study Participants
Single samples of blood and urine were obtained from
each of 61 refinery worker participants. The platinum and palladium
concentrations of every blood sample were below the analytical method's
detection limits. However, of the 58 urine samples obtained and analyzed,
6 had platinum concentrations above the platinum detection limit of
119
-------
1.4 |ag/l, and 34 had palladium concentrations above the 0.4 (Jig/I
detection limit for palladium. Because the detectable platinum
determinations were few and isolated, the sample results were simply
reported without any statistical analysis.
The palladium determinations from the New Jersey
workers were subjected to an appropriate statistical analysis. Each
palladium determination below the analytical detection limit was set
to the limit for the statistical analysis. The original data and their
logarithmic transformations were examined. The logarithmic transformatic
yielded the more normally distributed data; it was used for the subsequent
J
analyses. The mean and standard deviation were used to characterize
the palladium distribution, both for all the workers and for the workers
in each of the five work sections. A one-way analysis of variance by
•work section was conducted to test whether the mean urine palladium
level was the same for the workers in each work section.
Correlation analysis was used in attempting to relate
the ln(Pd) urine determinations to each of six potentially relevant
factors: age, race, cigarette smoking, length of employment, work
section, and work shift. The work sections were ordered from highest
to lowest anticipated palladium exposure: refinery (1), salts (2),
recovery (3), maintenance (4), and storeroom (5). For each factor,
the null hypothesis of zero correlation was tested against the two-sided
I /I T
alternative using the statistic ryn-2/y (1-r ) which has the t distribution
120
-------
with n-2 degrees, where n is the number of pairs on which the
correlation coefficient r was computed. R. A. Fisher demonstrated
that for this test of zero correlation, it is sufficient that only one of
(26)
the variates be normally distributed. The correlation analysis was
conducted for two situations: using all 58 palladium, determinations
with negative results valued at the detection limit, and using only
the 34 palladium determinations exceeding the detection limit.
121
-------
V. RESULTS
A. Baseline
1. Platinum and Palladium
Data for platinum and palladium in study participants of
Los Angeles and Lancaster are shown in Table 16. No detectable levels
were found in individual samples; thus, "less than" values (detection
limits) are shown. In an effort to obtain some idea of the actual levels
present in blood, a composite of blood from all age groups and both
sexes of Los Angeles and from Lancaster was analyzed for platinum
and palladium. Measureable levels were found for platinum as seen at
the bottom of Table 16.
Autopsy samples were collected in Los Angeles from a
pathologist at a teaching hospital. Table 17 shows the information
obtained for these autopsy cases. For each autopsy, samples of liver,
kidney, spleen, lung, muscle and fat v/ere collected. No detectable levels
of these two metals were found in these tissues. Table 18 shows the
"less than" values for each of these tissues.
Platinum and palladium v/ere also measured in ambient air,
soil and tap water samples collected in Los Angeles and Lancaster. No
detectable levels were found at the following detection limits:
Platinum Palladium
Ambient air <5 x 10~8Hg/m3 < 6 x 10'8|JLg/m3
Tap water < 0. 08 ppb < 0.0 24 ppb
Soil < 0 . 8 ppb < 0 .7 ppb
122
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TABLE 17. AUTOPSY CASES - LOS ANGELES
Sample I. D. Age Sex
A 7572
A 7593
A 7617
A 7653
A 7657
64
44
69
12
74
M
M
M
M
M
Smoking
History
No
Yes
Unknown
No
Yes
Cause of Death
Pancreatic CA
Cardiac arrest
Carcinoma larnyx
Aplastic anemia
Carcinoma urinary bladder
A 7561
A 7587
A 7621
A 7654
A 7658
67 F Yes Acute lymphacytic leukemia
41 F Unknown Adenocarcinoma cervix
79 F Unknown Hypotension/hypoproteinemia sep
65 F Yes Myocardial infraction
47 F No Hypertensae eerebrovascular
accident
124
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TABLE 18. PLATINUM AND PALLADIUM IN AUTOPSY
SAMPLES - LOS ANGELES
Liver
Kidney
Spleen
Lung
Muscle
Fat
Pt
Ppb
< 0.24
< 2.6
< 1. 3
< 1. 3
< 0. 9
< 1.3
Pd
Ppb
< 0. 6
< 6.7
< 3. 3
< 3. 3
< 2.2
< 1. 6
125
-------
These results indicate that baseline levels of platinum and
palladium in environmental samples and in human populations in the
Southern California area are extremely low. The levels in all instances,
other than composite samples, are below the detection limits of atomic
absorption.
L. Lead
a. Environment
The air lead determinations made from the samples
collected 80 feet downwind from the freeway in Los Angeles and outside
the residences of the Lancaster participants are presented in Table 19.
The statistical analysis of these air lead data is presented in Table 20.
The square root transformed data was used in conducting the t test,
because it gave acceptable variance equality for the Los Angeles and
Lancaster sites. The t test shows that the average lead concentration in
the air approximately 80 feet downwind from the San Diego Freeway in
Los Angeles was very significantly greciter than that in the air in the
backyards of the Lancaster participants.
The configuration and lead determinations of the soil
samples taken near the San Diego Freeway in Los Angeles are shown in
Figure 8. These lead determinations are plotted in Figure 9 as a
function of the distance in the prevailing upwind and downwind directions
from the San Diego Freeway at the two Los Angeles soil sampling
locations. Figure 9 illustrates the general agreement of the soil lead
126
-------
Table 19. Baseline Air Lead Sample Data
3
Air Lead Concentration, ;ag/m
Los Angeles Lancaster
Site Site
6.84 0.40
5.83 0.83
0.60
0.51
0.44
0.41
0.64
0.58
0.48
0.87
1.03
0.90
0.69
Number of samples 2 13
Mean 6.34 0.64
Standard Deviation 0.71 0.21
127
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TABLE 20.
COMPARATIVE ANALYSIS OF BASELINE AIR LEAD DATA
Data Transformations
Means
Los Angeles
Lancaster
Variances
Los Angeles
Lancaster
Equality of Variance
P Test Statistic
Variance equality
Equality of Means
t Test Statistic
P value
None
6.34
0.64
0.510
0.042
12.03
No, P=.005
Square Root
2.516
0.794
0.0155
0.0159
1.024
Yes
18.00
P« .001
Natural Log
1.843
-0.484
0.0128
0.1000
7.81
No, P=.02
128
-------
FIGURE 8.
BASELINE SOIL LEAD SAMPLE DATA
N
125 ft
117
10 ft
5043
W
o
o
w
t— I
Q
to
LEAD CONCENTRATIONS
IN SOIL, SAMPLES
Site; V.A. MEDICAL COMPLEX &
CEMETERY
10 ft
125 ft
296
100 ft
77
(CONTROL)
20 ft
100 ft
300 ft
234
Site; U. C.L.A. MARRIED STUDENT
HOUSING
129
-------
4800
3600
2400
1200
600
0
Feet
Lead Con
in Soil-
sentrationj
Samples
Legend
x U.C.L.A. Married
Student Housing
Site
o EPA Air Sampling
Site (V.A. Medical
Complex)
\
125 80 40 0 0 40 80 120 200 300
Upwind from Freew ;y Feet Downwind from Freeway
FIGURE 9. SOIL LEAD CONCENTRATION WITH DISTANCE
FROM THE SAN DIEGO FREEWAY
130
-------
data from the two Los Angeles sampling sites adjacent to the San Diego
Freeway with respect to distance downwind or upwind from the express-
way. Within ten feet of the expressway, the air turbulence created by
the vehicular traffic flow apparently distributes the emitted lead equally
on both the upwind and downwind sides of the expressway. However,
the rate of reduction of soil lead concentration is much more gradual on
the prevailing downwind side of the expressway. For example, at a
distance of 100 to 125 feet from the expressway, the downwind soil lead
concentration is from 3 to 9 times higher than the upwind soil lead
concentration.
The soil lead determination obtained at the Los
Angeles participants residence, the U.C.L.A. married student apart-
ments, is compared against the seven Lancaster soil lead determinations
in Table 21. The logarithmic transformation of the soil lead determinations
is chosen for conducting the Dixon gap test of the potential Los Angeles
outlier, because it best satisfies the normality assumption of the Dixon
test and because it yields the most conservative test. The Dixon test
indicates the Los Angeles sample definitely is an outlier from the
Lancaster soil sample population. Thus, the soil lead concentration at
the Los Angeles participants' apartment complex was significantly
greater than the soil lead concentration in the Lancaster participants'
backyards.
The lead concentrations were determined for five
samples of tap water obtained both from the Los Angeles participants'
131
-------
TABLE 21.
OUTLIER ANALYSIS OF BASELINE SOIL LEAD DATA
Lancaster Samples
I
2
3
4
5
6
7
Lancaster Mean
Lancaster Standard Deviation
Los Angeles Sample
Combined Site Statistics
Mean
Standard Deviation
Dlxon gap test statistic
Outlier
None
3633
Data Transformations
Square Root
Natural Log
54
43
49
79
62
83
98
66.9
20.2
7.35
6.56
7.00
8.89
7-87
9-11
9-90
8.09
1.23
60.27
3-99
3-76
3-89
4.37
4.13
4.42
4.58
4.16
0.30
8.20
4.67
1.45
0.815
Yes,
.001
132
-------
apartments and from the Lancaster participants' homes. The lead
data and its statistical analysis are presented in Table 22. There was
no significant difference between the mean lead concentrations of the
tap water supplied to the Los Angeles and Lancaster participants.
