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September 1975
Ecological 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 ECOLOGICAL RESEARCH series.
This series describes research on the effects of pollution on
humans, plant and animal species, and materials. Problems are
assessed for their long- and short-term influences. Investigations
include formation, transport, and pathway studies to determine the
fate of pollutants and their effects. This work provides the
technical basis for setting standards to minimize undesirable
changes in living organisms in the aquatic, terrestrial and
atmospheric environments.
This document is available to the public through the National
Technical Information Service, Springfield, Virginia 22161.
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EPA-600/3-75-010J
September 1975
ANNUAL CATALYST RESEARCH PROGRAM REPORT APPENDICES
Volume IX
by
Criteria and Special Studies Office
Health Effects Research Laboratory
Research Triangle Park, North Carolina 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF RESEARCH AND DEVELOPMENT
HEALTH EFFECTS RESEARCH LABORATORY
RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711
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CONTENTS
CATALYST RESEARCH PROGRAM ANNUAL REPORT
EXECUTIVE SUMMARY . .
INTRODUCTION
PROGRAM SUMMARY . . .
TECHNICAL CONCLUSIONS
DISCUSSION
REFERENCES
Page
1
5
7
17
22
45
APPENDICES TO CATALYST RESEARCH PROGRAM ANNUAL REPORT
VOLUME 1
A. OFFICE OF AIR AND WASTE MANAGEMENT
AT. AUTOMOTIVE SULFATE EMISSIONS
A2. GASOLINE DE-SULFURIZATION - SUMMARY. . .
A2.1 Control of Automotive Sulfate Emissions
through Fuel Modifications
A2.2 Production of Low-sulfur Gasoline • • •
1
53
55
90
VOLUME 2
B. OFFICE OF RESEARCH AND DEVELOPMENT
B1. FUEL SURVEILLANCE
B1.1 Fuel Surveillance and Analysis
B1.2 The EPA National Fuels Surveillance
Network. I. Trace Constituents in Gasoline
and Commercial Gasoline Fuel Additives .
B2. EMISSIONS CHARACTERIZATION
19
44
B2.1 Emissions Characterization Summary ....
B2.2 Sulfate Emissions from Catalyst- and Non-
catalyst-equipped Automobiles 45
B2.3 Status Report: Characterize Particulate
Emissions - Prototype Catalyst Cars .... 68
B2.4 Status Report: Characterize Particulate
Emissions from Production Catalyst Cars . . 132
B2.5 Status Report: Survey Gaseous and Particu-
late Emissions - California 1975 Model Year
Vehicles 133
B2.6 Status Report: Characterization and Meas-
urement of Regulated, Sulfate, and Particu-
late Emissions from In-use Catalyst Vehicles -
1975 National Standard 134
B2.7 Gaseous Emissions Associated with Gasoline
Additives - Reciprocating Engines. Progress
Reports and Draft Final Report - "Effect of
Gasoline Additives on Gaseous Emissions". - 135
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VOLUME 3
Page
B2.8 Characterization of Caseous Emissions from
Rotary Engines using Additive Fuel -
Progress Reports 220
B2.9 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Oxygen- and Sulfur-
containing Additives 232
B2.10 Status Report: Exploratory Investigation of
the Toxic and Carcinogenic Partial Combus-
tion Products from Various Nitrogen-
containing Additives 233
B2.11 Status Report: Characterize Diesel Gaseous
and Particulate Emissions with Paper "Light-
duty Diesel Exhaust Emissions" 234
B2.12 Status Report: Characterize Rotary Emissions
as a Function of Lubricant Composition and
Fuel/Lubricant Interaction 242
B2.13 Status Report: Characterize Particulate
Emissions - Alternate Power Systems (Rotary) • • 243
B.3 Emissions Measurement Methodology
B3.1 Emissions Measurement Methodology Summary. . . 1
B3.2 Status Report: Develop Methods for Total
Sulfur, Sulfate, and other Sulfur Compounds
in Particulate Emissions from Mobile Sources • • • 2
B3.3 Status Report: Adapt Methods for SO- and SO
to Mobile Source Emissions Measurements 3
B3.4 Evaluation of the Adaption to Mobile Source
SO_ and Sulfate Emission Measurements of
Stationary Source Manual Methods 4
83.5 Sulfate Method Comparison Study. CRC APRAC
Project CAPI-8-74 17
B3.6 Determination of Soluble Sulfates in CVS
Diluted Exhausts: An Automated Method 19
B3.7 Engine Room Dilution Tube Flow Characteristics. . 41
B3.8 An EPA Automobile Emissions Laboratory 52
B3.9 Status Report: Protocol to Characterize Caseous
Emissions as a Function of Fuel and Additive
Composition - Prototype Vehicles 89
B3.10 Status Report: Protocol to Characterize Particu-
late Emissions as a Function of Fuel and Additive
Composition 90
B3.11 Interim Report and Subsequent Progress Reports:
Development of a Methodology for Determination
of the Effects of Diesel Fuel and Fuel Additives
on Particulate Emissions 192
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Page
B3.12 Monthly Progress Report #7: Protocol to
Characterize Gaseous Emissions as a Function
of Fuel and Additive Composition 200
B3.13 Status Report: Validate Engine Dynomometer Test
Protocol for Control System Performance 218
B3.14 Fuel Additive Protocol Development 221
B3.15 Proposed EPA Protocol: Control System
Performance 231
VOLUME 4
B3.16 The Effect of Fuels and Fuel Additives on Mobile
Source Exhaust Particulate Emissions 1
VOLUME 5
B3.17 Development of Methodology to Determine the
Effect of Fuels and Fuel Additives on the Perform-
ance of Emission Control Devices 1
B3.18 Status of Mobile Source and Quality Assurance
Programs 260
VOLUME 6
B4. Toxicology
B4.1 Toxicology: Overview and Summary 1
B4.2 Sulfuric Acid Effect on Deposition of Radioactive
Aerosol in the Respiratory Tract of Guinea Pigs,
October 1974 38
B4.3 Sulfuric Acid Aerosol Effects on Clearance of
Streptococci from the Respiratory Tract of Mice.
July 1974 63
B4.4 Ammonium and Sulfate Ion Release of Histamine
from Lung Fragments 89
B4.5 Toxicity of Palladium, Platinum and their
Compounds 105
B4.6 Method Development and Subsequent Survey
Analysis of Experimental Rat Tissue for PT, Mn,
and Pb Content, March 1974 128
B4.7 Assessment of Fuel Additives Emissions Toxicity
via Selected Assays of Nucleic Acid and Protein
Synthesis 157
B4.8 Determination of No-effect Levels of Pt-group
Base Metal Compounds Using Mouse Infectivity
Model, August 1974 and November 1974 (2
quarterly reports) 220
B4.9 Status Report: "Exposure of Tissue Culture
Systems to Air Pollutants under Conditions
Simulating Physiologic States of Lung and
Conjunctiva" 239
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Page
B4.10 A Comparative Study of the Effect of Inhalation of
Platinum, Lead, and Other Base Metal Compounds
Utilizing the Pulmonary Macrophage as an Indicator
of Toxicity 256
B4.11 Status Report: "Compare Pulmonary Carcinogenesis
of Platinum Group Metal Compounds and Lead Com-
pounds in Association with Polynuclear Aromatics
Using |n_ vivo Hamster System 258
B4.12 Status Report: Methylation Chemistry of Platinum,
Palladium, Lead, and Manganese 263
VOLUME 7
B.5 Inhalation Toxicology
B5.1 Studies on Catalytic Components and Exhaust
Emissions 1
B.6 Meteorological Modelling
B6.1 Meteorological Modelling - Summary 149
B6.2 HIWAY: A Highway Air Pollution Model 151
B6.3 Line Source Modelling 209
B.7 Atmospheric Chemistry
B7.1 Status Report: A Development of Methodology to
Determine the Effects of Fuel and Additives on
Atmospheric Visibility 233
Monthly Progress Report: October 1974 255
B7.2 Status Report: Develop Laboratory Method for Collec-
tion and Analysis of Sulfuric Acid and Sulfates . • • 259
B7.3 Status Report: Develop Portable Device for Collection
of Sulfate and Sulfuric Acid 260
B7.4 Status Report: Personal Exposure Meters for
Suspended Sulfates 261
B7.5 Status Report: Smog Chamber Study of SO~
Photo-oxidation to SO^ under Roadway
Condition 262
B7.6 Status Report: Study of Scavenging of SO and
Sulfates by Surfaces near Roadways 263
B7.7 Status Report: Characterization of Roadside
Aerosols: St. Louis Roadway Sulfate Study .... 264
B7.8 Status Report: Characterization of Roadside
Aerosols: Los Angeles Roadway Sulfate Study . . . 269
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Page
VOLUME 8
B.8 Monitoring
B8.1 Los Angeles Catalyst Study. Background Pre-
liminary Report 1
B8.2 Lcs Angeles Catalyst Study; Summary of Back-
ground Period (June, July, August 1974) 13
B8.3 Los Angeles Catalyst Study Operations Manual
(June 1974, amended August 1974} 33
B8.4 Collection and Analysis of Airborne Suspended
Particulate Matter Respirable to Humans for
Sulfates and Polycyclic Organics (October 8, 1974) . . 194
VOLUME 9
B.9 Human Studies
1974
1
B9.1 Update of Health Effects of Sulfates, August 28,
B9.2 Development of Analytic Techniques to Measure
Human Exposure to Fuel Additives, March 1974
B9.3 Design of Procedures for Monitoring Platinum
and Palladium, April 1974
B9.4 Trace Metals in Occupational and Non-occupation
ally Exposed Individuals, April 1974
B9.5 Evaluation of Analytic Methods for Platinum and
Palladium 199
B9.6 Literature Search on the Use of Platinum and
Palladium 209
B9.7 Work Plan for Obtaining Baseline Levels of Pt
and Pd in Human Tissue 254
166
178
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Appendix B9.1
UPDATE OF
HEALTH EFFECTS OF SULFATES
August 28, 1974
Human Studies Laboratory
National Environmental Research Center
Environmental Protecton Agency
Research Triangle Park, North Carolina
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Studies of adverse health effects associated with exposure to air pollution
has been a continuing part of the CHESS program conducted by the Human Studies
Laboratory. A monograph "The Health Consequences of Sulfur Oxides: A Report
»
from CHESS" which summarizes the results of studies in New York City, Utah, and
the Chicago study areas and was published in June 1974. Since then, a second
series of individual research reports summarizing results from the eastern
United States and an additional year's effort in the New York metropolitan area
have been assembled in preliminary form and will be developed into the contents
of a second monograph, "The Health Consequences of Particulate Pollution". In
general, these studies confirm the adverse effects of air pollution reported in
the first monograph in that the incidence or prevalence of diseases are higher
in areas of highest pollution. Cigarette smoking is shown again to be a far
more significant form of pollution than are materials emitted into the atmosphere
by mobile or stationary sources. The data also indicate that lengths of
residence from 3 to 5 years apparently increase the probability that adverse
health effects will develop in a population and that there are significant
differences between the white and black races in the manner in which they
report adversities generally assumed to occur in conjunction with environmental
stresses.
*
The health parameters in the studies contained in the Particulate Monograph
are chronic respiratory disease, lower respiratory disease, pulmonary function,
acute respiratory disease, irritation of asthmatics, and irritation of symptoms
reported by the general population during an acute air pollution episode. In
each instance increased rates of adverse health status were associated with
• •
increases in the air pollution to which the population was exposed.
1
-------
The preliminary data suggest that total suspended particulate levels of
3 3 ''
about 100 yg/m in the presence of sulfur dioxide at levels about 100 yg/m
or less were not associated with significant increases in respiratory morbidity
in New York City. Other data indicated that in the southeastern United
3
States that total suspended particulate at levels lower than 70 yg/m annual
average in the presence of low levels of sulfur dioxide also were not strongly
associated with an elevated incidence of chronic bronchitis. Studies of
lower respiratory disease in New York City show that higher incidences were
associated with exposure to sulfur dioxide concentrations of approximately 50
3
to 425 yg, total suspended particulate concentrations of 60 to 185 yg/m , and
suspended sulfate concentrations ranging from 9 to 20 yg/m . In the southeastern
United States excess acute lower respiratory disease was associated with
3
annual mean levels of suspended particulate ranging from 103 to 168 yg/m
3
and suspended sulfate levels ranging from 10 to 13 yg/m , in the presence of
3
sulfur dioxide concentrations of less than 25 yg/m . In the low pollution
areas of the New York communities, respirable particulate amounted to approximate
70% of the total supsended particulates whereas in the Intermediate exposure
areas the respirable particulate amounted to between 54 and 70% of the total
suspended particulate matter. In the southeastern part of the country in the
low pollution area, respirable particulate amounted to nearly 53% of the
*
total suspended particulate and almost the same percentage of the total
suspended particulate consisted of fine particulate in the high exposure
»•
area. Pulmonary function studies in the southeastern area indicated that
reduced function was associated with higher pollution. Inter-area differences
in mean FEV0 75 as follows: Differences were greater in females than in
males, greater in whites than in blacks, and greater in younger than in older
• *
children. In the high pollution area, both older and younger children had
-------
received 50 to 70% higher lifetime doses of total suspended particulate than
had children in the low pollution area. In the low pollution area, RSP
levels fell about 20% from fall to winter and rose about 10% in the spring.
In the high pollution area, RSP levels fell about 10% from fall to winter and
rose about 25% in the spring. RSP levels in the high pollution areafor the
entire school year averaged 35% higher than those in the low pollution area.
A study of the incidence of acute respiratory disease in the south-
eastern United States suggested that small but consistent increases in illness
were associated with annual geometric mean levels of TSP ranging from 81 to
3 3
93 yg/m , or annual geometric mean levels of RSP ranging from 34 to 45 yg/m .
Additional pulmonary data are available from studies on the short-term
effects due to air pollutants. From the New York metropolitan area, there
was good evidence that effects of air pollutants upon the health of elderly
panelists appeared to have the strongest effects upon the well elderly but
similar health patterns were observed for the subjects with lung illness,
with heart illness, or with heart and lung illness. Best case threshold
3 3
estimates developed from preliminary analyses were 40 yg/m RSP, 75 yg/m
33 3
TSP, 4 yg/m suspended nitrates, 8 yg/m suspended sulfates, 60 yg/m S0?,
3
and 45 yg/m NO^- In the New York metropolitan area, studies demonstrated
increases in irritation symptom reporting for days designated as higher
pollution exposure, days when compared to a control period. However, no
pattern of response emerged in terms of relating specific irritation symptoms
to increases in any pollutant. The pollutants measured included total
suspended particulates, respirable particulates, the sulfate fraction of the
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participates, the nitrate fraction of the participates, and sulfur dioxide.