The building surfaces of the U.C.L.A. married
student housing facility were examined for lead, and the values were
less than 3.0 mg/g of dried paint.
b. Study Participants
The standard t test of two independent samples was
utilized to compare corresponding participant groups from the two sites
with respect to significant differences in population means. Site
comparisons were conducted for each tissue on the total participant
groups and on subgroups stratified by sex and age. The t test assumes
both sampled populations are normally distributed with equal variances.
The normality assumption was examined by testing
the skewness of the group observations. The skewness test was applied
to the data and its square root and logarithmic transformations to determine
which transformation produced the least skewed data (i.e., the trans-
formation under which the normal distribution assumption was best
justified). Table 23 displays the results of the skewness tests by P value.
The smaller the P value, the less justified is the normal distribution
assumption. P values above 0.05 are interpreted as accepting the normal
distribution assumption; such a result is denoted as OK in Table 23.
133
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TABLE 22.
COMPARATIVE ANALYSIS OF BASELINE TAP WATER LEAD DATA
Tap Water Sample Lead Concentrations
Square Root Transformation of
Tap Water Lead Data
Los Angeles
0.040
0.019
0.024
0.021
0.028
0.200
0.138
0.155
0.145
0.167
Square Root Transformation Statistics
Mean O.l6l
Standard Deviation 0.024
Variance 0.00060
Lancaster
0.036
0.022
0.019
0.021
0.022
0.190
0.148
0.138
0.145
0.145
0.154
0.021
0.00043
Equality of Variance
F test statistic
Variance equality
Equality of Means
t test statistic
Mean equality
1.38
Yes
0.50
Yes, (P=.64)
134
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"ABLE Z3. Skewness Test of Normal Distribution Under Various Transformations
of the Baseline Human Subject Lead Determinations
Transformation
None
Tissue
Blood
Long Hair
Short Hair
Urine
Feces
Group
Total
Male
Female
Total
Male
Female
Total
Male
Female
Total
Male
Female
Total
Male
Female
L.A.
P Value
<. 01
<. 01
<. 01
<. 01
<.01
<.01
«. 01
<-. 01
. 01
<. 01
<.01
< . 01
«. 01
-------
Inspection of Table 23 shows that, for most of the grouped participant
lead data, the natural logarithm transformation yields data for which
the normal distribution assumption is valid. In those few cases when
the natural log transformed data were not normally distributed, it still
gave less skewness to the data than either the untransformed or square
root transformed data. With respect to the t test's normality
assumption, the natural logarithm transformation of the blood, hair,
urine, and feces lead data is consistently preferable to either the square
root transformation or no transformation.
The validity of the assumption of equality of variance
between participants within the two t test compared groups was examined
by the standard variance ratio F test. Equality of variance was tested
for the comparable groups at the two sites using the untransformed tissue
lead data, the square root transformed data, and the natural log trans-
formed data. The F statistic and associated P value are presented for
each comparison in Table 24. P values above 0.05 are interpreted as
accepting the equality of variance assumption; such P values are simply
denoted as OK in Table 24. Examination of Table 24 discloses that the
natural log transformation is clearly superior to no transformation or
the square root transformation in equalizing the variability within the
compared groups. The natural log transformation yielded acceptable
variance equality in every case for the blood, urine, and feces lead data.
On the long and short hair lead data, the logarithmic transformation was
uniformly better than either the square root transformation or no trans-
formation in equalizing the variability of the compared groups.
136
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TABLE Z4. Test of Variance Equality Under Various Transformations of
the Baseline Human Subject Lead Determinations
Transformation
None
Tissue
Blood
Long Hair
Short Hair
Urine
Feces
Group
Total
Male
Female
Total
Male
Female
Total
Male
Female
Total
Male
Female
Total
Male
Female
F Statistic
3.32
3.52
2.53
1.98
7.98
1. 12
31. 35
45.63
9. 38
1.87
1.92
3.01
1.44
2.66
2.71
P Value
<§.. 001
<. 001
<. 001
<. 001
«. 001
OK
«. 001
«. 001
«. 001
<. 001
. 009
<. 001
.02
<. 001
<. 001
Square Root
F Statistic
1.94
1.98
1.58
2.07
3.82
1.55
6.14
8.16
3.57
1.04
1.47
1.22
1.07
1.31
1.80
P Value
<. 001
. 005
. 03
<. 001
<. 001
. 04
«.001
«. 001
<. 001
OK
OK
OK
OK
OK
. 008
Natural
F Statistic
1. 15
1. 16
1.02
1.41
2.35
1. 18
1.80
2. 13
1.48
1. 19
1.16
1. 14
1. 18
1. 11
1.29
Log
P Value
OK
OK
OK
.04
.004
OK
. 003
.006
OK
OK
OK
OK
OK
OK
OK
137
-------
Since the natural logarithm transformation was so
uniformly superior in achieving the t test assumptions, it was applied
to each set of compared data prior to the conduct of its t test. To assist
in interpreting the results based upon the natural log transformed data,
the geometric mean has been reported. The geometric mean is the
reverse (i.e., exponential) transformation of the mean of the natural log
transformed data back into the original lead concentration data scale.
A summary of the lead concentration data obtained
for each sex and age subgroup at the two sites is shown in Tables 25A,
25B, 25C, 25D, and 25E for the five tissues sampled. The data for
individual values for lead are provided in Appendix C. The statistics
contained in Table 25 are N (the number of participants in the group
providing at least one analyzed sample of the tissue), the arithmetic mean
of the untransformed data for the group (X), + the standard deviation of
the arithmetic mean (s —= s / \/N), and the geometric mean.
Table 25 reveals the general characteristics of the
lead concentration data from the two baseline sites for each of the five
types of samples. The average lead concentrations of the Los Angeles
participants were generally higher than those of the corresponding sex
and age group of Lancaster participants for the blood, long hair, short
hair, and urine samples. However, the average lead concentration in
the feces of the Los Angeles participants was about the same or less than
the average lead concentration in the Lancaster participants' feces
samples.
138
-------
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The validity of the Table Z5 observations was examined.
utilizing the t test of the logarithmically transformed lead concentration
data to determine the significance of the observed differences. The
results are presented via the two sided t test statistic and its P value in
Table Z6.
The mean lead concentrations in the blood, long hair,
short hair, and urine of the total group of Los Angeles participants were
very significantly higher than the corresponding mean lead concentrations
of the total group of Lancaster participants ( P «. 001 for each of the four
tissues). There was also a significant elevation of the mean blood lead,
long hair lead, short hair lead, and urine lead levels of the male and
female subgroups of Los Angeles participants over the corresponding
Lancaster group. The inferences for the comparable sex-age subgroups
across site were less consistent; this finding may be attributable to the
smaller sample sizes, the absence of any real difference, or both of these
factors. However, in general, the younger age group (1-16) tended to
show more significant lead level elevation in Los Angeles than the adult
age groups did.
In contrast, the feces lead levels of the Los Angeles
participants were significantly lower than those of the Lancaster
participants (P <.001). This effect was most pronounced for the two
adult female groups.
A more detailed statistical description of the site-sex-
age groups' lead levels in blood, long hair, short hair, urine, and feces
144
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Because of concern over possible adverse health
effects from the elevated lead levels found in the Los Angeles participants,
the sampling of high blood lead concentrations ^as examined further.
The number and percentage of the blood samples with lead concentrations
above 40 jag/100 ml are tabulated in Table 27. Only five blood lead
concentrations above 40 (j.g/100 ml were sampled: four from Los Angeles
boys aged 8, 8, 10, and 12; one from a 15-year-old Los Angeles girl.
The only blood lead level above 50 jag/100 ml was 58.8 jag/100 ml from
one of the 8-year-old boys.
The lead concentrations of the blood, hair, urine, and
feces samples from the participants at the two sites were also related
to various potentially pertinent factors in addition to sex and age. These
additional factors were preschool/nursery vs. children in school, length
of residence in the city, distance from the expressway, distance from
other major highways, type of air conditioning, level of cigarette smoking,
ethnic grouping, and occupation. Appendix F presents the geometric
lead concentration mean for all levels of each of these factors for each
of the five tissues sampled. Examination of Appendix F shows that none
of these factors exhibit a consistent effect at both sites. The apparent
factor effect generally results from the unequal allocation of the factor
among the participants at the two sites, or by correlation of the factor
with the sex or age of the participants.
147
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between some factor/site combinations and the lead concentration for
more than one tissue. The Los Angeles preschool and nursery children,
who remained in their apartment complex adjacent and downwind from
the San Diego Freeway all day, appear to have had slightly higher lead
concentrations in their blood, long hair, and short hair than did the older
Los Angeles school children (who attended schools at a considerable
distance from the expressway). The Los Angeles participants seem to
have increased lead levels in their long hair, short hair, and urine with
longer lengths of residence in Los Angeles. The Lancaster participants
living within two blocks of major highways appear to have higher lead
level s in their long and short hair than do the Lancaster participants
living farther from major highways. Los Angeles participants living in
non-air-conditioned homes seem to have higher lead concentrations in
their blood, long hair, and short hair than do the Los Angeles participants
whose homes had air conditioning.
The significance of each of these apparent relationships
was investigated using a t test. The results are presented in Table 28.
There is no significant elevation of the mean lead levels in the blood and
hair of the preschool and nursery Los Angeles children over those of the
older Los Angeles children. As the participants' length of residence in
Los Angeles increased, there was a very significant increase in their
mean urine lead level. However, the relationship of mean hair lead to
length of residence in Los Angeles remains uncertain. The Los Angeles
149
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residents whose homes were air-conditioned had significantly lower
average blood and short hair lead levels; than the Los Angeles
residents living in homes without air conditioning. The Lancaster
participants living within two blocks of a major highway had very
significantly higher mean short hair lead levels and significantly higher
mean long hair lead levels than the Lancaster participants living more
than a mile from any major highway. While some of the preceding
findings regarding the additional factors are significant, the indicated
relationships should not be construed to have been demonstrated. The
combination of uncontrolled factors and chance provides a plausible
alternative to these significant factors.
c. Autopsy - Los Angeles
Table 29 shows the results of the analysis of autopsy
tissues from Los Angeles for lead. As described earlier in this report,
these autopsy cases are from a hospital via a pathologist. They are not
from accidental death cases. The data are similar to those collected
for other lead studies. There are not sufficient samples to describe the
lead content with regards to age, sex, length of residency in Los Angeles,
smoking history, etc.
d. Sources of Variation in Human Lead
Determinations
Two blood, urine, and feces samples were obtained
on consecutive days from most of the Los Angeles and Lancaster
participants. Table 30 presents the between participant and within
152
-------
TABLE 29. AUTOPSY TISSUES (Los Angeles)
Lead Values (|J.g/g - Wet Tissue)
Tissue No. Kidney Fat Spleen Muscle Lung Liver
Male
1.
2.
3.
4.
5.
A 7653
A 7593
A 7572
A 7617
A 7657
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0.37
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participant variances of the natural log transformed lead determinations
within each site-sex-age-group. The P value is tabulated in the last
column of Table 30 for those groups having a significantly smaller within
group variance than the between group variance. In most groups, there
was no significant difference. The implication in these cases is that the
two samples obtained on consecutive days from one person display about
as much variability in their lead determinations as two samples taken
from two different people in the same group. The within group (i.e. ,
diurnal/sampling/analytical) variability is very large.
An additional blood sampling experiment was performed
to investigate the source of the within group variability. Sixteen blood
samples were obtained simultaneously from an adult male and processed
and analyzed according to the same procedures used with the baseline
blood samples. Two aliquots of each sample were processed and analyzed;
their lead determinations are presented in Table 31. An analysis of
variance of the logarithmically transformed blood lead determinations
is shown in Table 32. There are no significant differences between the
aliquots or between the samples.
The variance components estimated from the sampling
experiment have been compared against the participant and sampling
variances for the appropriate group (males aged 17 to 34) of Lancaster
and Los Angeles participants. The comparison is shown in Table 33.
The repeatability variance accounts for about 13% of the between
156
-------
Table 31. Blood Lead Determinations from Sampling Experiment
Blood Lead, jug/100 ml
Sample Aliquot A Aliquot B
1 5-86 7-19
2 7-74 7-35
3 6.28 7.67
4 6.77 9.02
5 6.09 6.88
6 6.76 6.92
7 6.99 7-02
8 9-42 7-39
9 7.12 7.25
10 9-32 7.79
11 7.10 8.60
12 6.36 6.90
13 6.18 7.35
14 8.17 7-35
15 7.99 6.18
16 7.99 9.89
157
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159
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participant variance. The simultaneous sampling variance accounts
for another 5%. The variability associated with sampling on consecutive
days contributes another 55% to the between participant variance.
Apparently there was much daily variability in the blood lead levels of
the participants in this study.
The individual blood lead analysis results are
presented in Appendix C. In regard to sampling variation, a scan of the
data disclosed that all 15 sampled blood lead concentrations above
30 jjtg/lOOml occurred in the first sample provided by Los Angeles
participants. Most of the elevated blood lead values occurred in children,
some of whom were not sampled for blood on the second day. Thus, of
the Los Angeles participants who provided two blood samples, there
were 10 blood lead concentrations above 30 (jig/100 ml; in each of these
ten cases, the first sample concentration analysis was above 30 (og/lOOml,
and the second sample value was below 30 (j.g/100 ml. This anomaly was
investigated further to determine whether there was a consistent lead
concentration bias between the first and second samples of the Los Angeles
and/or Lancaster participants.
A review of the blood shipment and lead analysis
procedures did not detect any erroneous blood lead values. The sequence
in which the lead analyses of the blood samples were performed was the
only facet of the lead analysis procedure that might be relevant to the
anomaly. All of the first samples were analyzed before any of the
second samples. However, to prevent a. site bias, the Los Angeles and
160
-------
Lancaster first sample lead analyses were properly interspersed;
so were the second sample lead analyses.
The cumulative sample distributions of the lead
concentration determinations for the 99 Los Angeles participants and
the 97 Lancaster participants who provided two blood samples are shown
below. For both Los Angeles and Lancaster, more of the high blood
l!Los Angeles Lancaster
First Second First Second
Sample Sample Sample Sample
# Samples 30|ag/100ml 10 0 00
# Samples 25|o.g/100ml 16 5 01
# Samples 20|j.g/100ml 28 14 35
# Samples 15|jLg/100ml 47 40 19 9
# Samples 10|j.g/100ml 70 79 48 36
# Samples 5|ig/100ml 98 97 90 91
Total Number of Samples 99 99 97 97
lead determinations occurred on the first sample than on the second
sample. The two-sample Kolmogorov-Smirnov Test was utilized to test
for significant differences between the first sample and second sample
distributions. Neigher for Los Angeles (D = .182; P = .08) nor for
Lancaster (D = .144; P = .27) did the first sample and the second
sample distributions differ significantly at the 0.05 level.
161
-------
The mean and standa.rd deviation of these paired
sample lead determinations are presented below, for both the value and
their natural logarithm transformations. Because the blood lead
Los Angeles Lancaster
First Second First Second
Sample Sample Sample Sample
Number of Samples 99 99 97 97
Original Values, |ag/ 100ml
Mean
Standard Deviation
Ln Transformation,
In ((Jig/ 100 ml)
Mean
Standard Deviation
16.45
9.80
2.652
0.539
14.22
5.29
2.582
0.400
10.71
4.68
2.262
0.506
9.96
4.45
2.212
0.414
determinations have a skewed distribution, t tests utilizing the natural
logarithm transformed values should be employed to test for bias between
the first and second sample lead determinations. Since the sample
determinations are paired, the paired comparison t test is the most
powerful for detecting shifts in the distribution. The two-sided paired
comparison t test of the logarithmically transformed blood lead
determinations shows no significant difference in means between the first
sample and the second sample, neither for Los Angeles (t = 1.17;
P = .25) nor for Lancaster (t = 1.00; P = . 32). While the preponderance
of the high Los Angeles blood lead determinations occurred on the first
sample, the statistical analysis of the pcdred samples discloses no
significant differences between the first sample determinations and the
162
-------
second sample determinations, neither in their overall distribution nor
in their location. There is no detectable bias between the first sample
and the second sample determinations.
210
e. Pb Analysis
210
Pb has been used as a tracer to determine the
sources of lead present in people. Terhaar and Aronow '
selected children with elevated blood leads that were known to have
consumed leaded paint and compared them with children with low blood
leads without exposure to leaded paint. They examined urine and feces
210
samples from these children for Pb and Pb. Their study was
designed to determine whether or not lead from dust was contributing to
the body burdens of lead in the children that were eating leaded paint.
210
Pb is very low in paint chips (0.005-0.07 p Ci/g), much higher in
airborne particulate (60-150 p Ci/g) and also high in dusts (3-30 p Ci/g).
F.rom these data, it would appear that the following
probably would occur in different situations.
Blood Feces
210 210
Major Sources of Lead Pb Pb Pb Pb
Paint high low high low
Dust high high high high
Air high high low low
Low lead exposure
(dietary only) low low low low
Reports in the literature have not demonstrated all
of these relationships, especially with respect to blood. In this project,
163
-------
samples of blood and feces were collected from children at the UCLA
site, along with particulate air and soil samples, for ^*^Pb analysis.
The objective was to obtain additional information relative to the sources
of lead at this site.
Airborne particulate samples yielded the following
results:
Los Angeles - UCLA site 1. 137 p Ci/g
UCLA site Z. 157 p Ci/g
These values are similar to those reported for
urban airborne particulate (60-150 pCi/g).
The ratio of 21QPb to 208Pb (stable) in the air
particulate matter collected at Los Angeles (UCLA site) is:
740
pCi Pb = 3. 012 average
mg
Applying this ratio to a 10-ml blood sample containing
approximately 40|ag of stable lead per 100ml of blood, there would be
210 21°
0.012 p Ci Pb present. The detection limit of the method for Pb
was 0.045 p Ci (average) for total blood sample, and the detection limit
for lOg feces (dry wt. ) was 0 . 05 p Ci/g.
210
Only one of the 30 blood samples analyzed for Pb
was positive. The blood sample had 18.7|ig of stable lead per 100ml of
210
whole blood, and 1.6pCi of Pb/lOml of blood was found. The other
blood samples were less than the detection limit. Of the thirty feces
samples examined three had detectable levels.
164
-------
These values were:
pCi/g
0.18
0.026
0.040
stable Pb Mg/g (wet)
2.22
1.21
A value of 0.044 pCi/g has been reported by TerHaar and Aronow as a
normal fecal
210
Pb value.
The data for soil samples are as follows:
210
Sample Identification
Pb-pCi/g (dry wt.) Stable Pb [qg/g (drywt.)
100 ft
20 ft.
100 ft
300 ft
. west of freeway
east of freeway
. east of freeway
. east of freeway
1.
2.
1.
2.
1.
2.
1.
2.
0.66
0.86
1.09
0.96
1.22
0.99
0.57
0.74
1.
2.
1.
2.
1.
2.
1.
2.