During the episode period, increases were variable from community to community
as was the pollutant exposure; but in most areas total suspended particulate
during the high pollution period, was 80 to 120% above that experienced during
the control period. This was equally true for the sulfate fraction of the
particulate matter.
While these data are preliminary and subject to revision, they do in
their present form suggest the general adequacy of the present primary air
q
quality standard for TSP (75 yg/m ) and indicate that a reasonable standard
for RSP, if it is determined that one is desirable, might be approximately 35
ng/m .
The Human Studies Laboratory has recently negotiated an option to the
CHAMP contract for the purpose of improving the monitoring of sulfate aerosols
in all CHESS areas by developing equipment and methods for measuring the
sulfate fraction of fine particulates. This same contractor under a separate
agreement also is to provide mobile field monitoring capability to permit
better characterization of actual human exposure to pollutants. Also, under
contract the Human Studies Laboratory will be gathering information on the
effects of catalytic converters on roadside pollution* levels and on the
levels of materials deposited in human tissues. Materials of greatest interest
will include lead and'noble metals. These studies are just now getting under
•-
way.
Completion of a human exposure chamber is anticipated in the forseeable
future. This facility will provide the Clinical Studies Branch of .the Human
Studies Laboratory with the capability of testing the effects of short-term
exposure to pollutants, singly or in combination, on both healthy and diseased
subjects. It is also anticipated that mobile laboratory facilities will be
n
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completed and delivered In the next few months. These facilities will permit
the assessment of the effects of air pollution in the general population
using the sophisticated equipment and techniques usually restricted to the
Clinical Laboratory. -Also, new epidemiologic studies will be initiated.
* —•
Some of these will be replications of prior studies; others will be new
» •
studies, but all will be designed to determine the relationship between
exposure to specific levels of air pollution and various acute or chronic
health status indicators. Indicators to be measured will include (a) prevalence
of CRO, (b) incidence of LRD, (c) chromosomal abnormalities, (d) aggravation
of symptoms in asthmatics, (e) pulmonary function.
Other studies to be initiated in the current fiscal year include (a)
validation of the self-administered CRD questionnaire, (b) estimation of
populations at risk, (c) biochemical or metabolic alterations associated with
exposure to NO,,.
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Appendix B9.2
DEVELOPMENT OF ANALYTIC TECHNIQUES TO
MEASURE HUMAN EXPOSURE TO FUEL ADDITIVES
FINAL REPORT
SwRI Project No. 01-3451-001
Contract No. 68-02-0595
Prepared for:
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
March 1, 1974
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I. OBJECTIVE
The principal objective of this investigation has been to develop
analytical and sampling methods to accurately measure human exposure
to fuel additives. An additional objective was to obtain some preliminary
information about the quantities of certain fuel additive residues in body
burdens of individuals exposed to relatively high concentrations of internal
engine exhaust emissions. Once the analytical and sampling methods were
perfected, then they could be utilized by the Environmental Protection
Agency to monitor human exposure to some of the more important and
commonly used fuel additives on a continuing basis. This will permit the
quantitation of the exposure to humans and provide the basis for prediction
of the expected effects of long term, low level exposures.
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II. INTRODUCTION
The Environmental Protection Agency has been charged with the
responsibility of measuring the exposure of humans to various air
pollutants and determining whether the amounts of these pollutants are a
potential hazard. They have the responsibility for setting acceptable
pollution levels and for enforcing the regulations to maintain levels below
the standards. This responsibility includes the residues resulting from
fuel additive components.
Fuel additives containing heavy metals are one of the more
important types of fuel additives currently in use in the United States. It
has been shown that trace metals may accumulate in various tissues and
possibly contribute to the incidence of carcinogenic, mutagenic and
teratogenic processes. Lead, manganese, copper, zinc, boron, calcium,
and silicon are all important trace element constituents in fuel additives .
There are other trace elements present as impurities, such as cadmium,
chromium, vanadium, nickel, and lithium. Many health officials consider
the optimum procedure for determing exposure to air pollutants to be via
measurement of body burden levels. This approach has been particularly
useful for monitoring heavy metals . The amounts of metal-containing
fuel additives used in the U.S. is large. The types of additives used may
vary, especially with the discontinuation of leaded gasolines.
-------
This project was designed to measure body burdens of five
heavy metals, namely cadmium, copper, lead, manganese and zinc.
Four substances (blood, urine, hair and feces) were selected to provide
data on the total body burden of these metals. Measurement of the metals
in blood and urine provides an indicator of total body burdens and will
also reflect short term exposure. Hair has been used as an indicator of
body burdens of the five metals and, in general, reflects a longer term
of exposure than do blood and urine. Feces measurements for lead and
cadmium were included to provide an estimation of the dietary contribution
to the total body burden of these two metals. It is known that 10% or less
of orrlly ingested lead and cadmium is absorbed, whereas 30% to 50% is
absorbed via inhalation. The project included three groups of individuals
exposed to relatively high concentrations of internal engine exhaust
emissions with each of the groups having its own matched control group.
Each of these six groups of individuals were to be sampled at four
separate times. Collection of blood, urine and feces samples was made
at specific times during the testing period, and hair samples were
collected over a four-month period at random times. The general plan
was to compare the body burdens of these metals in the individuals before
and after a weekend and before and after a vacation. This experiment
was designed to test the premise that short term changes in the levels of
the various pollutants in the environment would be reflected in changes in
the body burden levels of the metals. The design was also capable of
comparing body burdens of these compounds between each heavily exposed
9
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I
I group and its matched control group. For three of the metals - namely
!
; zinc, manganese and copper - an important aspect was to determine
whether or not body burdens could be related to environmental exposure
(primarily air). These three metals are present as normal biochemical
substances.
The exposed groups selected were (1) policemen working on foot
in downtown Houston, Texas , (Z) individuals working in covered garages
and (3) individuals living within two blocks of a major expressway in
metropolitan Houston. Each of these groups had a control group matched
for variables such as age, sex, smoking habits, education and ethnic
background. Other studies of this type have indicated that these variables
are important with regard to body burden levels of heavy metals. The
policemen and garage attendants were all male subjects; thus, the
individuals in the corresponding control groups were all male. Those
individuals living near a freeway and their controls were female.
Individuals between the ages of 18 and 53 were selected for study.
10
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1 .
III. EXPERIMENTAL
A. Design of Project
The program was designed to monitor six groups of individuals.
For convenience, these groups are labeled as follows:
Group 1 - Policemen
Group 1A - Control group for policemen
Group 2 - Garage attendants
Group 2A - Control group for garage attendants
Group 3 - Females living near freeway
Group 3A - Control group for females living near freeway
There were to be 36 people in each of the above groups, or a
total of 216 for the complete test. Each individual was to be sampled
four separate times for blood, urine, hair, andfeces. Measurements for
lead, cadmium, manganese, zinc and copper were to be made on all
samples of blood, urine and hair. On the feces samples, lead and
cadmium were to be measured. Hematocrits were to be run on all blood
samples; for all of the urine samples, specific gravities, total urine
volume, creatinine and coproporphyrin were to be measured.
The project was designed so that the first set of matched samples
were to be taken before and after a weekend. The second set of matched
samples (the third and fourth samples) were to be taken before and after
a vacation period. \
\
B. Selection of Experimental Subjects
Initial contact? with potential human volunteer subjects were
made using several approaches. For the policemen and their controls,
the initial contacts were coordinated with the director of personnel in
11
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charge of employees working for the City of Houston. During these
contacts, information was supplied regarding the objectives of the
i
program and by whom the program was supported, and detailed
information sheets concerning the overall program were given to the
personnel director. Permission was obtained to talk to potential
volunteers for the survey. Through this personnel office, appointments
V
were arranged with supervisory personnel for the police department
and for office employees in City Hall. The latter group was the source
of control subjects for the policemen.
The subjects for the women living near freeways and their controls
plus the controls for garage attendants were obtained through the
personnel offices of a large hospital in the Houston area and a medical
school. Permission to contact the subjects was obtained through the
personnel offices of these two organizations, and arrangements were made
to meet with potential volunteers as a group. Announcements were posted
on bulletin boards giving brief information about the survey and the time
and place of a meeting.
The garage attendants were contacted by visiting a number of the
covered parking garages, talking with the managers, and leaving information
sheets and instructions that there would be someone to visit the garage
within a day or so to talk to interested volunteers. Because of the limited
number of potential volunteers working in any one parking garage,
between 10 and 12 covered parking garages were contacted in the initial
12
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stages. In each of these initial contacts, the emphasis was to obtain
permission from the highest level necessary.followed by contacts with
the immediate supervisors and then the announcement of a meeting to
follow generally from 1 to 2 days to obtain information about the survey.
Initially, there was interest in obtaining the controls for the garage
attendants from large buildings in the downtown Houston area served by
a building custodian services group. A number of contacts were made
with these organizations, since for one of these buildings, several
hundred building custodians were employed daily. These contacts
resulted in none of the groups providing permission to talk with the
building custodians.
The initial contact with the potential human volunteer subjects
was in the form of a meeting to explain the general format of the survey,
to answer questions, and to pass out questionnaire forms to be filled out
by those interested in volunteering. A sample of the questionnaire form
used in the survey is presented in Appendix A. The questionnaire was
designed so that all information necessary for making a proper selection
was included. Some seventeen questions regarding the occupation, place
of residence, health, and personal statistics of the potential subject were
1
included.
i 13
-------
f
At the meetings, information sheets were distributed to those
interested, and any questions regarding the study were answered.
Those subjects who volunteered were told that questionnaires would be
examined and they would be notified via letter whether or not they had
been chosen for the survey. They were told at this initial meeting that
they would be paid $35 for the complete study - that is, to provide four
i
samples each of hair, blood, urine and feces. They were also told that
there would not be a partial payment of money for partial completion and
that they had to complete the full study in order to receive payment of
$35. Copies of the information sheets provided to the interested
volunteers are shown in Appendix B.
The response to the survey was excellent for the policemen and
their controls and for the females living near freeways and their controls;
however, the response of the parking garage attendants and of the building
custodians and attendants and orderlies in hospitals who served as controls
for the parking garage attendants was not nearly as good. To obtain a
sufficient sample for the parking garage attendants, a considerable
amount of effort was expended in contacts with covered garages in downtown
i
Houston to solicit volunteer participants .
The design goal was forty-five subjects from each group to allow
for selection between the various volunteers to match the exposed and
control groups with respect to age, sex, smoking habits, education, and
ethnic background. The exposed groups (groups 1, 2, and 3) were selected
-------
j first, and then the controls (1A, 2A and 3A) were matched as closely
as possible to the exposed groups with regard to the variables specified
above. For the parking garage attendants and their controls, there was
no surplus of volunteers, so the selection was minimal.
In the contacts with supervisors, managers, and other individuals
in charge of various groups contacted, it was emphasized that the
participation of their employees in the survey would not interfere with
their duties during working hours. The sampling was to be taken either
' at the beginning of their work day or at the end, and arrangements would
i
i
be made to meet the individuals and obtain samples in as rapid and
I efficient manner as possible. Only with these assurances was it possible
I
i to obtain permission to utilize these human subjects. The emphasis
I
throughout the survey was to bring the people who would take samples of
blood and collect urine and feces samples to the point where th.3
individuals were working. The alternate procedure, and one which would
have taken considerably less time and effort for the survey team, was to
provide a central location with the facilities for drawing blood, etc. and
have the human subjects travel to this spot. This was not followed
because of the probable poor response from potential volunteers and the
fact that the intent of the project was to sample at a specific time during
the week and during the day. The large number of subjects to be sampled
during the project and the fact that four different matched samples of
blood, urine, hair and fcces had to be taken required a much greater
degree of control than the central location would permit.
15
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The first sampling period was to coincide with a Friday and a
Monday to represent before and after a weekend. Letters were sent out
to the subjects selected for the study, indicating the time and place for a
meeting which was to be held on a Thursday, and the survey would
begin on the next day and a second sampling date on the following Monday.
A Houston telephone number was given for those subjects not able to .
attend the meetings. An alternate weekend was offered to these subjects.
When these meetings were held, the subjects were again informed of the
intent of the project and the details of the sampling schedule, and other
information was provided as needed.
On._e the subjects were fully informed about the program, those
that wanted to participate were requested to fill out and sign an informed
consent form. They were told that this was a requirement of the
Department of Health, Education and Welfare and were informed of the
purposes of this form. Each subject was given instruction sheets
specifying sample collection procedures, and each was given two containers
for collection of urine, two containers for fecal material and four plastic
bags for hair samples with four pre-addressed and postage paid envelopes
to be mailed to the SwRI laboratories.
A higher percentage of subjects dropped out of the program
(45 selected, 36 needed) than was expected. Some of the reasons given
were: loo little money for the amount of trouble involved; too much hair
required for each sample; and fear of the collection of blood samples. It
16
-------
is probable that the amount of money paid was marginal for the amount
of participation needed. Participation of many of the subjects was based
on the desire to assist in understanding the air pollution problems in
their area. For these subjects, the money paid was not the primary
inducement, but it was welcomed. For the garage attendants and their
controls, the money paid appeared to be one of the primary factors in
their participation in the survey.
The data contained in the questionnaire forms for the volunteer
participants were keypunched according to the format described in
Appendix A. The keypunched cards were sorted and listed for use in
selection matching between the exposure groups and respective control
groups of volunteer participants. For the analysis, ordered listings were
obtained regarding age, education, ethnic background, hair color, and
smoking habits of the volunteers.
An ordered listing of the Card 2 data (Card 2 contains the pertinent
parameters data obtained from the questionnaire forms) is presented in
Appendix C. This listing is ordered according to participant ID number
and contains data for all volunteers who were selected to participate and
who successfully fulfilled the sample collections. Table I presents in
summary form the data for the participants who volunteered for the project.
Table II shows these same data in schematic form. The principal
differences between'the control and exposed groups are in the policemen
and their controls. The controls are much better educated than the
policemen. The controls were selected from the male
17
-------
office staff in the City Hall of Houston, Texas, and many were engineers,
architects and other college graduates. The garage attendants are
slightly younger than their controls.