58
96
3490
3775
824
522
165
302
The results from these analysis are ID t as useful as
was expected because the detection limits obtained were not sufficiently
low. The air particulate samples and soil data are similar to those
reported elsewhere. The fecal values are low, as was expected, but the
data for blood are not useful because the sensitivity was not good enough.
A high average for blood would have been 0.012 p Ci per 10ml, but the
detection limit of the method was only 0.045 pCi per 10ml.
165
-------
More information is needed on this type of measurement
to prove its usefulness in defining the sources of lead. It has been
shown by TerHaar and Aronow that the measurements will differentiate
in children grith high blood and high fecal leads as to consumption of
lead primarily from paint or soils. Its usefulness has not been
demonstrated for airborne lead.
B. Mining
1. Environment
Air, water (from streams and ponds) and soil samples were
collected in an around the mining and ore processing facilities located
in Sudbury, Ontario. Most of these samples did not produce measurable
responses with AA. Table 34 shows the air data. The precious metals
area is located within the ore processing part of the plant, and this area
includes the final step performed by this plant on platinum and palladium
concentrates. Measureable levels were found in surface soil samples
located in two areas around the plant.
Soil
Pt Pd
Vermillion Mine 0.8 ppb 4.5 * ppb
Copper Cliff 0.8 ppb 2.0* ppb
* limit of detection 0 . 7 ppb
Water samples were negative for platinum and palladium,
and the detection limits are as follows: platinum 0.05 ppb, palladium
0.015 ppb.
166
-------
Table 34. Platinum and Palladium Concentrations in Air Samples
at the Sudbury Mine
Location within the Mine Metal Concentration,
Engineering Building
South Mine
Precious Metals Area
Furnace Room
Platinum Palladium
a a
a a
0.377 0.291
a a
a. Below detection limit of 0.003 ,ug/m
167
-------
i. Study Participants
As mentioned earlier in this report 49 male employees
in mining and ore processing at Sudbury were sampled twice for blood,
urine, and feces. A sample of short and long hair was also collected.
These samples were examined for content of platinum and palladium, and
no detectable levels were found. The detection limits for these types of
samples were given in Table 5.
3. Autopsy Cases
A total of nine male autopsy cases were collected in Sudbury
from individuals that had been previously employed by the mining and ore
processing plants in this area. Table 35 shows information collected on
these cases. Samples of liver, kidney, spleen, lung, muscle and fat were
collected from each autopsy. In all but the following samples, there
were no detectable levels of platinum and palladium.
Sample ID Pt
A d 20-75 - fat 4.5 ppb
A 100-75 - lung 3.7 ppb
A 114-75 - muscle 25.0 ppb
C. Refineries
1. Environment
In one of the refineries (sa,mples collected and analyzed by
the company), it was reported that 42 a:ir samples were collected in 15
different locations within the plant over a 9-month period. The values
168
-------
TABLE 35. AUTOPSY CASES - SUDBURY
Sample
ID
A 52-75
A 59-75
A 70-75
A 73-75
A99-75
A 100-75
A 106-75
A 114-75
A 120-75
Age
50
60
55
73
61
52
47
22
51
Sex
M
M
M
M
M
M
M
M
M
Smoking
History Cause of Death
Unknown Skull fracture
Yes Coronary infraction
Unknown Coronary thrombosis
Unknown Coronary thombosis
Unknown Myocardial infraction
Unknown Ischemic heart
Yes Coronary thrombosis
Yes Automobile accident
Yes Pulmonary edema/ischemia
169
-------
for platinum and palladium were very low and in all cases were within
the prescribed OSHA standards as set forth in the Federal Register,
Vol. 36, No. 157, dated August 31, 1971.
In the other refinery, the samples were collected by the
company but analyzed by this laboratory.
The working environment of the refinery was characterized
through 24-hour ambient air samples collected for five consecutive work
days in the refinery and salts sections of the plant. The platinum and
palladium concentration determinations obtained in the air sampling are
presented in Table 36. Note the relatively high palladium air
determination obtained on Monday in the refinery work section. This air
o
sample, whose palladium concentration was at least 0.356 |j.g/m ,
probably represents a valid palladium determination. However, because
of the possibility of contamination, the statistics for the refinery area
palladium data set were calculated both including and excluding the Monday
sample. Table 36 shows weekly average platinum concentrations of
33 3
0.159 |o.g/m and 0.180 |j.g/m and palladium concentrations of 0.085 |ag/m
3
and 0.028 |ag/m , respectively, in the refinery and salts sections.
Without the Monday sample, 0.017 was the weekly average palladium
concentration in the refinery section. In general, the platinum concentration
appears to have been higher than the palladium concentration in the air
inside this refinery. However, all the measured ambient air levels of
platinum and palladium were well below the OSHA standards.
170
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171
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2. Study Participants
One of the refineries examined 17 of their employees
(substantially all of whom by the nature of their work were involved in
operations associated with the chemical processing of platinum and
palladium) for platinum and palladium in urine and blood samples. No
platinum or palladium was found. The detection limits given (by the
refinery) were 60 ppb for platinum and 20 ppb for palladium.
Samples of blood and urine were collected from 61 refinery
workers by the other refinery and analyzed in this laboratory. The
levels of platinum and palladium in blood were below the detection limits
(1.4 ppb platinum and 0.4 ppb palladium).
Six of the 58 urine samples obtained and analyzed had
platinum concentrations above the detection limit of 0.10 (a.g/1. These
six determinations which ranged from 0.23 (ag/1 to 2.58 (j.g/1 are presented
in Table 37. It is noteworthy that each urine sample with a detectable
platinum concentration also had a palladium level above 1.0 p.g/1. The
workers with detectable platinum levels were not confined to any
particular, work section within the refinery.
Thirty-four of the 58 workers submitting urine samples had
urine palladium concentrations above the 0.21 fig/I detection limit. The
sample determinations are presented by refinery work section in Table 38.
The mean and standard deviation of the palladium determinations for
each work section and for the total refinery are also shown in Table 38.
The mean palladium urine concentration was 1.07 (j.g/1; the maximum
172
-------
Table 37. Platinum Concentrations in Urine Samples from
the Six New Jersey Refinery Workers with Detectable
Platinum Levels
Urine Platinum Worker's Corresponding
Concentration Work Urine Palladium
jug/1 _ Section Concentration,
0.23 Maintenance 1.59
0.49 Refinery 2.93
0.66 Refinery 1.05
1.22 Salts 2.42
1.24 Salts 6.27
2.58 Storeroom 7-4l
Notes:
The urine samples of 58 refinery workers were analyzed for
platinum.
The minimum detectable urine platinum concentration was
0.10 pg/l.
173
-------
TABLE 38. NEW JERSEY RE-FINERY WORKER URINE
PALLADIUM CONCENTRATIONS CLASSIFICATION
' BY REFINERY WORK SECTION
Urine Palladium Concentration,
Refinery Work Section
Refinery Salts
Sample
Determinations: a a
2.12 5.91
0.81 a
0.35 a
1.01 a
a 1.21
1.05 0.95
a a
2.93 2.12
a 6.27
a 0.63
0.31
Statistics:
No. of Samples 12 11
Mean 0.80 1.68
Std. Dev. 0.88 2.28
Recovery
0.13
a
0.31
a
0.28
0.36
6.67
0.27
a
0.11 -
a
0.25
Q_
a
a
1.3*
0.77
a
0.62
a
20
0.68
1.11
Maintenance
0.77
2.83
0.28
a
a
a
1.59
0.17
0.60
3.09
1.66
0.16
12
1.03
1.03
Storeroom Refinery
Total
a
7.11
a
3 58
2.61 1.07
1.16 1.68
Below minimum detectable urine palladium concentration of 0.21 jug/1
174
-------
determination was 7.41 |ag/l. The urine samples were collected overnight
Monday and returned on Tuesday. Despite the high air palladium
concentration in the refinery section on Monday, Table 38 does not
indicate any obvious relationship between a worker's work area and his
urine palladium concentration.
The original urine palladium data presented in Table 38
and their natural logarithm transformations have been examined with
respect to the normality of their distribution. The logarithmically
transformed data, having a mean of -0.67 and a standard deviation of
1.09 over all 58 observations, is much less skewed. The assumption
that this logarithmically transformed data has a normal distribution
appears to be warranted.
A one-way analysis of variance by refinery work section
was conducted on the natural log transformed urine palladium concentration
data. Table 39 presents the mean and standard deviation of the natural
log transformed data in each refinery work section. The logarithmic
transformation does tend to equalize the urine palladium variability
within each work section. Table 39 also contains the analysis of variance
by work section. There was no significant difference in the mean
urine palladium concentration among the workers in the five refinery
work sections (F = 0.991 < F (4,53) = 2.55). In fact, there is just as
.05
much urine palladium variability among the workers within a single work
section as between workers in different work sections.
175
-------
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Correlation analysis was used to explore any relationship
of the urine palladium determinations to the available social and
occupational variables. Table 40 presents the results of the correlation
analysis of the logarithmically-transformed urine palladium determinations
with the age, race, cigarette smoking, length of employment, work
section, and work shift or the refinery worker participants. The
correlation analysis shown in Table 40 was conducted both for all 58
workers with analyzed urine samples and for the 34 workers with
detectable urine palladium levels. There are no significant correlations
of urine palladium with any of these six factors for either worker data
set. The variability in the workers' urine palladium concentrations
cannot be explained in terms of the available social and occupational
factors.
177
-------
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-------
References
1. Johnson, D. E. , Tillery, J. B. and Prevost, R. J. ,
Trace metals in occupationally and nonoccupationally exposed
individuals, Environ. Health Persp. , 10, 151-158(1975).
2. Bowen, H. J. M. Trace Elements in Biochemistry,
Academic Press, New York, 1966, p. 197.
3. Yoakum, A. M. , Stewart, P. L. and Sterrett, J. E.
Method development and subsequent survey analysis of biological
tissues for platinum, lead, and manganese content, Environ.
Health Persp. , 10, 85(1975).
4. LeRoy, A. F. Interactions of platinum metals and their
complexes in biological systems, Environ. Health Persp. ,
10, 73(1975).
5. Bumgarner, J. and Yoakum, A. M. A critical review of
analytical methods for the determination of platinum and
palladium in biological tissues. In-house technical report,
Bioenvironmental Laboratory Branch, National Environmental
Research Center, Research Triangle Park, N. C. ,
September 10, 1973.
6. Aggett, J. and West, T. S. Atomic absorption and fluorescence
spectroscopy with a carbon filament atom reservoir. Determination
of gold by atomic fluorescence and atomic absorption spectroscopy
with an unenclosed atom reservoir, Anal. Chim. Acta. , 55,
349(1971). ~
7. L'vov, B. -V. The potentialities of the graphite crucible method
in atomic absorption spectroscopy, Spectrochim. Acta. 24B,
53(1969). ~
8. Mulford, C. E. Solvent extraction techniques for atomic
absorption spectroscopy, Atomic Abs. Newslett. , 5, 88(1966).
9. Adriaenssens, E. and Knoop, P. A study of the optimal conditions
for flameless atomic absorption spectrometry of iridium, platinum
and rhodium, Anal. Chim. Acta., 68, 37(1973).
10. Guerin, B. D. The determination of the noble metals by atomic
absorption spectrophotometry with the carbon-rod furnace,
J_. S. Afr. Chem. Inst. , 15, 230(1972).
11. Janouskova, J. , Nehasilova, M. and Sychra, V. The determination
of platinum with the HGA-70 graphite furnace, Atomic Abs.
Newslett., 12, 161(1973).
179
-------
12. Khattak, M. A. and Magee, R. J. Spectrophotometric determination
of platinum after extraction of the stannous-chloro complex by
high molecular weight amines, Talanta, 12, 733(1965).
13. Khattak, M. A. and Magee, R. J. Spectrophotometric
determination of palladium after extraction of the chloro-stannous
complex by tri-n-octylamine, Anal. China. Acta. , 35, 17(1966).
14. De, A. K. , Khopkar, S. M. and Chambers, R. A. Solvent
Extraction of Metals, Van Nostrand Reinhold, London, 1970, p. 23.
15. Davidson, C. M. and Jameson, R. F. Complexes formed
between the platinum metals and halide ion. I. Extraction of
hydrohalic acids by solutions of Amberlite LA-2 in carbon
tetrachloride, Trans. Faraday Soc. , 59, 2845(1963).
16. Davidson, C. M. and Jameson, R. F. Complexes formed between
the platinum metals and halide ions. II. Extraction of haloplatinates
by solutions of salts in Amberlite LA-2 in carbon tetrachloride
and in cyclohexane, ibid. , 61, 133(1965).
17. Hwang, J. Y. , Ullucci, P. A. and Mokeler, C. J. Direct
flameless atomic absorption determination of lead in blood,
Anal. Chem. , 45, 795(1973).
18. Mitchell, D. G. , Ryan, F. J. andAldous, K. M. The precise
determination of lead in whole blood by solvent extraction-atomic
absorption spectrometry, Atomic Abs. Newslett. , 11, 120(1972).
19. Kubasik, N. P. and Volosin, M. T. A simplified determination
of urinary cadmium, lead, and thallium, with use of carbon rod
atomization and atomic absorption spectrophotometry, Clin.
Chem. , 19, 954(1973).
20. Hammer, D. I. , Finklea, J. F. , Hendricks, R. H. , Hinners,
T. A. , Riggan, W. B. and Shy, C. M. Trace metals in human
hair as a simple epidemiologic monitor of environmental
exposure,, Trace Substances in Environmental Health-V. 1972.
A symposium, D. D. Hemphill, Ed. , University of Missouri,
Columbia.
21. Rantala, R. T. T. and Loring, D. H. New low-cost Teflon
decomposition vessel, Atomic Abs. Newslett. , 12, 97(1973).
180
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22. Smith, R. G. and Windom, H. L. Analytical handbook for the
determination of arsenic, cadmium, cobalt, copper, iron, lead,
manganese, mercury, nickel, silver and zinc in the marine and
estuarine environments. Technical report series number 72-6,
Georgia Marine Science Center, University System of Georgia,
Skidaway Island, Georgia.
23. Dr. Joseph Bumgarner, EPA, Research Triangle Park, N. C. ,
personal correspondence.
24. Dixon, W. J. Analysis of Extreme Values, Annals of Mathematical
Statistics, 21, 488-506(1950).
— ...-..—-.. f***
25. Snedecor, G. W. and Cochran, W. G. Statistical Methods,
6th ed. , The Iowa State University Press, 1967, p 86.
26. Fisher, R. A. Biometrika, 10, 507(1915).
27. TerHaar, G. and Aronow, R. , New information on lead in diet
and dust as related to the childhood lead problem, Environ.
Health Persp. 7, 83 (1974).
181
-------
APPENDIX A
INDIVIDUAL INFORMATION ON PARTICIPANTS FROM
LOS ANGELES AND LANCASTER
182
-------
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184
-------
APPENDIX B
DETERMINATION OF SAMPLE SIZE TO ANALYZE
VACUTAINER CONTAMINATION STUDY
185
-------
A 95% Confidence interval around a true mean value, |i, is
given by:
X- (1.96) (^-) < v. <_ X + (1.96) (-^=r)
where
X = sample mean
-------
APPENDIX C
INDIVIDUAL LEAD VALUES FOR PARTICIPANTS
FROM LOS ANGELES AND LANCASTER
187
-------
Los Angeles, California
188
-------
LOS ANGELES, CALIFORNIA
Sample I.D.
201
207
208
209
210
211
212
213
214
215
216
217
218
220
221
222
223
224
225
226
227
230
231
232
233
234
235
237
240
241
242
243
244
245
246
247
248
249
250
251
252
Blood-Lead Raw Data
p.g/100 ml whole blood
Sample No. 1
14.67
10.33
13.12
25.50
11.54
9.03
23.75
20.35
18.92
34.98
18.24
9.92
22.35
27.92
14.93
12.35
17.22
19.98
13.50
9.03 •
9.76
24.96
39.92
11.87
8.49
13.51
21.08
12.53
7.44
16.26
20.31
21.22
16.95
21.28
19.57
20.94
16.12
15.43
17.84
Sample No . 2
19.91
9.25
29.02
10.34
13.65
3.63
7.30
21.76
12.35
8.18
7.37
11.06
20.41
18.12
12.85
5.47
7.87
28.40
9.02
19.14
5.65
19.62
8.21
_ _ _
12.51
20.69
15.95
16.07
20.22
189
-------
LOS ANGELES, CALIFORNIA.
Sample I.D.
253
254
255
256
257
258
259
260
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
285
286
287
288
289
290
291
297
298
302
303
304
305
306
Blood-Lead Raw Data
|ig/100 ml whole blood
Sample No. 1
30.12
- 42.39
15.97
18.46
11.33
10.45
22.06
13.50
14.61
19.34
27.16
38.45
11.37
12.45
23.70
33.37
9.25 .
49.41
58.83
16.73
11.83
15.36
49.36
20.78
18.34
12.24
23.92
31.13
6.67
27.41
36.58
5.89
• 26.56
32.57
7.07
23.15
Sample No. 2
20.88
•V «* M
12.54
3.63
8.25
25.28
16.71
_ __
12.71
12.35
13.25
8.60
20.57
___
11.77
— _ _
— _ _
20.18
16.03
13.09
13.07
19.51
13.53
14.99
9.07
-__
_ __
14.49
11.00
15.04
10.45
15.40
14.99
18.02
10.23
190
-------
LOS ANGELES, CALIFORNIA.
Sample I.D.
307
309
310
311
312
313
400
401
402
403
404
405
406
407
408
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
430
431
432
433
434
435
436
Blood-Lead Raw Data
^jig/IPO ml whole blood
Sample No. 1
16.47
9.88
9.25
9.89
33.78
15.96
11.43
40.79
9.88
14.33
8.67
4.75
10.21
15.84
29.57
16.66
5.77
11.12
11.49 -
11.03
5.11
9.31
8.09
21.55
12.47 - '
15.93
22.12
5.13
12.00
6.40
16.94
9.58
23.92
7.76
9.21
8.99
15.39
4.95
8.40
6.79
Sample No . 2
10.27
8.53
10.87
15.07
27.08
17.73
14.58
11.40
15.74
16.88
18.77
13.08
19.03
8.06
13.09
12.75
8.98
10.32
15.80
11.31
<1.50
19.38
13.66
11.16
11.26
9.14
7.75
19.97
26.04
14.39
16.61
10.01
16.58
17.35
11.76
12.11
191
-------
LOS ANGELES, CALIFORNIA
Blood-Lead Raw Data
Hg/100 ml whole blood
Sample I.D. Sample No. 1 Sample No. 2
437 7.25 22.28
438 8.91 10.37
439 13.12
440 18.70
441
442 10.87 9.35
443 <1.50 -- r <1.50
444 25.41
445 9.21 14.23
446 12.90 10.34
447 12.39 15.18
448 13.13 20.90
449 15.31 19.25
192
-------
LOS ANGELES, CALIFORNIA '
Feces-Lead Raw Data
p.g/g wet weight
Sample I.D.