The Card 1 data containing names and addresses of the volunteer
participants are on file at Southwest Research Institute and will be
maintained, in confidence, for future reference if a justified requirement
arises in the future. The Card 1 data provide a direct correspondence
between the arbitrarily assigned ID numbers and the names and addresses
of specific volunteers.
As stated earlier, one of the objectives of this project was to
compare a group of people exposed to relatively high concentrations of
engine exhaust to a matched control group of people exposed to lesser
quantities of engine exhausts. From the data shown in Tables I and II, it
would appear that the groups were matched quite well for the variables
of interest. The control subjects all worked in the central part of
Houston, Texas. Each worked inside an air conditioned building. The
majority of these subjects lived within the Houston City limits (control
females lived more than 2 blocks from a freeway); thus, each was exposed
to higher concentrations of air pollutants than individuals that lived and
worked in a rural area. It is important to understand that these control
groups should have been exposed to lower concentrations of engine exhaust
fumes than the group of subjects they were matched with, but they do not
represent low exposure groups.
18
-------
C. Collection of Samples
As mentioned above, the first set of samples was taken on a
Friday and the following Monday. The second set of samples was
taken before the Christmas vacation (December 20, 1972) and after
Christmas vacation (January 2, 1973). A short meeting was held the
day before each sampling period to instruct the participants on how to
collect the samples and to pass out urine and feces containers for that
sampling period.
The urine samples were overnight specimens. The subjects
were instructed to begin collecting urine in the container provided
any time after supper (generally between 6 and 10PM) and to continue
collecting the total urine output until they reported to the sample
collection survey team, or SAM the next morning. Urine was collected
in wide-mouth polyethylene containers, one-half gallon size. The
polyethylene containers were washed thoroughly with deionized water
prior to their use on the project. Subjects were cautioned against putting
anything into these urine containers other than their urine. The
polyethylene containers for fecal samples were also washed with
deionized water, and the subjects were instructed to collect the fecal
sample anytime during the interval that the urine was collected that was
convenient for them . The subjects were instructed to bring the urine
and fecal samples with them at the time and place assigned for collection
of their blood sample k At that time, 20ml of whole blood was taken from
each individual using a B&D vacutainer, low lead content (0.5 microijrarru;
19
-------
or less) containing sodium "heparin as an anticoagulant. The collection
of blood samples was conducted by laboratory technicians under the
supervision of a physician. The blood samples were placed in styrofoam
boxes containing wet ice. The fecal samples were placed in styrofoam
containers with dry ice.
The policemen and their controls were sampled as they came on
duty (between 6 and 8 AM and 3 and 4 PM). The females living near
freeways and their controls plus the controls for the garage attendants
were sampled at the end of their work day (5 to 7 PM). The garage
attendants were sampled at different times during the day to
accommodate the different work shifts of the garage attendants. Generally,
this covered a. time period from 8 AM to 5 PM. Most of the garage
attendants worked shifts ranging from 4 to 8 hoars in length.
i
Four subjects from group 3 and four subjects from group 3A were
i
selected at random, and each was asked to collect samples of dust from
their vacuum cleaners and samples of tap water from their homes.
I
Once all samples had been collected for a particular day, they
were transported to the SwRI laboratories located in Houston. The blood
samples were processed for hematocrit determinations and to collect
blood plasma. A small amount of whole blood was needed for certain
analyses, and the remainder was used for preparation of plasma via
centrifugation. Once this had been conducted, the whole blood and blood
*
plasma samples were frozen. For the urine samples, the volume was
20
-------
determined, specific gravity measurements made, and then approxi-
mately a Z50-milliliter aliquot was put into a polyethylene container and
made to approximately 1% acetic acid and then frozen. The frozen
samples of urine, blood and feces were then transported to the San
Antonio laboratories and kept frozen until analyses were made.
The subjects were instructed to collect four separate hair
samples (at least 2 to 3 grams per sample) at their usual haircut or at
intervals of approximately one month during the testing period. It was
suggested that they could collect hair from their combs or brushes on a
daily basis to accumulate the required quantities of hair. The subjects
were cautioned against including hair from someone else. The subjects
were instructed to put the hair clippings into the plastic bags provided.
and then mail them to the SwRI laboratories. They were told that when
they had completed the sampling for four urines, four bloods, and four
feces and in addition had mailed in four samples of hair, their checks
for $35 would be mailed to them.
The principal problem in the collection of samples was one of
subjects forgetting to show up at the proper time and place or forgetting
to bring the proper samples. Every effort was made to accommodate the
subjects, including making visits to their homes to pick up their samples.
Collection of the samples from garage attendants located at some six
different locations was probably the most difficult part of the collection.
*
Because of the poor response to our survey request, there were small
21
-------
numbers of individuals located at each of these garages. The survey *
team had to make numerous stops to complete the sample collection
for this group. Although the decision to send the survey team to the *
individuals participating in the survey resulted in considerable effort, '.
I
it probably is the optimum procedure to obtain samples at the correct :
time and place from this number of individuals.
?
i
0. Methods of Analysis of Samples i :
1. Metal Analyses i
: - i
a. HAIR 1
Cadmium, Copper, Lead, Manganese and Zinc ;
Preparation of human scalp hair for analysis by atomic
absorption spectrophotometry'was based on the method of Hammer et al
(2)
and Harrison et al . The washing procedure was modified in that the
E.D.T.A. w«^sh was eliminated. All five metals were determined by
aspiration of the digested hair solution into an acetylene-air flame using
a single-slot burner head. Wavelength, slit setting, hollow cathode
(3)
current, and gas flow rates were set as suggested by the manufacturer.
I
A Deuterium Background Corrector was used with all metal determinations,
and for the zinc analysis a 1:40 dilution with deionized water was necessary.
b. BLOOD
Cadmium and Lead
Cadmium and lead analyses were carried out on whole
(4) (5)
blood using the procedure of PJdiger and Coleman . The "method of
additions" was used to establish a blood standard which was then used to
* A Perkin-Elmer 306 Atomic Absorption instrument was used
for the trace metal analyses.
22
-------
quantitate the unknown blood samples. A Deuterium Background
Corrector was used with both analyses.
Copper and Manganese I
Whole blood, diluted with deionized water 1:15 for copper
analysis and 1:1 for manganese analysis, was analyzed using a graphite-
furnace by the methods of Matousek and Stevens . A Deuterium
!
Background Corrector was used with both metals analyzed. Instrument
operating parameters were:
Copper:
Wavelength .... 324.7 nm Dry 30secatlOO°C
Slit 3.0mm Ash 40 sec at 800 °C
Source 15 mA Atomize ... 7 sec at 2500 °C
Damping No. 1 Gas • N2 at 20 Psi/N°-3 •5
Sample Volume. . 5 ul
Manganese:
Wavelength 279. 5 nm Dry 30 sec at 100 °C
Slit 1.0 mm Ash 70 sec at 600 °C
Source 16 mA Atomize ... .7 sec at 2400°C
Damping No. 1 Gas N^ at 20 psi/No.3.5
Sample Volume. . 10 pi
I
Zinc
Zinc was determined in a 1:40 dilution of plasma with deionized
water using the methods of Dawson and Walker and Sprague and Slavin
The diluted plasma was aspirated into an air-acetylene flame using the
instrumental operating parameters recommended by the manufacturer
A Deuterium Background Corrector was utilized.
23
-------
c. URINE
Cadmium
Cadmium in urine was analyzed by a modification of
(10) (11) (4)
the Hauser et al , Kahn and Sebestyen , and Ediger and Coleman
procedures. A lOOul aliquot of acidified urine was used in the Delves
cup procedure and analyzed using the instrument manufacturer's
recommended parameters . The Deuterium Background Corrector
was also used. Matrix effects were corrected for by using the "method
of additions" to establish a urine standard.
Copper, Lead, and Manganese
The graphite furnace was utilized in the analysis of
these three metals. The procedures used were patterned after those of
Amos et al and Davidson and Secrest . It was necessary to dilute
the urine 1:1 with dilute HC1 (0. IN) before analyzing for manganese.
The Deuterium Background Corrector was used on all three metal
determinations, as was the "method of addition", to establish a urine
standard. The following instrumental parameters were used:
Copper
Wavelength 324.7 nm Dry 30 sec at 100°C
Slit 3.0 mm A eh . . . . . . . 25 sec at 1000 °C
Source 16 mA Atomiy.c ... .7 sec at E500°C
Damping No. 1 Gao N^> at 20 psi/No.5
Sample Volume. 25>J. (grooved graphite tube)
Lead
Wavelength Z83.3nm Dry 30 sec at 100°C
Slit 1.0mm Ash 30 sec at 450°C
Source 8 mA Atomize ... 7 sec at 2100°C
Damping No. 1 Gas N-, at 20 psi/No.4
Sample Volume . 10(^1 (grooved graphite tube)
24
-------
Manganese
Wavelength 279.5 nm Dry 30 sec at 100°C
Slit 1.0 mm Ash 50 sec at 600°C
Source 16 mA Atomize .... 5 sec at 2" ^0°C
Damping No. 1 Gas N2 at 20 psi/No.4
Sample Volume. . 25|jl (grooved graphite tube
Zinc
Zinc in urine was determined by the method of Dawson
(8)
and Walker using the aspiration into an air-acetylene flame of a 1:1
dilution of the urine with deionized water. Instrument parameters are
those recommended for zinc analysis by the manufacturer . The
Deuterium Background Corrector was utilized, and the "method of
additions" used to establish a urine standard.
d. FECES
Cadmium and Lead
(13)
A wet-digestion procedure similar to that of Adrian
was used to digest the feces. Heavy-walled, 100-ml centrifuge bottles
were used to digest 5-gram samples of the feces. A perchloric acidinitric
acid solution 1:1 was used for the digestion. The acid digest was filtered
through a Reeves Angel, glass fiber filter and rinsed three times with 1%
UNO . The filtrate and rinses were collected in a 25-ml volumetric
flask and made to volume with deionized water prior to analysis.
Cadmium and lead were determined on the digested feces
utilizing the graphite furnace. The Deuterium Background Corrector was
used in both cadmium and lead analysis. The "method of addition" svc: .s
25
-------
used for both metal determinations to establish a feces standard to
calculate the concentration of the unknown samples. Instrument settings
were:
Cadmium
Wavelength.... 228.8 nm Dry 30 sec 100°C
Slit 1.0mm Ash 30 sec 300°C
Source 10 mA Atomize. ... 7 sec 1500° C
Damping No. 1 Gas N£ at 20 psi/No.4
Sample Volume. . 15ul (grooved graphite tube)
Lead
Wavelength 283.3 nm Dry 30 sec at 100°C
Slit 1.0 mm Ash 30 sec at 450°C
Source 8 mA Atomize 7 sec at 2100°C
Damping No. 1 Gas N? at 20 psi/No.4
Sample Volume. . 10|jl (grooved graphite tube)
e. PRECISION ACCURACY & RECOVERY STUDIES
Methods used to collect data on the precision and
recovery studies were performed under the same conditions (i.e. sample
preparation, dilutions, instrument operating parameters, etc.) that were
used to prepare and analyze the samples.
(1) Detection Limit
Detection limit is defined as that concentration of
metal which, under the given operating conditions, will produce a response
(signal) that is twice the average background noise (i.e. a signal-to-noise
ratio of 2:1). This value is calculated from the peak produced by a low
concentration spike sample.
26
-------
(2) Sensitivity
Sensitivity is defined as that concentration of
analyte which will give 1% absorption (Abs.). This value is also
calculated from the peak produced by a low concentration spike sample.
(3) Quality Controls
To overcome the matrix effect pf the samples, a
"sample standard" was made by spiking a given sample (e.g. blood, urine,
etc.) with several different concentrations of analyte. The "method of
additions" was used to determine the natural concentration of the metal of
interest in that "sample standard". This "sample standard" was then run
after every 5 to 10 samples as a quality control and as a means to obtain
a factor to calculate the metal concentrations in the unknown samples.
Periodically, this sample standard was made up fresh
and recalibrated with a frequency depending upon the rate of degradation
of the sample matrix. The concentration factor applied to the unknown
samples was calculated using the average values of the quality controls
which bracket those samples. This way, a continuous check was maintained
upon the analytical parameters.
(4) Blood
Two approaches were used in determining the precision
of the analytical methods for blood (and plasma). First, five to ten
individual blood samples (same blood) were spiked at a low and a high
concentration of the analyte. These samples were each analyzed 3 to 8 times
for each metal. Second, data from the quality controls actually analyzed
27
-------
with the samples were collected and used to calculate the precision.
Since both methods gave similar results, the data
/
from the quality control samples have been reported.
(a) Cadmium /
Analysis of six (6) unspiked bloods (quality
control samples) for cadmium by the Delve,s Cup technique gave a mean
concentration of 1.1 jig/lOOml blood, a standard deviation of jf 0.3 ug/lOOml
blood, and a relative standard deviation (RSD) of 25.7%. Analysis of seven (7)
spiked blood quality control samples (1. Oug/100ml) gave a mean concentration
of 1.3 jig/100 ml, a standard deviation of +_ 0.3 ug/100ml, and a RSD of 19.5%.
Using these operating parameters, the detection
limit is 0.38 ug/lOOml, and the sensitivity is 0. 02 jig/100 ml for 1% Abs.
(b) Copper
Ten (10) unspiked blood samples were analyzed
by the graphite furnace for copper. The mean concentration was
60 jig/100 ml, a standard deviation of + 3.5 (jig/lOOml, and a RSD of 5 .8%
Ten blood samples spiked (Cu) at 75 jig/lOOml gave a standard deviation of
+_ 5.4 (jLg/100ml and a RSD of 4.0%. The calculated detection limit for
this method is 3.5(j.g/100 ml, and the sensitivity is 0. 96 fag/100 ml for
1% Abs.
(c) Manganese
Unspiked blood samples (5) diluted with water,
(1:1), were analyzed for manganese by the graphite furnace technique. Mean
\
28
-------
concentration was 0 .7 jig/100 ml, standard deviation was ^ 0 .14 p.g/ 100 ml.
and RSD was ZO.0%. Ten spiked blood samples (1.5 jag/100ml) were also
analyzed for manganese. The standard deviation was +^ 0.12 fig/100 ml,
and the RSD was 5.5%. Detection limit is 0.16 ug/100 ml, and the
sensitivity is.0.05 ng/100 ml for 1% Abs.