201
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
230
231
232
233
234
235
239
240
241
242
243
244
245
246
247
248
249
250
251
252
Sample No. 1
•M »
--
0.01
1.70
0.83
0.65
0.71
1.00
0.62
0.48
0.08
-_
0.24
1.20
0.69
0.62
2.11
0.30
0.41
--
0.23
0.29
--
0.30
__
0.19
0.29
--
0.52
0.23
0.17
2.07
0.46
__
0.53
1.54
--
0.37
--
0.20
1.99
193
Sample No . 2
0.54
0.28
0.58
3.31
1.78
0.42
0.81
0.80
2.04
0.29
1.18
0.97
0.41
3.83
2.62
3.57
-_
__
1.17
0.86
0.14
0.01
0.65
0.29
0.18
0.30
1.48
10.19
0.51
0.38
0.23
--
0.61
0.76
1.61
0.65
0.73
0.83
0.17
0.61
-------
LOS ANGELES, CALIFORNIA '
Feees-Lead Raw Data
|j.g/g wet weight
Sample I.D. Sample No. 1 Sample No. 2
253 4.71 1.48
5.40
254 1.98 2.37
255 0.53 2.22
256 0.31 0.41
257
258
259 0.25 0.19
260 0.91 1.08
265 __ 1.21
266 -- o.84
267 0.40 1.09
268 0.22 0.11
269 - o.56
270 0.00 0.05
271 1.62 0.84
272
273 0.62 1.15
274 0.77
275 0.65 0.85
276
277
278 -- 1,22
279 0.42 1_
280 0.81
281 1.64 l.OO
282 -- 2.40
283 1.69
285 - o.26
286 1.54
287 0.10 0.37
288 -- i.5i
289 0.30 '—
290 0.61 0.22
291 - o.29
297 0.60 1.84
298 0.47 0.73
302 0.42 0.48
303
304 3.22 1.56
194
-------
LOS ANGELES, CALIFORNIA '
Feces-Lead Raw Data
weight
Sample I.D.
305
306
307
309
310
311
312
313
400
401
402
403
404
405
406
407
408
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
430
431
432
Sample No. 1
0.90
0.57
0.41
0.14
0.98
0.48
0.30
0.48
__
_ _
0.53
0.60
--
2.49
0.69
0.47
0.48
0.27
0.29
0.33
--
0.64
0.64
--
0.30
0.54
0.15
0.36
0.79
0.58
0.64
0.66
0.37
0.49
0.28
0.42
--
0.38
195
Sample No . 2
1.40
0.56
0.87
0.78
1.02
0.16
0.97
0.41
0.77
1.10
0.01
0.18
1.20
1.32
0.70
0.55
0.58
0.71
0.17
0.02
0.21
--
0.52
0.01
0.79
0.28
0.11
0.87
0.10
0.37
0.56
1.09
0.48
0.65
0.47
0.59
--
0.27
0.77
-------
LOS ANGELES, CALIFORNIA '
Fece;s-Lead Raw Data
wet weight
Sample I.D. Sample No. 1 Sample No. 2
433 -- 0.85
434 0.93 0.55
435 0.30 0.30
436 0.53 0.31
437 0.70 0.84
438 1.21 0.76
439
440 0.83 1.41
441
442 0.46
443 0.96
444
445
446 0.24
447 -- 0.08
448 -- 0.80
449 0.91
196
-------
LOS ANGELES, CALIFORNIA
Hair-Lead Raw Data
Sample I.D,
201
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
230
231
232
233
234
235
239
240
241
242
243
244
Short
26
12
4
-
14
24
5
6
_
_
23
37
_
101
28
-
136
47
155
79
54
52
82
35
50
23
6
45
_
13
308
12
_
Hair
.67
.05
. 32
-
.47
.66
.74
.49
_
_
. 34
.29
_
. 37
. 15
-
.47
. 75 •
. 52
.49
.86
. 10
. 32
. 39
.21
.03
.20
.63
_
.26
.59
. 58
_
Long
11
27
4
124
-
14
7
3
2
14
73
-
_
72
38
-
27
-
-
-
-
-
54
71
42
-
37
5
21
148
157
31
280
271
378
17
180
169
Hair
. 51
. 52
. 54
.49
-
. 31
.45
. 62
.83
.30
.63
-
_
. 34
.05
-
.63
-
-
-
-
-
.25
.33
. 30
-
.39
.92
.71
. 14
. 19
.98
. 34
.89
.74
. 77
. 87
. 10
199. 01
197
-------
LOS ANGELES, CALIFORNIA
Hair-Lead Raw Data
Sample I.D.
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
285
286 -- 146.71
198
Short Hair
38.30
26.17
44.01
89.89
145.37
109.14
69.49
--
9.03
--
62.77
14.27
25.91
—
7.61
<0.70
33.16
63.84
37.00
—
3.08
8.97
22.72
41.99
71.24
310.10
80.23
--
275.41
408.16
68.90
51.78
, 21.98
53.68
50.89
42.09
Long Hair
120.36
137.32
51.34
22.99
40.84
130.03
103.03
88.91
>
33.90
18.61
47.65
59.36
—
27.65
73.44
21.17
3.24
25.35
61.03
48.63
9.33
6.36
13.19
3.63
14.17
--
—
—
100.54
__
_ —
85.24
77.62
20.55
50.86
39.32
__
-------
LOS ANGELES, CALIFORNIA
Hair-Lead Raw Data
t^g/g
Sample I.D.
287
288
289
290
291
297
298
302
303
304
305
306
307
309
'310
311
312
313
400
401
402
403
404
405
406
407
408
410
411
412
413
414
415
416
417
Short Hair
151.37
36.55
—
- -
31.46
—
32.06
58.99
18.80
43.15
—
—
56.87
8.33
28.10
- -
49.61 •
—
- _
- _
—
—
--
100.76
—
104.00
133.44
--
8.79
—
--
--
3.82
86.67
Long Hair
43.78
148.67
55.33
9.44
40.23
19.47
57.50
22.75
46.85 -
13.01
21.72
22.55
14.30
112.15
68.48
7.90
6.64
65.61
17.20
28.66
45.48
177.27
225.60
80.94
31.00
30.63
22.92
72.31
22.88
29.80
8.35
9.37
3.74
23.25
12.36
31.20
86.67
99.12
199
-------
LOS ANGELES, CALIFORNIA
Hair-Lead Raw Data
Sample I. D,
418
419
420
421
422
423
424
425
426
427
428
430
431
432
433
434
435
436
437
438
439
440
441
442
443
444
445
446
447
448
449
Short Hair
26.49
—
—
—
14. 97
3U08
30.98
<0. 70
28.89
14. 12
85.47
79.81
27.02
88. 00
14. 34
10. 23
10.96
29. 74
21. 64 '
--
—
114.07
48. 39
—
51.00
8.35
37. 17
--
107.33
Long Hair
17. 18
28.03
59.63
14.31
—
19.38
5.30
1.27
13. 51
5.08
—
4.51
9.48
29.08
46.49
13.95
6.37
7.69
7.48
41.40
'97.84
72. 10
154.40
22.97
80. 14
35.46
1.76
12.23
18. 62
94.94
121. 15
200
-------
LOS ANGELES, CALIFORNIA
Urine-Lead Raw Data
H-gA
Sample I.D.
201
207
208
209
210
211
212
213
214
215
216
217
218
220
221
222
223
224
225
226
227
230
231
232
233
234
235
239
240
241
242
243
244
245
246
247
248
249
250
Sample No. 1
14.3
2.7
7.2
8.3
13.5
13.1
5.4
5.7
10.9
23.0
18.7
37.5
5.4
4.4
10.3
2.7
2.7
11.4
22.1
6.6
2.1
5.0
26.3
19.7
33.7
5.2
33.2
25.9
33.7
11.6
4.7
3.3
12.5
18.8
11.0
19.7
25.1
14.1
24.4
<0.6
201
Sample No . 2
8.8
3.9
10.7
5.8
3.9
17.4
11.4
6.9
37.6
8.5
5.0
—
5.6
6.6
7.2
7.6
9.0
18.0
14.8
5.4
--
15.1
--
17.8
19.4
12.2
11.3
8.4
5.2
22.9
34.9
15.5
5.5
14.0
13.5
9.2
35.0
12.7
9.0
11.6
__
-------
LOS ANGELES, CALIFORNIA
Urine-Lead Raw Data
Sample I.D.
251
252
253
254
255
256
257
258
259
260
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
285
286
287
288
289
290
291
297
298
302
Sample No. 1
15.6
31.7
77.4
3.2
9.6
13.0
32.4
„ _
1.7
7.7
35.2
9.8
11.6
4.5
9.3
7.3
26.2
17.0
2.1
38.7 '
--
9.6
34.3
18. 2
39.7
6.7
2.3
4.6
25.7
--
3.2
4.7
6.6
10.8
6.3
13. Z
6.Z
2.Z
3.6
Sample No . 2
11.7
15.3
19.3
10.7
9.9
7.8
16.6
25.2
11.2
.6.4
10.1
11.3
6.8
6.1
3.6
2.4
21.8
25.7
14.1
20.9
~ _
18.6
13.2
29.7
18.3
22.6
-------
LOS ANGELES, CALIFORNIA
Urine-Lead Raw Data
Sample I.D.
303
304
305
306
307
309
310
311
312
313
400
401
402
403
404
405
406
407
408
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
430
431
Sample No. i
<0.6
30.1
25.8
2.6
7.7
_ _
36.2
7.4
10.7
11.6
20.9
6.6
21.4
25.3
27.5
3.7
2.7
5.9
20.0
15.3
7.9
15.2
11.6
6.8
11.6
13.7
0.7
12.5
13.0
7.2
3.3
12.6
22.0
14.3
24.5
18.2
12.3
16.8
25.5
4.3
26.7
Sample No. 2
6.0
18.5
10.2
8.5
14.1
13.1
6.3
1.6
6.5
8.0
6.9 8,
14.0
22.3
4.0
10.2
4.7
13.3
12.2
18.0
11.2
3.6
10.6
2.4
6.0
9.2
10.4
3.6
4.4
17.6
10.7
11.9
10.0
7.3
4.9
5.7
13.6
14.8
16.9
19.5
19.5
13.4
203
-------
LOS ANGELES, CALIFORNIA
Urine-Lead Raw Data
Sample I.D. Sample No. 1 Sample No. 2
432 <0.6 12.1
433 10.8 18.3
434 12.3 8.0
435 -- 9.6
436 7.6 16.0
437 -- 4.7
438 17.6 14.1
439 44.7 15.1
440 9.3 17.8
441 76.0 23.8
442 3.4 24.5
443 5.2 21.8
444 13.5 14.1
445 9.8 17.8
446 5.2 4.1
447 - 4.9
448 18.6 13.1
449 17.9 27.3
204
-------
Lancaster, California
205
-------
LANCASTER, CALIFORNIA^
Sample I.D.
001
002
006
007
008
010
Oil
01Z
013
014
016
023
028
029
030
031
034
036
038
043
044
045
046
052
053
054
055
056
057
058
063
064
066
067
068
069
070
071
072
073
074
Blood-Lead Raw Data
|j.g/AGO ml whole blood
Sample No. 1
13.65
10.73
7.73
___
.14.75
10.17
12.31
16.34
15.39
4.62
13.89
5.98
8.85
6.40
7.38
16.34
12.46
13.46
8.01
4,35.
14.04
14. 61
6.43
17.56
9.03
8.16
11.12
12.74
10.74
9.16
8.23
10.32
<1.50
5.47
9.45
8.98
12.31
15.48
8.87
21.28
8.14
Sample No. 2
8.24
___
6.63
24.43
13.69
9.97
11.57
8.27
5.97
15.56
5.78
9.19
9.09
9.31
10.46
6.81
6.92
12.80
9.73
5.61
___
12.45
4.93
___
13.68
13.14
5.68
8.12
7.01
7.62
5.59
8.59
3.01
8.66
8.05
7.20
10.04
6.54
11.29
7.20
206
-------
LANCASTER, CALIFORNIA
Sample I.D,
075
079
080
081
083
084
085
087
088
089
090
091
094
096
097
098
099
100
106
107
108
109
110
111
112
114
115
116
118
119
120
121
124
125
126
127
128
129
130
131
132
133
Blood-Lead Raw Data
[j.g/100 ml whole blood
Sample No. 1
13.40
12.45
7.88
7.32
9.16
9.16
6.75
<1.50
16.96
15.61
16.97
9.63
15.90
14.84
5.00
8.26
10.49
9.18
11.12
6.97
8.27
21.29
6.09
14.11
21.76
24.17
15.03
14.23
12.29
8.71
3.28
5.44
17.49
5.01
15.63
9.12
9.03
8.51
4.65
12.52
10.01
Sample No. 2
16.44
3.84
8.17
9.30
9.95
8.15
9.09
5.49
12.62
6.60
9.66
7.35
16.82
5.34
14.89
8.87
14.53
14.53
7.10
5.15
14.65
20.18
4.85
8.43
25.34
24.86
5.73
8.91
6.73
6.92
11.10
24.38
4.76
12.37
7.01
7.92
13.25
10.89
207
-------
LANCASTER, CALIFORNIA
Sample I.D.
Blood-Lead Raw Data
lag/400 ml whole blood
134
139
140
141
142
143
144
145
146
147
149
150
151
152
153
154
155
160
163
164
165
167
168
169
170
171
172
173
174
175
450
451
452
453
454 8.51
455 7.94
456 9.87
Sample No. 1
11.95
18.47
13.48
10.85
9.93
13.39
5.91
8.31
13.70
12.07
7.51
5.14
4.22
7.96
19.94
5.82
17.96
12.19
12.19
9.42
5.55 •
9.46
8.88
11.71
5.53
11.59
6.69
6.69
18.47
18.86
7.56
6.40
5.91
Sample No. 2
12.77
7.15
__ _
7.21
11.35
r <1.50
12.45
6.47
12.19
12.25
6.01
8.05
-__
10.77
4.45
12.66
12.69
7.29
9.92
8.89
___
___
10.78
13.33
9.85
6.35
20.70
18.38
- -_
_ — _
8.13
208
-------
LANCASTER, CALIFORNIA
Sample I.D.
001
002
006
007
008
010
Oil
012
013
014
016
023
028
029
030
031
034
035
036
038
043
044
045
046
050
052
053
054
055
056
057
058
063
064
066
067
068
069
Feees-Lead Raw Data
fig/g wet weight
Sample No. 1
0.37
0.29
0.22
0.59
0.70
1.29
1.10
0.86
0.96
0.33
2.14
5.07
0.95
0.65
5.41
--
0.95
2.06
0.96
--
0.40
1.22
1.30
1.53
4.02
0.44
0.81
1.16
2.54
0.92
3.63
0.39
0.46
- 0.64
1.51
1.27
__
Sample No . 2
0.35
0.49
0.11
1.60
0.54
1.08
__
0.44
0.73
0.60
1.94
0.69
1.17
0.59
2.38
2.13
2.18
_ _
--
0.77
0.02
1.91
1.67
0.74
II
0,61
0.32
0.44
0.67
0.25
1.65
1.49
0.29
0.82
0.35
0.26
2.61
0.52
0.48
209
-------
LANCASTER, CALIFORNIA
Sample I.D.
070
071
072
073
074
075
076
079
080
081
083
084
085
087
088
089
090
091
094
096
097
098
099
100
101
106
107
108
109
110
111
112
114
115
116
118
119
Feces-Lead Raw Data
Hg/g wet weight
Sample No. 1
<1.50
0.86
0.44
1.58
1.78
0.24
0.31
0.58
0.72
1.08
0.85
0.64
0.88
1.40
2.65
2.02
1.18
3.14
0.29
2.06
--
1.11
1.57
0.42
2.48
2.38
2.04
0.94
1.44
1.18
0.67
0.86
1.01
Sample No. 2
0.36
1.09
0.97
3.50
0.43
0.32
•. _
_ —
0.51
1.28
2.56
0.31
0.13
3.78
4.29
1.38
1.19
1.66
0.43
1.68
0.33
1.38
0.33
0.36
3.09
2.85
0.46
0.53
0.56
2.63
0.75
1.40
0.47
0.66
210
-------
LANCASTER, CALIFORNIA
Sample I.D.
120
121
124
125
126
127
128
129
130
131
132
133
134
139
140
141
142
143
144
145
146
147
149
150
151
152
153
154
155
160
163
164
165
167
168
169
170
171
172
173
Feces-Lead Raw Data
(j.g/g wet weight
Sample No. 1
0.99
1.49
1.27
3.47
0.37
3.04
2.67
1.31
1.12
2.28
2.82
2.10
3.94
1.42
0.42
0.60
0.73
1.38
0.09
0.04
0.67
1.17
2.29
0.84
1.24
1.26
0.80
0.33
0.84
3.71
1.23
1.16
1.14
0.45
1.10
--
0.56
0.78
Sample No . 2
1.30
1.46
— *.
1.46
— —
3.45
0.58
0.94
1.07
1.42
1.30
1.58
1.79
0.54
— _
0.42
0.47
0.06
0.50
0.16
0.93
0.63
2.00
1.09
1.32
0.67
1.24
1.11
1.16
--
0.91
0.33
0.22
0.92
0.15
--
0.44
0.57
0.84
211
-------
LANCASTER, CALIFORNIA
Feces-Lead Raw Data
|jig/g wet weight
Sample I.D. Sample No. 1 Sample No. 2
174 0.40 1.03
175 0.20
450 0.20 0.00
451 1.04
452 1.10
453
454 0.45
455 -- 0.68
456
212
-------
LANCASTER, CALIFORNIA
Sample I.D.
001
OOZ
006
007
008
010
Oil
012
013
014
016
017
023
028
029
030
031
034
035
036
038
043
044
045
046
050
052
053
054
055
056
057
Hair-Lead Raw Data
Short Hair
2.71
2.95
13.64
13.59
10.37
<0.70
6.69
15.11
--
8.29
20.78
22.94
9.42
9.25
--
10.06
8.37
43.34 •
14.98
--
3.57
3.48
<0.70
7.98
11.69
5.80
8.14
4.93
5.03
--
—
41.39
--
43.51
--
16.27
Long Hair
14.91
13.05
3.90
9.83
2.77
—
20.05
9.07
11.43
3.39
1.75
—
23.60
4.48
13.35
12.16
7.61
16.12
--
7.76
7.12
—
14.78
13.35
2.61
4.01
44.40
42.78
14.38
98.76
121.48
9.08
12.87
213
-------
LANCASTER, CALIFORNIA
Sample I.D.