(d) Lead
Lead analysis by the Delves Cup method on
nine (9) unspiked bloods (quality controls) gave a mean concentration of
17 fig/100 ml, a standard deviation of j- 3.7 fig/100 ml, and a RSD of 22.1%.
Nine (9) spiked bloods (25 jag/100 ml) analyzed for lead gave a standard
deviation of jf 9.2 fig/100 ml and a RSD of 22. 0%. Detection limit of the
Delves Cup technique is 4.8 fog/100 ml, and the sensitivity is 0.65 fig/100 m
for 1% Abs . i
i
i
(e) Zinc
Zinc was analyzed on ten (10) unspiked plasma
samples (quality controls) by aspirating the diluted (1:1) plasma into an
air-acetylene flame. The mean concentration was 93 fig/100 ml, the
standard deviation was +_ 2.3 (j.g/100 ml, and the RSD was 2.5%. Eight (8)
spiked plasmas (100 jig/100 ml) were analyzed for Zn by the same method.
The standard deviation was jf 9.6 ng/100 ml, and the RSD was 5.0%. The
detection limit is 9.8 |ag/100 ml, and the sensitivity is 1.8 |ag/400 ml
for 1% Abs.
29
-------
(5) Urine
Only the data from the quality control samples run
with the analysis of the urine samples were used to calculate the
i
precision of the urine analysis.
• (a) Cadmium
Ten (10) unspiked urine quality controls
analyzed by the Delves Cup technique were used for cadmium determinations.
The mean concentration was 1.0 jag/liter, a standard deviation was
+ 0.4 fig/1, and the RSD was 40.6%. Twelve spiked urines (lfig/1) gave
a standard deviation of + 0.5 fig/1 and a RSD of 26.1%. Calculated
detection limit for this method was 0.63 fig/I with a sensitivity of 0.02 fig/1
for 1% Abs .
(b) Copper
Unspiked urine quality controls (6) analyzed for
copper by the graphite furnace technique gave a mean concentration of
13.2 |JLg/l, a standard deviation of _+_ 1.1 fig/1, and a RSD of 8.4%. Quality
control urine (5) spiked at 10 fig/1 gave a standard deviation of + 3.5 fig/1
and a RSD of 15.0%. The detection limit is 1.1 fig/1, and the sensitivity
is 0.2 fig/I for l%Abs.
(c) Manganese
Manganese determined by the graphite furnace
•
in the unspiked urine quality controls (4) gave a mean concentration of
1.8 fig/1, a standard deviation of + 0.6 fJ.g/1 and a RSD of 35.6%. Ten
spiked quality controls (5|ig/]) gave a standard deviation of -f- 1 .2 fig/I and a
30
-------
RSD of 18-4%. Detection limit is 0.51 (ig/1, and the sensitivity is
0.14 fig/I for 1% Abs.
i
(d) Lead /
Unspiked urine quality controls (8) analyzed
for lead by the graphite furnace gave a mean of Z6jj.g/l, a standard
deviation of _+ 4.0 ng/1, and a RSD of 15.7%. Four spiked urine (100 ug/1)
f
quality controls gave a standard deviation of +_ 3.7 |ig/l and a RSD of 3.7%.
The detection limit is 4.6 ug/1 with a sensitivity of 1.3 ug/1 for 1% Abs.
(e) Zinc
Nine (9) unspiked urine quality controls were
used for the determination of zinc by flame technique. The mean
concentration was 13.2 ug/1, standard deviation was + 0.6 p.g/1 and the
RSD was 4.5%. Nine (9) spiked quality controls (50 ug/1) gave a standard
deviation of + 3.2 fig/1 and a RSD of 5.1%. Calculated detection limit of
this method is 2.3 ug/1, and sensitivity is 0.31 ug/1 for 1% Abs. r
I
!
(6) Hair 1
All hair analyses were done by the flame technique.
A large quantity of hair (approximately 30g) from one
individual was used in the precision and recovery study. A total of 45
spiked and unspiked hair samples and standards were analyzed using the
conditions previously stated for each analyte metal. Spikes were added to
the individual hair samples immediately after the digestion acids had been
added.
31
-------
" Recovery of analyte is based on 10 ml standard
solutions that have been spiked with the analyte metals at the same
concentrations as the spiked hair samples final volume (10 ml) should
be if all the metal were recovered.
Summary of the results is given below.
Sample
Cadmium
unspiked
spiked
(1.25 ug)
Copper
unspiked
spiked (5ug)
Manganese
unspiked
spiked (5ug)
Lead
unspiked
spiked (5ug)
Zinc
unspiked
spiked (10 fig)
n
5
5
5
3
5
5
5
5
5
5
mean
Mg/g
-
1.98
3.16
17.0
21.5
0.3
5.2
14.6
19.2
154.
164.
Std.Dev.
ug/g
+ 0.12
+ 0.13
+ 0.45
+ 0.25
+ 0.1
+_ 0.3
+ 0.52
+ 0.70
+ 6.5
± 5'7
Detection Sensitivit
RSD % Limit ug/g for
% Recovery ug/g l%Abs.
"5.8 — 0.31 J.05
4.0 80.0
2-6 •" 4.4 2.4
1.1 88.3
26'7 '•• 0.42 0.03
4.9 94.0 ,
|
3'6 0.40 0.03
3.6 97.5
i
4-2 — 3.2 2.2 '
3.5 100
(7) Feces
A homogenized fecep sample combined from several
samples was used in this study. Approximately 5 grams of the homogenized
*
feces were used per sample. A total of 47 spiked (0.25 to 10fig/g) and
unapiked samples were analyzed by the method given previously for feces
32
-------
analysis. Spikes were added immediately after the digestion acids had
been added to the feces. Recovery of the analyte is based upon the
comparison of the spiked feces with standards spiked at the appropriate
levels (i.e. spiked at the levels that would be found in the final volume
of the spiked feces samples if there were 100% recovery).
(a) Lead
, The unspiked feces samples (5) analyzed by
the graphite furnace technique for lead content gave a mean concentration
of 1.35 p.g/g, a standard deviation of _+ 0.01 ug/g, and a RSD of 0 .7%. Five
spiked feces samples (2.5 ug/g) analyzed for lead gave a mean concentration
of 2.8 ng/g, a standard deviation of + 0.6 ng/g, and a RSD of 22.9%.
Detection limit for lead by this method is 0.07 |ag/g with a sensitivity of
0.04 pg/g for 1% Abs. Lead recoveries in spiked feces samples ranged
from 94.8 to 103.1 %.
(b) Cadmium
Cadmium determination in unspiked feces
samples (5) gave a mean concentration of 0.55 fxg/g, a standard deviation
of-f 0.11 ng/g, and a RSD of 20.4%. Five (5) spiked feces samples
(0.25 |JLg/g) gave a mean of 0 . 8 ng/g, a standard deviation of H^ 0 .08 \iglg,
and a RSD of 10%. The calculated detection limit is 0.02 ng/g, and the
sensitivity is 0.01 |ag/g for 1% Abs. Recoveries ranged from 75.8 to
82.3%.
33
-------
(8) Summary
The methods of analysis used to measure the trace
metal content of blood, hair, urine, and feces were adequate (i.e.
R.S.D.<25%) except for (1) cadmium in blood and urine and (Z)
manganese in urine and hair.
The analytical methods used for each trace metal
determined were consistent with the state-of-the-art of that particular
atomic absorption spectrophotometric technique used. Improved
procedures are necessary, especially for cadmium in blood and urine.
2. Clinical Analyses
Specific Gravity - Urine
After all samples had been picked up from the subjects,
specific gravities were determined, usually at the end of the day, using
a urinometer.
, Total Volume - Urine
Urinary volume was measured at the same time as specific
gravity. Volume measurements were obtained by weighing the urine in
the sample bottle, subtracting the bottle weight and applying the specific
gravity factor. A 250-ml aliquot with 1% acetic acid was frozen and
*
shipped to the analytical laboratory.
34
-------
The capillary tube method was used to run hematocrits on
each blood sample. Convenience and blood collection times during the
day made it necessary to run the hematocrits at the end of the day.
Creatinine in Urine
Urinary creatinine was determined according to the method
described in Manual of Clinical Laboratory Procedures, Znd edition, 1970,
published by the Chemical Rubber Company.
Coproporphyrin in Urine
Urinary coproporphyrin was determined following the
procedure of Talman, E.L., "Porphyrins in Urine", in Standard
Methods of Clinical Analysis, vol. 2, D. Seligson, ed. (1958).
!
E. Results i
1. Clinical Data ;
The data from the subjects for hematocrits, coproporphyrin
creatinine, urine volume and urine specific gravity are in Appendix D.
The average hematocrits and standard deviation for the six groups ase
as follows: \
Standard Deviation
3.99,
i
\
2.93
3.92
3.41
\
3.24
2.32
35
Group 1
Group 1A
Group 2
Group 2A
Group 3
Group 3A
Average
45.2
45.6
46.7
43.4
39.7
39.7
-------
These Values appear to be normal for each group. There is a
statistically significant difference between Groups 2 and 2A which may
be due to the slight age difference between these two groups. The
median ages of the groups are shown in Table in.
E. Trace Element Data
The complete raw data from the analyses of hair, blood,
I
urine and fecal samples for the trace elements are included in Appendix D.
Copper, manganese, lead and cadmium are reported as ug/100 ml of
whole blood, while zinc values are jj.g/100 ml of blood plasma. Hair
values are listed as ug/g of washed hair. Urine values are in ug per
liter. Cadmium and lead in feces are listed as ug/g.
The data are compiled by groups and by tests. The code for
the groups are as follows:
Group 1 - Policemen
Group 1A - Control for Policemen
Group 2 - Garage Attendants I
Group 2A - Control for Garage Attendants I
Group 3 - Females near Freeways ',
Group 3A - Control for Females i
i
The four collections of samples are listed as tests i, 2, 3, and 4.
i
Blood, urine and fecal samples were taken at four specific times from !
the volunteers, and they are matched samples. Tests 1 and 2 were before
and after a weekend. This sampling period was in November of 1972.
Tests 3 and 4 represented before and after a vacation. These samples
were taken in late December, 1972 and early January, 1973 to cover the
Christmas holidays.
36
-------
Hair samples were collected by the individual volunteers
at random time intervals over a four-month period. The first sample
collected was Test 1,'the second Test 2, etc.
The data were examined statistically by use of a t test using
paired comparisons. These calculations produced the test statistic tc
which is based upon Student's t distribution:
s
where x is any random variable, p. is the true mean of the distribution of
x, and s is a sample standard deviation. For the test of the difference
between means of two groups, t is defined as
c
S-
x4 - x2
where
li^-DS,2* (n2-l, S22l
nl + n2 " 2
nl + n2
_nl ' n2 _
with
n . , the size of sample 1
n_ , the size of sample 2
S. , sample variance of sample 1
S , sample variance of sample 2
The presumptions are
1)
= 0
~ X
2) The populations from which the two samples
were drawn have equal variances.
. 37
-------
Then t within acceptable limits implies a mean of zero, which
implies
Comparisons were made between the groups (positive
versus control) for all tests and between the groups for each test. In
addition, comparisons were made within groups between Tests 1 and 2
and Tests 3 and 4. These statistical comparisons are considered the
minimum necessary to understand the significance of these data. It is
understood that the Environmental Protection Agency will conduct a
thorough statistical treatment of these data.
a.) Copper
The arithmetic means for copper levels in blood, urine
and hair for the six groups of subjects (all four tests combined) are shown
in Table IV. Along with the means are the standard deviations and
sample sizes. At the bottom of the table are shown the results of the
statistical analysis of this data. At a 95% confidence limit (p = .05),
there are significant differences between groups for blood and urine.
For policemen (1) and their control (1A), there is a negative correlation
\
in blood and a positive correlation in urine. For garage attendants (2)
and females living near freeways (3), there are positive correlations in
blood but no significant differences in urine or hair. From these data, it
£
s\>
is not clear whether or not the differences seen are related to exposure to
exhaust products. - \
38
-------
Although not examined statistically, there are larger
quantities of copper in females than males in blood, urine and hair. It
has been reported that females have higher levels of copper than males.
It has also been shown that oral contraceptives increase copper levels.
Table V shows the averages for each test for copper
in blood, urine and hair. These data were also examined using the t test
for differences between groups for each test and for differences within
groups between Tests i and 2 and Tests 3 and 4. The differences between
groups for each test were similar to the statistical data between groups
for all the tasts. There were few significant differences between Tests
1 and 2 and Tests 3 and 4. This is summarized in Table VI for blood and
urine samples. Similar comparisons with hair showed no significant
differences. There was no indication that copper levels were affected
by weekends away from work or short vacations.
b.) Manganese
Table VII shows the results obtained for manganese.
There are five significant differences between groups, but four of these
are negative (control group higher than exposure group). The large
standard deviation seen in group 3A hair is due in large part to relatively
high values for one individual. This was the only female Mexican-American
in the study.
Table VIII shows the averages for each test. Table IX
summarizes the statistically significant differences between Tests 1 and 2
and between Tests 3 and 4 for blood and urine samples. No significant
differences were seen in hair samples.
• 39
-------
c.) Zinc
• The results for zinc are shown in Table X. There
are only two significant differences - one positive and the other negative.
There are lower levels of zinc in blood and urine of females, while
higher levels are found in hair. It has been reported that oral contra-
ceptives lower zinc levels in blood and urine. The average values are
considered within normal ranges for females.
Table XI shows the average values for each test.
Statistical comparisons within groups produced the results in Table XII.
d.) Cadmium
A summary of the data for cadmium is shown in
Table XIII. The levels of cadmium are low in all specimens. These low
levels pushed the analytical methods to the limit of their effectiveness.
There are five significant differences at the 95% confidence limits, with
three of these positive and two negative. The differences between 3 and 3A
for blood would have been significant except for the large standard
deviations. This is also true for hair levels between 2 and 2A.
Table XIV shows the averages for each test. The
statistical comparison of groups test by test shows that the differences
between 1 and 1A and 2 and 2A in urine are consistent in all four tests.
Table XV summarizes the statistical comparisons within groups. No
significant differences were found with the hair samples. It is
possible that the levels of cadmium in urine are related to the exposure
to exhaust products.
40
-------
e.) Lead
Table XVI includes the comparison between groups
(all tests) for lead. There are significant differences for the male
volunteers (policemen-1 versus controls-lA and garage attendants-2
versus controls-2A) in blood and hair. There were slightly higher levels
(significant at 0.1 level) in females living near freeways -3 than their
controls - 3A in blood. In urine, there are significant differences
>
between groups 1 and 1A and 3 and 3A. In this same table are shown
data for urine coproporphyrin. There is a highly significant difference
between females living near a freeway and their controls (tc = 4.0351).