063
064
066
067
068
069
070
071
072
073
074
075
079
080
081
083
084
085
087
088
089
090
091
094
096
097
098
099
100
101
106
107
108
109
110
Hair-Lead Raw Data
f^g/g
Short Hair
4.00
14.33
14.10
27.01
7.20
14.34
7.88
3.78
4.51
13.08
13.36
2.21
1.76
—
5.78
7.51
--
2.83
4.88
4.10
16.47
12.92
1.12
__
24 . 93
20.39
24.58
26.75
—
--
--
--
5.83
4.20
9.48
5.09
7.11
—
Long Hair
10.27
15.79
29.08
6.21
<0.70
9.14
13.60
4.22
22.82
9.86
3.10
53.45
7.31
9.75
4.71
5.33
13.84
12.26
7.33
15.99
13.22
24.19
5.01
34.06
22.53
28.02
28.65
17.06
3.57
16.61
6.42
9.88
—
17.84
15.47
214
-------
LANCASTER, CALIFORNIA
Hair-Lead Raw Data
Sample I.D.
Ill
112
114
115
116
118
119
120
121
124
125
126
127
128
129
130
131
132
133
134
139
140
141
142
143
144
145
146
147
149
150
151
152
153
154
Short Hair
5.93
27.51
— _
12.28
4.23
19.51
24.14
—
47.85
56.41
16.32
19.88
—
—
45.80
2.54
--
46.79
19.87
7.40
22.67
40.57
9.78
942.00
764. 00
819. 00
--
7.92
13.45
—
22.23
10.31
10.76
Long Hair
5.99
39.61
2.70
-JQ.70
12.51
2.42
27.12
24.48
24.68
16.63
--
8.37
10.17
27.84
34.35
--
<0.70
4.81
0.94
<0.70
6.63
108.52
18.29
4.27
14.07
42.51
9.49
131. 35
3826. 80
312.07
8.59
6.46
15.45
28.25
25.58
3.91
3.33
215
-------
LANCASTER, CALIFORNIA
Sample I.D.
155
160
163
164
165
167
168
169
170
171
172
173
174
175
450
451
452
453
454
455
456
Hair-Lead Raw Data
Short Hair
20.89
11. 95
29.06
27.68
16.46
6. 90
--
16. 11
8.69
12. 67
11. 37
22. 59
--
20.20
--
--
14.01
31. 19
5. 96
9.31
Long Hair
50. 78
9.01
42. 65
14. 36
5.08
2. 67
3. 80
3. 71
33.49
—
8. 33
24.03
15.22
7.78
<0.70
11. 73
4660. 70
19. 14
16. 39
39.40
13. 50
7.94
10.24
216
-------
LANCASTER, CALIFORNIA
Sample I.D.
001
002
006
007
008
010
Oil
012
013
014
016
023
028
029
030
031
034
036
038
043
044
045
046
052
053
054
055
056
057
058
063
064
066
067
068
069
070
071
072
073
Urine-Lead Raw Data
M; A
Sample No. 1
17.0
7.4
46.8
1.3
20.0
2.5
20.4
5.3
12.8
1.4
5.9
8.5
11.5
9.2
4.1
10.0
6.0
8.3
14.0
20.0
18.5
13.5
3.6
19.5
4.7
9.7
8.8
6.6
5.7
2.3
4.1
6.0
1.4
5.6
11.3
12.5
21.3
Sample No . 2
9.1
12.7
8.5
28.9
5.6
8.8
27.3
2.1
6.3
<0.6
8.5
3.5
9.8
5.0
3.6
7.0
4.8
4.4
<0.6
5.2
10.1
--
4.4
14.0
1.6
<0.6
12.4
1.4
8.9
11.0
0.8
<0.6
<0.6
2.5
4.3
1.2
5.3
6.5
--
4.8
11.9
217
-------
LANCASTER, CALIFORNIA
Urine-Lead Raw Data
Sample I.D.
074
075
079
080
081
083
084
085
087
088
089
090
091
094
096
097
098
099
100
106
107
108
109
110
111
HZ
114
115
116
118
119
1ZO
121
124
125
126
127
128
129
130
131
132
133
134
Sample No. 1
9.5
0.8
14.4
6.8
5.8
20.7
9.0
7.0
9.7
19.4
32.4
9.7
5.9
22.1
26.5
_ __
6.6
10.4
12.4
2.3 .
4.8
19.9
5.7
11.0
13.1
13.8
6.3
6.8
16.7
3.0
10.4
7.0
<0.6
4.6
3.6
9.6
10.3
3.5
7.5
3.7
32.5
<0.6
30.5
6.5
218
Sample No . 2
7.3
2.9
11.5
2.0
19.7
9.9
12.1
<0.6
1.0
11.7
209.2
5.3
7.0
4.7
16.2
9.9
—
<0.6
8.7
37.2
7.8
<0.6
6.3
6.6
3.2
10.2
5.9
6.3
19.1
3.0
3.3
4.7
6.3
2.9
2.3
<0.6
3.3
11.0
16.4
11.2
0.8
2.3
9.1
<0.6
-------
LANCASTER, CALIFORNIA
Urine-Lead Raw Data
Sample No. 1
12.0
21.0
11.7
13.1
7.8
<0.6
27.7
9.2
17.3
6.8
31.5
33.5
2.7
4.7
11.6
7.7
12.9
11.0
<0.6
7.4
5.9
26.0
7.4
__
11.6
4.9
2.0
20.8
12.2
13.6
12.9
6.4
2.5
Sample No . 2
14.2
3.9
9.2
2.1
0.7
2.1
7.5
8.7
12.1
10.2
1.7
14.5
19.0
4.6
5.3
14.7
4.2
14.5
9.8
2.9
2.5
<0.6
9.3
5.5
8.2
9.3
3.2
1.7
<0.6
6.8
8.6
- -
—
_ _
Sample I.D.
139
140
141
142
143
144
145
146
147
149
150
151
152
153
154
155
160
163
164
165
167
168
169
170
171
172
173
174
175
451
452
453
454
455
456 7.0
450 12.3
060 -- 3.7
219
-------
APPENDIX D
THE LABELING CODE
220
-------
The Label Code (15 Characters)
lolumns
.-4
Variable
Format
Valid Codes
Human subjects 4N
identification number
Location code 4AN
Soil Location Code 4AN
Water Location Code 4AN
Sewage Location Code 4AN
Sample medium
IAN
Sample analysis
IAN
7-*
Site
2AN
Four digit ID number taken
from subject's question-
naire
Location of air or dust
samples
S is the first character;
columns 2-4 are sequential
numbers
W is the first character;
columns 2-4 are sequential
numbers.
R is the first character;
columns 2-4 are sequential
numbers.
A - Air sample
B - Blood Sample
D - Dust Sample
F - Feces Sample
H - Hair sample (out from scalp)
I - Inner Hair Sample
(close to scalp)
R - Raw sewage sample
S - Soil sample
T - Throat swab sample
U - Urine sample
W - Water sample
Z - Sputum sample
1 - Abdominal fat sample
(umbilical area)
2 - Psoas muscle sample
3 - Liver (right lobe)
4 - Pancreas (tail)
5 - Kidney cortex
(blank) - General (Collection)
A - antibodies
B - bacteria
H - mercury
M - trace metals
P - parasites
V - viruses
Site identifying code
CH - Chicago
LA - Los Angeles
LC - Lancaster, California
NJ - New Jersey
221
-------
Columns
Variable
Format
Valid Codes
10
11
Sampling period
Sampling sub-
subperiod (Air,
and dust samples)
12-15 Project number
IN
Sampling subperlod IN
(day) (Site samples)
or sample number
(human subject
samples)
IN
4N
1,2,3,4,5,6,7,8,9
(blank), 1,2,3,4,5,6,7,8,9
3881, 4005, 4007, etc.
222
-------
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223
-------
APPENDIX E
ANALYSIS VARIABLES IN LEAD
224
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/1-76-019
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
BASELINE LEVELS OF PLATINUM AMD PALLADIUM IN HUMAN
TISSUE
5. REPORT DATE
March 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Donald E. JoFinson, R, John Prevost, John B. Tillery,
David E. Camann and John H. Hosenfeld
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Southwest Research Institute
8500 Culebra Road
San Antonio, Texas 78284
10. PROGRAM ELEMENT NO.
1AA601
11. CONTRACT/GRANT NO.
68-02-1274
12. SPONSORING AGENCY NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research and Development
U.S. Environmental Protection aqency
Research Triangle Park. N.C. 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
EPA-ORD
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report presents the results of an epidemiological study of populations
living near a freeway in Los Angeles, California, and in the high desert region of
Lancaster, California, for concentrations of platinum, palladium, and lead in blood,
urine;, hair, feces, autopsy tissues, ambient air, surface water and soil. Platinum
and palladium are determined in samples from miners in Sudbury, Ontario, Canada, and
metal refinery workers in New Jersey.
Analytical methods are developed for platinum, palladium, and lead using
atomic absorption spectrophotometry.
The objective is to determine baseline levels of platinum and palladium in the
population and environment prior to wide-spread use of catalyst-equipped vehicles.
Lead is determined to ascertain the future epidemiological effect of non-leaded
gasoline.
Platinum and palladium concentrations were below the detection limit for Los
Angeles, Lancaster, and Sudbury samples. Refinery workers' urine and refinery air
samples has detectable concentrations of both metals.
Higher lead values were observed in Los Angeles samples taken near the San
Diego Freeway than in samples taken in the high desert area of Lancaster, California.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COS AT I field/Uroup
Platinum
Palladium
Lead
Bioassay
Air pollution
Water analysis
Soil analysis
Catalytic converters
06, F
8. DISTRIBUTION STATEMENT
RELEASE TO PUBLIC
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
252
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
237
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