Table XVII shows the averages for each test. The
statistical comparisons between groups for each test are very similar
to the overall comparisons. Table XVIII summarizes the statistical
comparisons within groups. There were no statistical differences within
groups for hair or fecal samples.
f.) Water and Vacuum Cleaner Dust
Table XIX shows the results of analysis of water samples
from homes of individuals in Groups 3 and 3A and water samples from places
of work for Groups 1, 1A, 2A, 3 and 3A. The water from City Hall is
high in zinc; however, high zinc levels were not found in Group 1A.
\
Table XX shows the data for house dust of subjects
selected at random from Groups 3 and 3A. The data are similar for the two
groups. The lead levels are low (4.6-24.3 fJ-g/g) compared with data from
other studies of lead in household dust of urban areas (500-900(ig/g).
-------
LV. CONCLUSIONS
1. It has been demonstrated that it is possible to survey free
living populations for body burdens of trace metals and to relate these
body burdens to airborne exposures. In order to make these comparisons,
it is essential that the test group of subjects be well matched with a
control group for variables such as age, sex, hair color, smoking
habits, occupation, ethnic background, place of residence and socio-
economic status.
2. Good participation was achieved for four of the six groups of
subjects. For policemen and females living near freeways and their
controls, there were 180 subjects selected from those that volunteered,
and 144 completed the study (80%). Many of these subjects participated
because of a real interest in air pollution in their city. The participation
from garage attendants and their controls was not nearly as good. Over
300 potential volunteers were contacted, and fewer than 90 filled out a
questionnaire. Only 56 of these completed the study. It appeared that
the sum of money offered to these individuals ($35) was borderline for
the amount of participation required.
For future studies that include populations of the latter type, it is
recommended that the subjects be paid as much as $50 for their services.
This assumes that.the same extent of participation is required, i.e.,
four matched samples of blood, urine, feces and hair.
42
-------
3. Body burdens of copper, manganese and zinc were not
significantly elevated as a result of exposure to internal combustion
engine exhaust products. This study has provided a considerable Quantity
of base line data which can be utilized for comparison with data generated
in the future. When the quantities of lead fuel additives consumed are
substantially decreased, it is likely that the usage of other fuel additives
will be increased. Several of the candidate fuel additives contain these
t
three trace metals. Two hundred subjects, both male and female, have
been sampled four times for three different specimens for data on these
three metals. The test groups of subjects (policemen, garage attendants,
and females near freeways) were exposed to predominantly air pollution
from internal combustion engine exhaust products with a smaller portion
from industrial sources.
4. Levels of lead in blood and hair samples from male subjects
appear to be rather high in both test and control groups. In a previous
(1)
study by Hammer et al on school boys, there were listed five metal
exposure rankings according to their expected exposure. Their two
highest rankings were in lead smelting areas. The levels of lead of
subjects in these two areas were 20.9 and 15.6 jig/100 ml of blood
(arithmetic means). The lowest ranking level had 5.4 jj.g/100 ml of blood.
In this study, blood levels were 28 .3, 23.1, 21.3 and 18.4 |dg/100 ml of
blood for the male subjects exposed predominantly to airborne lead from
internal combustion engine exhaust products. The average age of the
-------
subjects in this study was between 25 and 30. It has been shown in
numerous studies that young children have higher lead levels than do
adults.
Hair levels for the school boys in the two highest exposure
rankings were 80.2 and 32.3 jig per gram of hair. For the study
reported here, the values were 47.6, 29.7, 23.5 and 13.1 ug/g of hair.
5. There are significant differences (95% confidence limits) between
policemen and their matched controls for lead in blood, urine and hair.
For the garage attendants and their controls, there are significant
differences for blood and hair. For females living near freeways, there
were higher levels than their control subjects for lead in blood, urine
and hair, although only urine was statistically significant at the 95%
confidence limit.
There were no significant differences for any of the test groups
versus their controls for lead in fecal samples. Measurement of fecal
lead provides an indicator for the relative amounts of lead consumed in
food or drink. Since there were very little differences for fecal lead
between groups, it is concluded that the differences seen in blood, urine
and hair reflect exposure to airborne lead. It is likely that the majority
of this arises from lead used as a fuel additive.
i
6. There are differences between males and females for levels of
lead in blood and hair. Males had blood lead levels between 28.3 and
18.4, while females were 12.9 and 11.9 fig/100 ml of whole blood.
Hair levels for males were 47.6 to 13.1 fig/g of ihair, and females hair
44 i
-------
values were 7.4 and 6.0. Lead in urine and feces were similar for
males and females.
The female subjects (both positive and control) worked in the
same buildings with the control subjects for the garage attendants.
From these data, it appears that females metabolize lead differently
than do males.
7. A part of this study was to find out if short periods of time
(1 to 9 days) away from work would alter body burdens of the five trace
metals. The preliminary statistical treatment of the data indicates that
the levels of the five trace metals were not changed as a result of a
weekend 01 a short vacation.
8. Cadmium levels in urine appeared to reflect exposure to airborne
cadmium for male subjects but not for females. The differences seen
in hair and blood of males did not vary with the expected exposure
gradient.
9. Future studies of the type reported here should include children
i
and perhaps elderly people.
-------
REFERENCES
(1) Hammer, D.I., F. Fink lea, R.H. Hendricks, T.A.Hinners,
W. B. Riggan and C. M. Shy, "Trace Metals in Human Hair as
a Simple Epidemiologic Monitor of Environmental Exposure",
Trace Substance in Environmental Health V, (1972). A
Symposium, D.D. Hamphill, ed., University of Missouri,
Columbia.
(2) Harrison, W.W., J. P. Vurachek and C. A. Benson, "The
Determination of Trace Elements in Human Hair by Atomic
Absorption Spectroscopy", Clinica Chimica Acta, 23(1969)83-91.
(3) "Analytical Methods for Atomic Absorption Spectrophotometry",
Perkin-Elmer Corp, March 1973, Norwalk, Conn.
(4) Ediger, R.D., and R . L. Coleman, "Determination of Cadmium
in Blood by a Delves Cup Technique", Atomic Absorption
Newsletter, Vol. 12, No. 1, (1973).
(5) Ediger, R.D. and R. L. Coleman, "A Modified Delves Cup Atomic
Absorption Procedure for the Determination of Lead in Blood",
Atomic Absorption Newsletter, Vol. 11, No. 2 (1972).
(6) Matousek, J.P. andB. J. Stevens, "Biological Application of
the Carbon Rod Atomizer in Atomic Absorption Spectroscopy, 1.
Preliminary Studies on Mg, Fe, Cu, Pb, and Zn in Blood and
Plasma", Clinical Chemistry, Vol. 17. No. 5 (1971).
(7) Amos, M.D., P.A. Bennett, K.G. Brodie, P.W.V. Lung and
J. P. Matousek, "Carbon Rod Atomizer in Atomic Absoprtion and
Fluorescence Spectrometry and its Clinical Applications",
f Analytical Chemistry, Vol. 43, No. 2 (1971)
| (8) Dawson, J.B. and B.E. Walker, "Direct Determination of Zinc
> in Whole Blood, Plasma and Urine by Atomic Absorption
I Spectroscopy", Clinica Chcmica Acta, 26 (1969) 465-475.
| \
1 (9) Sprague S. and W. Slavin, "Determination of Ion, Copper, and
Zinc in Blood Serum by an Atomic Absorption Method Requiring
Only Dilution", Atomic Absorption Newsletter, Vol. 4, 228 (1965).
(10) Hauser, T.R., T.A. Hinners.and J. L. Kent, "Atomic Absorption
Determination of Cadmium and Lead in Whole Blood by a Reagent-
Free Method", Analytical Chemistry, Vol. 44, No. 11 (1972).
46 ;
-------
(11) Kahn, H.L. andJ.S. Sebestyen, "The Determination of Lead
in Blood and Urine by Atomic Absorption Spectrophotometry,
with the Sampling Boat System", Atomic Absorption Newsletter,
Vol. 9. No. 2. (1970).
(12) Davidson, I.W.F. and W.L. Secrest, "Determination of Chromium
in Biological Materials by Atomic Absorption Spectrometry Using
A Graphite Furnace Atomizer", Analytical Chemistry, Vol. 44,
No. 11, (1972).
(13) Adrian, W. J., "A New Wet Digestion Method for Biological
Materials Utilising Pressure", Atomic Absorption Newsletter,
Vol. 10, No. 4 (1971).
-------
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-------
TASLE II. SCHEMATIC ANALYSIS OF PARTICIPANTS
Education I Ethnic [ Smoking | Jiair Color
18-26 27-35 36-
0-12 13-16 Peg
Non-
White White
Non-
Smoke Smoke
Brown Black Red Blonde \\hite
Group I/IA
1 h*1
n
n
•—11
Group n/IIA
"
n
i_
r-n
dL
Group III/IIIA
n
r-*
ULiln
rf
_•__ j_
Exposed G r o • jpi
f Control Group
""' ' ^ ""'~' _
49
-------
IH
TABLE m. MEDIAN AGE OF SUBJECTS
Group
1
1A
2
2A
3
3A
Median
31
30
25
30
26
25
jtange
20-46
* 19-53
18-45
22-50
18-47
21-32
50
-------
TABLE IV. COPPER
Grp.
1
1A
2
2A
3
3A
BLOOD fog/ 100ml
Std. Sam.
Mean* Dev. Size
63.1 19.69 139
74.8 14.06 153
66.9 17.34 119
57.8 18.01 98
9*6.3 31.06 118
74.1 20.81 134
URINE , jig /liter
Std . Sam .
Mean* Dev . Size
8.8 5.35 142
7.6 4.93 153
7.4 6.47 113
8.7 5.68 98
13.5 8.94 110
12.4 7.45 128
HAIR ,ig/g
.c+d . Sam
Mean* Dev . Size
12.5 6.34 136
14.1 7.98 153
12.8 8.62 72
14.7 7.89 99
32.0 24.75 104
27.4 28.30 126
*Arithmetic mean
Statistical Differences Between Groups (All Tests)
1 vs 1A
2 vs 2A
3 vs 3A
BLOOD
Sig.
p=.Q5
yes
yes
yes
tc
-5.8738
3.7841
6.7258
Sig
URINE
•
p=.05 tc
yes
no
no
2.0259
-1.4762
1.0134
Sig.
p=.05
no
no
no
HAIR
tc
-1.8748
-1.4581
1.2813
51
-------
Tes* . GROUPS
Blood
IJL g/lOOml
1
2
3
4
1
87.8
57.3
53.0
55.0
1A
78.6
74.9
71.3
74.5
2
74.4
75.3
60.0
'57.5
2A
51.8
47.8
47.1
83.9
. 3
96.2
103.0
101.1
84.1
. 3A
.4.6
69.3
75. 1
78.1
Urine .
Hg/liter
Hair
Hg/g
1
2
3
4
1
2
3
4
9.3
7.8
9.6
8.3
13.3
12.6
12.8
11.5
7.7
. 7.7
6.9
8.0
14.2
14.3
14.3
13.8
8.5
9.1
5.8
6.1 "
13.1
12.5
13.2
12.7
5.4
8.8
9.7
10.9
16.2
13.7
15.3
13.6
10.5
12.2
13.8
18.1
29.8
31.0
29.5
37.3
9 3
X • — /
11.9
13.9
15.4
30.2
26.5
25.2
27.8
52
r "**"*r^T TTIf"V»T'——'*—«f*—3s--\*-ic - w^-Tpjr-v_w .
-------
TABLE VI. COMPARISONS OF TESTS
WITHIN GROUPS - Copper
Blood
1
1A
2
2A
3
3A
Test 1 vs Test 2
significant p =. 05
yes
Test 3 vs Test 4
significant p = .Q5
-yes
yes
Urine
1
1A
2
2A
3
3A
-yes
53
-------
TABLE VIL MANGANESE
Grp.
1
1A
2
2A
3
3A
JDJ-iUV
Mean*
2.0
2.7
2.4
2.1
'2.1
2.4
JJLJ ng/ 100ml
Std. Sam.
Dev. Size
£
1.22 139
1.85 153
.97 117
.88 95
.77 117
.93 132
URINE jig /liter HAIR ue/e
Std.
Mean* Dev.
6.6 4.39
7.8 8 . 94
5.3 5.79
10.1 9.80
12.2 12.42
8.4 11.44
Sam.
Size
142
153
115
98
110
117
I +~f -
-------
TABLE VIII.MANGANESE
T«st GROUPS
Blood
fi g/100 ml
Urine
\i.g /liter
Hair
Jig/g
~
1
2
3
4
1
2
3
4
1
2
3
4
1
2.2
2.1
* 2.1
1.6
5.0
6.2
4.6
10.7
4.1
3.2
3.8
2.9
1A
3.1
. 2.8
2.6
2.6
12.6
10.3
3.2
5.3
2.9
2.7
2.8
3.3
2
2.1
2.5
2.2
2.7
5.7
4.4
.5.7
5.6
7.6
6.8
8.9
8.9
2A
2.7
2.1
2.0
1.7
5.0
9.3
14.4
11.7
6.5
7.9
7.3
8.5
. 3
2.1
1.8
2.0
2.4
14.0
9.4
8.8
17.1
3.6
2.8
3.4
3.8
. 3A
2.5
2.6
1.9
2.3
15.0
3.4
9.6
4.7
8.3
6.4
6.2
7.3
55
-------
1A. OUMKAKiSOINSi UJf TJbiSTb
WITHIN GROUPS - Manganese
Test 1 vs Test 2 Test 3 vs Test 4
Blood
significant p = .Q5 significant p = .Q5
1 * -- yes
1A
2
3
3A
1 -- , -yes
1A — , -yes
Urine 2
2A -yes
3 yes
3A yes yes
56
-------
TABLE X . ZINC
Grp.
1
1A
2
2A
3
3A
BLOOD jig/ 100ml
Std. Sam.
Mean* Dev. Size
/
339.9 51.26 141
306.5 45.99 153
317.5 70.92 117
309.9 59.61 98
254.3 49.73 116
251.4 66.06 132
URINE -p.g /liter
Std . Sam .
Mean* Dev . Size
305 186.8 141
308 186.1 154
449 251.4 109
218 131.8 96
167 112.6 112
177 106.7 125
HAIR ji.g/g
Std . Sam
Mean* Dev . Size
171.0 47.56 127
172.3 45.77 154
173.4 109.88 72
166.2 99.93 99
221.2 72.26 105
250.1 114.76 126
*Arithmetic mean
Statistical Differences Between Groups (All Tests)
1 vs 1A
2 vs 2A
3 vs 3A
Sig
BLOOD
p=.05 tc
yes
no
no
5.8747
.8411
.3850
URINE
Sig.
p=.05
no
yes -8
no
tc
.1108
.0978
.7280
HAIR
Sig.
p=.05
no
no
yes -2
tc
.2303
.4364
.2429
57
-------
test GROUPS
Blood *2
jig/100 ml 3
4
1
Urine 2
Hg /liter 3
4
1
Hair 2
Hg/g 3
4
1
354.4
369.7
316.8
317.8
1A
340.8
294.9
272.2
314.9
2
278.6
311.2
343.2
339.1
2A
329.7
299.4
308.1
304.1
3
280.7
234.3
236.1
265.5
. 3A
247.5
210.1
259.3
297.3
196.
220.
455.
358.
260.
332.
251.
392.
505.
496.
470.
304.
190.
181.
278.
223.
141.
180.
186.
163.
215.
172.
151.
164.
174.3
167.0
168.7
174.2
168.7
185.2
167.7
167.5
197.7
182.6
153.8
151.5
186.6
173.7
148.4
156.5
206.0
230.3
228.8
220.6
243.1
253.8
259.4
244.4
58
-------
TABLE XH. COMPARISONS OF TESTS
WITHIN GROUPS - Zinc
Test 1 vs Test 2
significant p =. 05
Test 3 vs Test 4
significant p =. 05
Blood
1
1A
2
2A
3
3A
>es
yes
yes
- yes
— yes
— yes
Urine
1
1A
2
2A
3
3A
— yes
yes
- yes
yes
59
-------
TABLE XHI.CADMIUM
Grp.
1
1A
2
2A
3
3A
BLOOD pg/lOOml URINE jig/
Std. Sam. Std.
M^ean5!- Dev. Size Mean- Dev.
.5 .67 139 1.4 l.OE
.7 .85 155 .6 .44
.5 .52 120 .8 .62
. .4 .44 98 .5 .22
7
.9 1.1 120 .6 - .61
.8 1.7 135 .6 .4C
*Arithm.etic mean
Grp.
1
1A
2
2A
3
3A
FECES ng/g
Std. Sam.
Mean* Dev. Size
.19 .07 141
.20 .11 130
.30 .21 93
.24 .13 98
.27 .16 105
.23 .13 124
liter HAIR \iglg
Sam. Std. Sam
Size Mean* Dev. Size
» 142 1.1 2.09 llc
1 155 1.1 2.02 15C
( 114 1.0 .97 71
\ 98 2.2 2.10 9*
r 110 .6 .41 IQi
) 117 .7 .55 11:
I
Statistical Differences Between Groups (All Tests)
BLOOD URINE
p=.05 tc p=.05 tc p=
1 vs 1A yes -2.7122 yes 8.7999 no
2 VE 2A yes 2.4093 yes 5.1880 ye
3 vs 3A no .8695 no - .1671 no
HAIR FECES
.05 tc p=.05 tc
.1073 no -1.0536
s -4.4842 yes 2.3505
-1.6070 yes 2.0704
60
-------
TABLE XIV.CADMIUM
Test GROUPS
1
Urine ' 2
fig/liter 3
4
1
Hair 2
Hg/g ?
4
1
Feces 2
3
4
1
1
.7
.6
.4
.4
2.5
1.2
1.1
1.0
1.1
1.0
1.3
1.1
. 17
. 18
.19
.21
1A
.6
.4
.4
1.6
.7
.5
.5
.9
1.1
1.1
1.0
1.1
.21
.22
.21
.16
2
.8
.8
.3
.3
1.1
.9
.8
.5"
0.9
1.0
1.0
1.2
.24
.23
.44
.27
2A
.5
.5
.2
.2
.5
.5
.5
.5
2.4
2.5
2.1
1.9
.23
.22
.27
.22
3
.9
1.0
. .9
.9
.3
.8
.5
.8
.6
.6
.6
.6
. 31
..23
.26
.26
. 3A
1.7
.7
.3
.2
.6
.8
.5
.6
.7
.6
.7
.7
.22
. 19
.27
.24
61
-------
TABLE XV. COMPARISONS OF TESTS
WITHIN GROUPS - Cadmium
Blood
Test ± vs Test 2
significant p = .Q5
1
1A
2
2A
3
3A
Test 3 vs Test 4
significant p = .Q5
-yes
yes
Urine
1
1A
2
2A
3
3A
yes
yes
-yes
-yes
yes
-yes
62
-------
Grp.
1
1A
2
2A
3
3A
BLOOD fig/ru Oml I
Std . Sam .
Mean* Dev. Size Me
23.1 9.21 141 24
18.4 7.38 150 19
28.3 10.33 119 26
21.3 9.70 95 27
12.9 4.47 120 32
11.9 4.28 117 19
*Arithm tic mean
Grp.
1
1A
2
2A
3 "
3A
FECES fig/g
Std . Sam .
Mean* Dev. Size
'2.5 2.87 141
2.3 2.72 125
2.4 1.68 92
2.2 2.44 96
2.9 2.18 105
2.7 3.94 123
JKIIMJi. jig /liter
Std. Sam.
;an* Dev. Size
.8 21.89 144
.0 19.64 160
.5 25.38 124
.8 19.80 100
.0 25.47 120
.5 21.25 144
1
HA1K Hg/g
Std . Sam
Mean* Dev. Size
23.5 38.61 13
13.1 15.92 14
47.6 46.42 7
29.7 29.62 10
7.4 10.61 10
6.0 5.51 12
URINE
Coproporphyrin fig /1 00 ml
Std . Sam .
Mean Dev. Size
3.1
3.5
3.8
3.1
3.0
2.0
\
2.55 144
L.56 160
4.22 124
2.61 100
2.41 128
1.54 144
\
Statistical Differences Between Groups (All Tests)
\
\
BLOOD URIN
1 vs 1A
p=.05 tc p=.05
yes 4.7726 yes 2
1 vs 2A yes 5.0098 no
> vs 3A no 1.8926 yes 4
E HAIR
tc p=.05 tc
.4464 yes 3.018
.4254 yes 3.082
.3452 no 1.275'
\
FECES
P-.05 tc
5 no .5648
3 no .4107
1 no .3474
63
-------
TABLE XVTL. LEAD
Teat GROUPS
1
Urine 2
fig/liter 3
4
1
Hair 2
3
4
1
Feces 2
3
4
1
25.0
26.1
17.3
23.7
.39.1
32.8
20.0 '
7.2
38.5
21.7
19.9
13.1
2.5
3.1
2.0
2.3
1A
18.3
22.6
17.6
15.1
20.6
18.1
21.6
15.5
16.0
12.9
11.2
12.3
2.6
2.1
2.4
2.0
2
29.6
31.3
25.8
26.4
11.9
37.0
28.7
28.2
52.7
47.2
50.8
38.3
2.3
1.8
2.4
3.1
2A
17.4
25.9
22.4
19.2
32.4
25.5
22.7
30.5
34.5
30.3
26.7
27.4
3.2
2.6
1.6
1.5
. 3
12.6
14.0
12.1
13.0
28.3
33.7
36.3
29.7
9.9
9.3
4.0
6.1
3.5
2.7
2.5
2.9
. 3A
M^-^Bi^^M
13.0
11.1
11.1
12.6
19.6
11.4
26.9
20.0
5.4
6.3
5.7
6.5
2.5
2.1
2.7
4.1
-------
TABLE XVra. COMPARISONS OF TESTS
WITHIN GROUPS - Lead
Test 1 vs Test 2 Test 3 vs Test 4
significant p= .05 significant p = . 05
1 - yes
1A - yes
2
Blood 0 A
2A - yes
3
3A
* - -- yes
1A
«"»• L :.yes ::
3
3 A yes
65
-------
TABLE XIX. WATER ANALYSIS
concentration in fjg/liter
Sample Identification Cd Cu Mn Pb Zn
Group 3 (Homes)
No.
No.
No.
No.
No.
1
2
3
4
5
a.
1.
0.
0.
0.
4
1
3
3
6
6
74
58
0
22
1.
10.
5.
6.
0.
4
3
5
8
8
0
2.5
0
0
0.1
72
48
36
462
0
0.6
0.3
0.4
0.2
0.4
11
12
6
7
4
0.7
2.2
5.3
12.7
0.8
0
0
0.6
0.7
0
189
144
243
513
674
Average , 0.5 44 5.0 0.5 124
Group 3A (Homes)
No. 1
No. 2
No. 3
No. 4
No. 5
Average 0.4 8 4.3 0.7 353
Group 1
Police Station 0.2 360 9.0 0 164
Group 1A
City Hall 0.5 85 8.3 0.2 1113
Groups 2A, 3, 3A
Baylor Col. of Med. 0.7 92 8.9 2.8 738
Methodist Hosp. 0.4 88 5.1 7.6 328
66
-------
0.5
0.4
0.3
3.1
9.3
5.9
4.7
7.3
5.8
6.3
Z0.6
4.9
16. Z
5Z.1
17. Z
TABLE XX. DUST ANALYSIS
Concentration in jig/gram
Sample Identification Cd Cu Mn Pb Zn
Group 3 (Homes)
No. 1
No. Z
No. 3
Average 0.4 6.1 5.9 10.6 Z8.5
Group 3A (Homes
No.l Z.7 9.7 5.9 Z4.3 Z0.7
No. Z
No. 3
No. 4
No. 5
No. 6
Average 0.8 5.Z 5.0 11.3 Z9.1
0.3
0.6
0.4
0.5
0.3
4.3
6.Z
5.0
Z.8
3.3
9.8
3.1
Z.9
5.4
3.0
4.6
10.4
9.8
9.0
9.4
14.6
61.8
Z5.3
Z3.8
Z8.7
67
-------
The questionnaire form used during the study to obtain information
for selecting participants among those volunteering their services is
presented in this Appendix. The form was designed to obtain the necessary
information regarding address, occupation, health status, and personal
statistics from each potential participant so that proper selection could
be made. The form was designed for keypunching into two keypunch cards.
Card 1 contains name and address data and Card 2 the occupation,
health, and personal data required for the selection criteria employed.
The numbers in parenthesis throughout the questionnaire form are the
keypunch coding. Information obtained from the respective questions
were punched in the columns specified in parenthesis in either Card 1
or Card 2, as indicated. A unique three-digit identification number was
assigned to each potential volunteer for which a questionnaire was
obtained, and the questionnaire form was labeled with this number.
The unique ID number was keypunched into all data cards related to
the volunteer subject and was used throughout all sampling procedures
to label samples and results from a specific volunteer.
Specific instructions regarding keypunching the questionnaire form
are given in the final three pages of this Appendix.
69
-------
FORM APPROVED
By: Environmental
CARD 1 (1) Protection Agency
I.D.
(2 - 4)
EXPOSURE TO FUEL, ADDITIVES
QUESTIONNAIRE
NAME:
(5 - 24)
ADDRESS:
Street (25 - 44) City (45 - 59) Zip (60 - 64)
TELEPHONE:
(65 - 71)
Please write on the lines above -
your full name, street address, city,
Zip Code and telephone number (ex-
clude Area Code).
The information requested in this
questionnaire will be held in strict
confidence.
70 P. E.G. 1 2 3 (72)
-------
I.D. #
(2 -
1.
What is your present occupation?
(5 - 6)
2. Do you currently have a second full-time or part-time occupation
in which you are frequently exposed to irritating smoke, dust, or
fume s ?
(7)
1.
2.
Yes
No
2a.
IF YOU ANSWERED "NO" TO QUESTION "2", SKIP THE NEXT
THREE-QUESTIONS BELOW.
If the answer to question 2 is "Yes, " what kind of irritant are you
exposed to? (For example: auto exhaust fumes, coal dust, cutting
oils, smelter fumes, raw cotton dust. )
(8 - 9)
2b. If the answer to question 2 is "Yes, " what kind of work do you
perform in this job? (For example: maintenance, assembly line,
supervisor. )
(10 - 1
2c.
3.
If the answer to question 2 is "Yes, " how long have you been ex-
posed to the irritant stated? (12)
1. Less than one year ,
2. One to five years
3. Six to ten years i
4. More than ten years '•
\
Have you ever smoked as many as five packs of cigarettes, that is,
as many as 100 cigarettes during your entire life? (13)
1.
2.
Yes
No
71
-------
Do you now smoke cigarettes?
1.
2.
Yes
No
If you are a current or an ex-cigarette smoker, how many cigarettes
do (did) you smoke per day?
1. Less than 1/2 pack per day (1-5 cigarettes per day)
2. About 1/2 pack per day (6 - 14 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)
If you are a current or an ex-cigarette smoker, how old were you
when you first started smoking?
Years
If you are an ex-cigarette smoker, how old were you when you last
gave up smoking?
Years
What is your marital status?
1.
2.
3.
4.
5.
Single
Married
Separated
Divorced
Widowed
What educational level has been completed by the head of the
household?
1. Elementary School
2. Part of High School
3. High School Graduate
4. Trade, Technical or Business School Beyond High School
5. Part of College
6. College Graduate
7. Graduate School Including Advance and Professional
Degrees
72
(14)
(15)
(16 - 17)
(18 - 19}
(20)
(21)
-------
10.
11.
12.
How long have you lived in your present city or town? (Check
one answer only)
1. Less than one year
2. One year
3. Two years
4. Three years
5. Four years
6. Five years
7. Six years
8. Seven years
9. Eight years
10. Nine years
11. Ten years
12. Eleven years
13. Twelve years or more
What was your age in years on your last birthday?
Years
(22 - 23
What is your sex?
(24 - 25
(26)
1.
2.
Male
Female
13.
What is the natural color of your hair?
(27)
1.
2.
3.
4.
5.
6.
Brown
Black
Red
Blond
Gray
White
14. Have you ever had any of the lung related problems listed below?
(Indicate all that apply).
1. Asthma
2. Emphysema
3. Tuberculosis
4. Histoplasmosis
5. Bronchiectasis
(28)
73
-------
15. Have you ever had a .thyroid problem?
(29)
1.
2.
Yes
No
16. Do you live within two blocks of a freeway?
(31)
1.
2.
Yes
No
17.
1.
2.
3.
4.
YOU HAVE FINISHED THE QUESTIONNAIRE
THANK YOU
DO NOT MARK BELOW THIS LINE
(32)
74
-------
Item
Card*
ID#
Name
Address
Telephone
CARD #1
Columns
2-4
5-8
9-24
25-64
j
65-71
Comments
The number 1 is punched
in the column
Three Digit Number Assigned
Initials
Last Name
As Shown
As Shown
75
-------
Item
Card #
ID*
Ql -Occupation
QZ-Other Emp.
Q2a-Irritants
Q2b-Duties
Q2c-How Long
Q3-Have Smoked
Q4-Do Smoke
Q5-How Many
Q6-When Started
Q7-V/hon Quit
CARD ?2
Column
1
2-4
5-6
7
8-9
10-11
12
13
14
15
16-17
18-19
Comments
The number 2 is punched in
this column
(The same as Card Hi)
1 - Policeman
2 - Attendant
3 - Custodian
4 - Orderly
5 - Clerk/Secretary
6 - Hospital Technician or
Nurse
7 - Police Control Group
9 - Other
As Shown
1 - Auto Exhaust
2 - Coal Dust
3 - Cutting Oils
4 - Smelter Fumes
5 - Raw Cotton Cust
6 - Cigarette/Cigar Smoke
7 - Other
1 - Guard
2 - Maintenance
3 - Assembly Line
4 - Supervisor
5 - Waitress
6 - Sales
7 - Secretary
8 - Other
As Shown
i
As Shown
As Shown
As Shown
As Shown
As Shown
76
-------
I
—QS- Married
Q9-Education
Q10-Length Lived in Town
Qll-Age
QlZ-Sex
Q13-Color of Hair
Ql4-Lung Problems
Q15-Thyroid
Q16-Live Near Fwy
Q17-Ethnic
Location Code
Group Identification
20
21
22-23
24-25
26
27
28
*
29
31
32
35
79-80
As Shown
As Shown
i
As Shown
As Shown
As Shown
As Shown
As Shown (6 is key-punched
for any multiple problem)
As Shown
As Shown
1 - White
2 - Negro
3 - Mexican-American
4 - Other
0 - Baylor College of Medicine
1 - Travis Garage
2 - HNG Garage
!,3 - Ten-Ten Garage
4 - 1st City Nat. Bk Garage
5 - Texas Nat. Bk of Commerc
Garage
6 - Texas Medical Ctr Garage
7 - Houston PD
8 - Houston Civic Center
9 - Methodist Hospital
i
1/1A - Police/Police Control
2/2A - Garage/Garage Control
3/3A - Females/Females
Control
77
V*»ir,T«
-------
STUDY TO MEASURE HUMAN EXPOSURE TO FUEL ADDITIVES
FOR The Environmental Protection Agency
BY Southwest Research Institute
AT Houston, Texas '
Southwest Research Institute is conducting a study for the
Environmental Protection Agency (EPA Contract No. 68-02-0595) to
measure human exposure to fuel additives. The design of this study
: is that certain trace metals will be measured in hair, blood and urine
samples from people ordinarily exposed to relatively high levels of engine
exhaust fumes and in individuals with lesser exposure to these pollutants.
To conduct this study, some two hundred and forty volunteer
participants are needed. The following types of volunteers will be
selected: ,
I
Policemen and City Office Staff ,
;
40 Daytime Shift, outside work, regular exposure to
auto exhaust fumes <
40 Any shift, indoors, away from regular exposure to
auto exhaust fumes j
i
Housewives, Nurses, Female Office Staff, Female Building Custodians
- . " . 40 Living near (within two blocks) a freeway
40 Not living near a freeway
Male Garage Attendants
40 Working in area of covered auto garage
Male Building Custodians
40 Working away from regular exposure to auto exhaust fumes
79
-------
The information obtained will assist the Environmental Protection Agency
to assess the types and quantity of pollutants to which populations which
make large use of freeways are exposed. This type of data is essential
to insure that the air we and our children breathe is safe. Each parti-
cipant will be informed of the results of the project when it is completed.
Samples will be collected four times during the project (4-6
months) for each of the three types: scalp hair, blood and urine. Samples
will be taken after a work day, after a non-work day and before and after
a vacation. A small amount of the participants' hair clippings will be
saved at the time of normal hair cut. Participants will be given sample
containers which can be mailed to us. The night before giving a blood
sample the participants will collect ail urine (in a contained supplied by
us) beginning after supper (6-8 PM) and continuing until the next morning
when a blood sample will be given (8-10 AM). Twenty milliliters of
blood will be taken by a nurse and under a physicians supervision. All
aspects of these experiments involving human subjects will be conducted
in accordance with the PHS Surgeon General's issuance, "Protection of
the Individual as a Research Subject" dated May 1, 1969. Each participant
will be paid $25 for the complete study - that is, four samples of blood,
urine and hair clippings.
INFORMATION REGARDING SOUTHWEST RESEARCH ;
INSTITUTE :
i
Southwest Research Institute is a public service organization devoted
to applied research and franchised under the laws of the State of Texas
as a not-for-profit corporation. A staff of 1150 persons at facilities
in San Antonio, Houston, and Corpus Christi, Texas, Bloomfield, >
Connecticut, and Washington, D. C. , provide a broad spectrum of
highly competent personnel with professional, technical, and administrative
training. The research activities of this institute include investigations
into virtually all areas of physical, engineering, behavioral, or social
sciences.
REFERENCES
Mr. George W. Bichsel, Associate City Manager, City of San Antonio, Texas
Mr. Robert J. MacDonald, Director of Intergovernmental Services,
City of San Antonio, Texas
80
-------
SCHEDULE OF ACTIVITIES
STUDY TO MEASURE HUMAN EXPOSURE TO FUEL ADDITIVES
1. Initial Meeting with Employers
Employer Permission
Information Regarding Access to Bulletin Board,
Auditorium, etc.
2. Advertisement of Study to Potential Participants
Bulletin Boards
Handouts
Employer Announcement
3. Meeting with Potential Participants to Fill Out Questionnaires
Information Regarding Study
Fill out Questionnaires
4, Selection of Participants
5. Initial Gathering of Samples Before and After a Work Day
(Near Place of Work)
6. Gathering of Samples Before and After Vacation (At South-west
Research Institute Office, 3600 S. Yoakum Blvd. , Houston,
Texas 77006, Phone: 713-522-0726
7. Payment of 25 dollars to each participant completing study.
MAJOR STUDY POINTS
240 Volunteer Participants
4 Collections of Blood, Urine, Hair Clippings
No Interference with Normal Work Activities
$25 to Each Participant
81
-------
EVERYONE TALKS ABOUT PQLL.U 1
HERE'S YOUR CHANCE TO HELP DO SOMETHING ABOUT IT
NEED 80 MALE VOLUNTEERS FOR A RESEARCH STUDY
HOUSTON PD - 40 DAYTIME SHIFT OUTDOORS (ON FOOT OR 3 WHEEL VEH. )
PASADENA PD - 40 ANY SHIFT INDOORS OR IN PATROL CARS
Southwest Research Institute is conducting a study for the
Environmental Protection Agency (EPA Contract No. 68-02-0595) to
evaluate human exposure to fuel additives. The study will involve
the measurement of certain metals in hair, blood and urine of subjects
who in their normal course of work are exposed to exhaust fumes from
internal combustion engines.
We need your assistance in contacting potential volunteers.
The participation of these individuals in this study \vill net interfere
with their jobs. We need male policemen between the ages of 18 and
45 who work a daytime shift outside. They should work primarily
within the downttrvn Houston Area. At least 40 volunteers will be
needed for this group. A control group of policemen (same age group)
of at least 40 will also be required. These volunteers should have jobs
that require them to spend most of their time indoors or in patrol cars.
The control subjects will be from the Pasadena P. D.
Urine, blood and hair samples will be collected from each
subject four times during the study. The subjects will be paid $25
for their services. Collection of samples will be under the supervision
of a physician and the collections will be made outside of working hours.
Information covering all aspects of the project will be supplied to the
subjects. All aspects of these studies involving human volunteer subjects
will be conducted in accordance with the PHS Surgeon General's issuance,
"Protection of the Individual as a Research Subject", dated May 1, 1969-
EARN AN EXTRA $25
COMPLETE INFORMATION REGARDING THIS PROGRAM WILL BE GIVEN OUT
Where: Roll Call Area
*
When: 30 minutes preceding morning and afternoon roll call, Tuesday,
October 17, 1972.
82
-------
, MALE OFFICE STAFF
EVERYONE TALKS ABOUT POLLUTION
HERE'S YOUR CHANCE TO HELP DO SOMETHING ABOUT IT
NEED 40 MALE VOLUNTEERS FOR A RESEARCH STUDY
Work Inside
Any Shift
Southwest Research Institute is conducting a study for the
Environmental Protection Agency (EPA Contract No. 68-02-0595) to
evaluate human exposure to fuel additives. The study will involve
the measurement of certain metals in hair, blood and urine of subjects
who in their normal course of work are exposed to exhaust fumes from
internal combustion engines.
We need your assistance in contacting potential volunteers.
The participation of these individuals in this study will not interfere
with their jobs. We need male office staff between the ages of 18 and
45 who are employed by the City of Houston. These volunteers should
have jobs that require them to spend most of their time indoors away
from auto emissions.
Urine, blood and hair samples will be collected from each
subject four times during the study. The subjects will be paid $25
for their services. Collection of samples will be under the supervision
of a physician and the collections will be made outside of working hours.
Information covering all aspects of the project will be supplied to the
subjects. All aspects of these studies involving human volunteer subjects
will be conducted in accordance with the PHS Surgeon General1 s issuance,
"Protection of the Individual as a Research Subject", dated May 1, 1969.
EARN AN EXTRA $25
COMPLETE INFORMATION REGARDING THIS PROGRAM WILL BE GIVEN OUT
83
-------
GARAGE ATTENDANTS
EVERYONE TALKS ABOUT POLLUTION
HERE'S YOUR CHANCE TO HELP DO SOMETHING ABOUT IT
NEED 40 MALE VOLUNTEERS FOR A RESEARCH STUDY
Southwest Research Institute is conducting a study for the
Environmental Protection Agency (EPA Contract No. 68-02-0595)
to evaluate human exposure to fuel additives. The study will involve
the measurement of certain metals in hair, blood and urine of subjects
who in their normal course of work are exposed to exhaust fumes from
internal combustion engines.
We need your assistance in contacting potential volunteers.
The participation of these individuals in this study will not interfere
with their jobs. We need males between the ages of 18 and 45 who
work primarily within a covered parking lot. At least 40 volunteers
will be required.
Urine, biood and hair samples will be collected from each
subject four times during the study. The subjects will be paid $25
for their services. Collection of samples will be under the supervision
of a physician and the collections will be made outside of working hours.
Information covering all aspects of the project will be supplied to the
subjects. All aspects of these studies involving human "olunteer subjects
will be conducted in accordance with the PHS Surgeon General's issuance,
"Protection of the Individual as a Research Subject", dated May 1, 1969.
EARN AN EXTRA $25 \
I
COMPLETE INFORMATION REGARDING THIS PROGRAM WILL BE GIVEN OUT
Where:
When:
-------
MALE HOSPITAL BUILDING CUSTODIANS
EVERYONE TALKS ABOUT POLLUTION
HERE'S YOUR CHANCE TO HELP DO SOMETHING ABOUT IT
NEED 40 VOLUNTEERS FOR A RESEARCH STUDY
Southwest Research Institute is conducting a study for the
Environmental Protection Agency (EPA Contract No. 68-02-0595) to
evaluate human exposure to fuel additives. The study will involve
the measurement of certain metals in hair, blood and urine cf subjects
who in their normal course of work are exposed to exhaust fumes from
internal combustion engines.
We need your assistance in contacting potential volunteers.
The participation of these individuals in this study will not interfere
with their jobs. We need male building custodians between the ages
of 18 and 45. At least 40 male volunteers will be needed and they will
serve as a control group for comparison to results for males regularly
exposed to exhaust fumes in their normal course of work.
Urine, blood and hair samples •will be collected from each
subject four times during the study. The subjects will be paid $25
for their services. Collection of samples will be under the supervision
of a physician and the collections will be made outside of working hours.
Information covering all aspects of the project will be supplied to the
subjects. All aspects of these studies involving human volunteer subjects
will be conducted in accordance with the PHS Surgeon General's issuance,
"Protection of the Individual as a Research Subject", dated May 1, 1969.
EARN AN EXTRA $25
COMPLE TE INFORMATION REGARDING THIS PROGRAM WILL BE GIVEN OUT
1
Where: \
When:
85
-------
NURSES, FEMALE OFFICE STAFF, AND FEMALE BUILDING CUSTODIANS
EVERYONE TALKS ABOUT POLLUTION
HERE'S YOUR CHANCE TO HELP DO SOMETHING ABOUT IT
NEED 80 FEMALE VOLUNTEERS FOR A RESEARCH STUDY
40 LIVING NEAR (WITHIN 2 BLOCKS) OF A FREEWAY
40 NOT LIVING NEAR A FREEWAY
Southwest Research Institute is conducting a study for the
Environmental Protection Agency (EPA Contract No. 68-02-0595) to
evaluate human exposure to fuel additives. The study will involve
the measurement of certain metals in hair, blood and urine of subjects
who in their normal course of work are exposed to exhaust fumes from
internal combustion engines.
We need your assistance in contacting potential volunteers.
We need females between the ages of 18 and 45 who live within 2 blocks
of a freev/ay in the metropolitan Houston Area. At least 40 volunteers
will be needed for this group. An additional 40 female volunteers (same
age group) who do not live near a freeway and preferably live on the
fringe of the metropolitan Houston Area.
Urine, blood and hair samples will be collected from each
subject four times during the study. The subjects will be paid $25
for their services. Collection of samples will be under the supervision
of a physician and the collections will be made outside of working hours.
Information covering all aspects of the project will be supplied to the
subjects. All aspects of these studies involving human volunteer subjects
will be conducted in accordance with the PHS Surgeon General's issuance,
"Protection of the Individual as a Research Subject", dated May 1, 1969.
EARN AN EXTRA $25
COMPLETE INFORMATION REGARDING THIS PROGRAM WILL BE GIVEN OUT
Where:
When:
86
-------
APPENDIX C
LISTING OF RESIDENCE, EMPLOYMENT,
HEALTH, SMOKING HABITS, AND PERSONAL DATA
FOR VOLUNTEER PARTICIPANTS
87
-------
A listing of the keypunch card data for Card 2 (as defined in
Appendix A) for all volunteer participants who successfully fulfilled the
sample collections. The volunteer participants are identified by
the assigned arbitrary three-digit ID number (columns 2-4) and this
listing is ordered, numerically, regarding the ID number. Personal
data for all human subjects on which the conclusions of this study are
based are included in this listing. Conversely stated, data for persons
who for some reason were not selected as participants or for some reason
failed to complete the required sample collections (and, thus, were
removed from the study data base) are not included in the listing .
88
"TW^r-""*" """ --'.
«•'•«•'.• - A
-------
APPENDIX D
CLINICAL DATA
Hematocrits
Coproporphyrin
Creatinine
Volume/Specific Gravity
Trace Elements - Blood
Cadmium, Copper, Lead, Manganese, Zinc
Trace Elements - Hair
Cadmium, Copper, Lead, Manganese, Zinc
Trace Elements - Urine
Cadmium, Copper, Lead, Manganese, Zinc
Trace Elements - Feces
Cadmium, Lead
89
-------
HEMATOCRIT
CROUP NO. 1
test
l.D.
No.
C22
1
r'J
2
4^
3
35
4
49
f C f
155
f • :• -
024
"C13
029
OH
030
020
033
015
016
069
036
040
049
008
039
027
055
032
042
034
023
045
026
053
012
047
014
017
067
071
070
i
-18
45
-•:.
47
• 1-7
55
45
47
48
43
49
47
51
43
46
45
54
49
49
44
45
48
49
45
49
44
47
37
48
46
48
45
49
47
.; <}
•t-t
47
44
-i~t
45
" 45
46
49
42
47
46
46
40
45
44
51
46
47. 5
42. 5
44
43
45
47
48
46
46
38
45
44
46
46
49
44
-'•
49
"4
45
<5
44
50
47
47
43
40
21
41
-
40
49
45
47
48
44
42
34
46
46
43
47
46
46
37
47
46
50
45
44
42
i ~* "j
i J.4.
4 6
4 n
42
44
49
41
45
47
45
46
_
44
45
43
46
48
-
16
43
46
45
48
47
49
46
44
38
46
46
47
46
47
44
GROUP NC
I.D. No.
350
3-^
323
312
347
334
329
285
336
326
321
313
284
320
340
253
318
339
258
343
283
327
330
351
337
314
338
315
349
324
328
341
286
325
333
345
316
319
331
31 M ;
). 1A
Test
1
47
£. 3
•- y
46
_
44
43
51
49
47
44
_
46. 5^
47
45
49
44
46
48
48
54
45
46
45
47
44
45
46
47
_
46
49
43. 5
49
46
45
48
46
45
48
2
45
45
47
42
43
40
40
49.5
38
42
51
_
45
43
47
44
46
44
48
47
_
40
46
42
43
43
-
46
42
45
47
45
54
49
42
45
44
42.5
-
3
44
4
47
45 i 45
~ 42 45
45
43 43
t
-
49 48
-*9 47
40 50
43 46
53 49
49 1 41
_
_
49
44
46
43
45
48
45
41
44
48
45
42
43
43
46
45
48
45
49
45
44
49
46
37
37
45
|_ 49
46
46
45
46
43
45
47
44
45
47
47
44
53
46 1 46
43 | 43
46 46
47
45
46 | 46
49 48
i
1
t
I
-------
GROUP NO
. I.D. No.
' 50'
, 279
2t>4
, r-4
, 273
2B1
, 003
, 001
, 504
, 502
. 269
, 270
. 262
266
405
066
402
058
404
006
005
065
276
002
501
275
278
061
505
277
271
. 2
1
-' ' . 5
5^
48
55
50
44. 5
45
—
43
44.
44
45
45
46
51
44
45
49
46
46
47
42. 5
50
50
46
46
51
47. 5
48
50
47
T e
2
4 5
53
40. 3
52. 5
4V. 5
45
45
43
44. 5
46
43
44
44
44
50
45
4i
47.5
47.5
48.5
47
42
50
53
47.5
49
51
46. 5
49
48
45
s t
3
.'--,
58
••\ ~i
53
47
45
42
40
42
41
39
42
42
43
49
41
43
49
44
46
43
43
49
51
45
46
46
44
47
44
45
4
53
53
48
55
..
50
45
45
45
43
44
45
44
-
-
52
-
44
48
47
47
42
53
-
47
48
51
51
45
48
47
45
;
I 1!
92
GROUP NC
I.D. No.
246
298
25°
307
291
287
248
299
303
-401
304
309
249
257
305
288
400
251
255
292
290
261
250
301
601
/
/
j
> i ^
'I . '
., "*
• ' .x
, 2A
1
43
48
47
47. 5
47
41
46. 5
36
45
42
39
34
44
46. 5
45
48
46
45
40. 5
—
41
43
46
40
42
T e s
2
42
46. 5
46
35
47
40
47
40
45
42
41
45
44
49
44
-
42
44
41
45
40
45
45
40
48
t
3
40
42
46
48
45
42
47
47
to
42
44
44
44
39
48
44
.44
44
39
46
41
43
46
42
48
4
42
4 -.
49
50
43
3b
41
43
34
41
-
.58
39
45
44
46
42
44
42
43
37
46
43
-
48
;
-------
HEKIATOCRIT
GROUP NO. 3
I.D. No. } 1
: -. I 40
Test
2 1 3 1 4
40 j !>
GROUP NO
I.D. No.
jn j'l I'si
. 3A
Test
1
4 1
2
T r~
3
~ "
4
-•. :
311
1 41
40
n3
2ii3
236
Z97
149
176
nno
161
177
600
110
139
230
129
204
Z96
222
094
210
098
122
224
294
295
i
31
3B
39
42
41
40
40
40
39
41
38
32
41
40
46
35
42
37
43
45
38. 5
42. 5
38
44
31
3J:
38
42
42
38
41
41. 5
3o
42
39
35
35
41
45
37. 5
42. 5
37
41
37
40. 5
41
40
45
I 33
3o
_
41
41
-
42
45
40
43
^
34
40
42
43
37
_
40
40
39 ,
40
43
-
-
38
5c
_
43
40
41
39
43
39
41
38
34
39
40
39
47
3 5
38
43
39
45
39
-
_
93
- ^ i
i •'.-
227
083
24'
13o
215
IbO
'""^
097
226
213
126
229
195
233
175
157
209
188
225
134
166
125
170
123
182
214
186
172
244
234
118
109
169
206
.-
37
43
3B
39
39. 5
42
37
43
39
40
37
41. 5
43. 5
36. 5
41
40
38
41
38
36.5
39
38
38
38
36
37. 5
42
42
43. 5
40. 5
40
38
37
37. 5
40
- _
'0
--3
* *
33
40
43
37
43
38. 5
38
40
42
40
35
41
40
40
40
39
3S.5
37
39
38
_
38
40
43
43
42
40. 5
37
37
38
38
39
_
40
41
« i
39
"* '^
39
-
44
39
41
36
_
42
36
43
37
42
41
45
36
42
.
38
39
37
36
39
42
40
42
39
.
..
41
i
-
i 41
4 1
4!
40
-
-
j. \
42
44
3 5
43
41
36
-0
40
39
42
34
40
42
„
37
41
39
37
_
43
_
44
39
44
39
—
-------
URINE - Great inine
mg/100 ml
1
i
\ Group 1
I ^moi^e"
[ OZZ
i 054
; 03S
; oz9
j 030
On.O
', 033
r* t ~.
!
i
1
U I O
069
036
040
003
1 039
i
027
J 032
• 042
} 023
?
026
053
012
047
014
017
071
(non
046
035
024
013
019
015
049
055
034
045
067
070
Test GroupJA.
, 3 4 (smokers)
67 o 125.6 11". 0 75.2 350
148'7 8d. 3 127. 6 100.3 348
S-J !S:1 -I '- S
;r. £:? ,r,:: 1- -
-lUj . u
135.1
194.6
73.5
94.1
122.8
173.9
63.3
161.7
102.2
108.5
A A 1 1
14 1 . J
204 .7
* ?.Z . 8
55.3
44.8
108.5
89.9
206.8
smokers)
91.3
119.0
150.8
180.6
144.5
» e Q [\
168.0
122.8
118.6
46.9
114.4
151.5
106.4
136.1 120.5 145.5
177.4 76.4 47.6
Ib0.5
198.1 83.4 Ib0.6
144 2 146.4 160.6
454.7 88.5 77.7
.,, a ao 7 190.7
164 .O 77.*
.-it, ^74 92.8
175 . 3 D i -^
-ITS 3 100.4 155.5
i 1 3 • J i W >-• •
on f, 56 1 40.1
7\J . D j u • *
169.0 82.1 26.1
185.5 146.7 95.6
30 8 81.4 82.8
51 4 85.3 72.7
92.7 41.8 143.0
164.8 45.7 145.5
196.0 132.6 138.0
181.6 67.7 125.4
431.9 135.1 97.8
74.2 61.8 47.6
181.6 88.0 107.9
247.4 233.3 130.4
,AA 7 50.2 125.4
1*t*± , £, _/ v * fc*
144. z 106.1 165.6
AC.A 7 109 6 140.5
1 DTT . ' i " ' • v
-177 7 83 8 82.8
1 £ 1 . 1 uj."
7A -, 29 0 62.7
(O . J L. 7 . ^
102.9 74.2 75.2
747 4 108.8 . 125.4
£^« ' • " A V «-» • v»
.nc n 70 0 148.0
U UD • u t v» . w
94 t
313
284
t "> A
320
340
253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
(non
323
312
347
334
285
326
258
343
327
330
351
338
324
328
341
Test
J__ _?_ _1_ _±_
llo 3 158.1 206.5 70.1
2l4'o 139.6 239.5 127.4
246-.3 156.1 253.6 129-5
189 7 98.6 277.3 121-0
163'.3 172.5 264.5 174.2
110. 3 112-9 179-0 97.7
AA A 7ft 7 151.1 29.7
44 . 1 ^" •
125.7 195.1 254.2
105 9 149.9 120.3
H4 7 174.6 254.9
174'.3 — 38.1
139 0 131.4 54.9
156.6 195.1 258.8
123.5 78.0 255.1
267.0 76.0 84.5
102.7 82.1
_, c 4C9 7
119.1 135.5 152.2
* ~i n 4 U ~> 7 709 3
147,9 \oe..f- C.VT.J
„ „ on i -l^"! 8
78 0 90.3 ija.o
88.3 43.1 55.9
184.8 146.3 305.2
176.6 174.6 229.6
110.9 73.9 156.3
119.1 154.0 63.7
154".0 88.3 167.2
smokers)
200.8 225.9 262.8
260.6 156.1 292.0
46.3 156-1 253.6
A n-^ f\ 4 A.A Q
192.0 193.0 144.-*
O A*7 A
211.8 202.8
r\"y A -tA"^3
141.2 92.4 atjJ.-J
118.3 123.2 186.2
_ A i *7 4 Q
176.5 205.4 271.9
133.5 108.8 283.2
39'.0 63.6 164.1
___. f* *J ( k. (•
201.3 225.9 266. V
J M Q *
176.7 --- I78-3
127.3 92.4 271. <
195.1 215.6 283. (
jooa -1419 190.
188.7 1*17.7 •»'
.«r A ->ni t 195.
130.5
108.3
118.9
101.9
40.3
180.5
93.4
45 .0
118.9
110.4
78.6
40.3
118.9
110.4
38.2
180.5
104.0
159.3
150.9
129.5
140.2
106.2
97.7
116.8
108 .5
63.7
131 .7
74 3
• * * •*
i 89. 2
) 106.2
j 93.4
1 91.3
-------
URINE - Creatinine
me, /100 ml
Group
2
(smokers) _ 1 _
503
2 (-.4
004
273
231
504
Z"'0
262
!li/->
; 405
i 066
i 058
; 002
1 275
» 061
t
{
s
}
(
(non
279
003
001
50Z
269
402
404
006
005
065
776
6 1 U
501
J v *
278
t. 1 v»
505
J V/«/
277
w I '
271
229.1
172.9
197.9
27.0
191.6
62.5
162.5
181.2
172.9
10S.3
56.2
93.7
187.5
smokers)
79.1
145.8
108.3
291.7
210.4
147.9
191.6
154.1
284.5
22.9
158.3
208.3
166.6
162.5
166.6
143.7
Test
Vi >3 V
. —
Group 2A
., -—
196.9 51.5
63.4 48.0
140.0 151.1
17.1) ---
107.2 45.7
153.8 32.2
262.4 208.3
249.9
135.6
236.6
61.5
287.0
54.7
118.1
168.5
39.3
295.0
176.3
148.8
120.3
111.6
225.5
246.0
266.5
34.8
164.0
Z18.8
109.4
262.6
164.1
144.4
ti^.'i
84.7
128.2
215.2
208.3
70.9
100.7
145.9
27.4
206.0
98.4
194.6
155.7
77.8
27.4
119.0
107.6
20.6
70.9
171.7
162.5
194.6
167.1
100.7
4 (smokers) J
•• m
1Q0.8
37.3
123.1
102.5
22.5
194.9
100.5
246.2
114.8
86.1
114.8
61.5
63.6
147.7
118.9
88.2
162.0
96.4
182.6
110.7
32.1
— — — —
164.1
57.4
180.5
77.9
142.2
298
307
291
287
248
299
303
401
309
305
288
292
601
261
250
(non
\
246
259
304
249
257
400
251
255
290
301
70.6
70.6
66.3
40.6
194.8
278.4
t — f, *
1 D 0 . -i
128.4
299.8
126.3
201.3
181.6
199.6
167.7
53.9
smokers)
205.5
253.5
288.6
273.0
278.4
175.6
321.2
219.6
175.6
83.7
Test
2
D
- —
67.3 83. 5
169.6 102.5
30.2 193.6
195.1 34.9
226.2
164.5
265.1
36.4
226.2
215.2
168.6
106.9
39.0
167.3
203.6
308.5
308.5
246.8
90.3
64.5
294.8
133.7
100.7
123.4
70.8
125.8
76.9
144.5
221.4
158.5
195.8
111.8
163.1
67.6
83.9
144.5
97.9
76.9
130.5
165.5
58.2
102.5
86.2
102.5
135.2
149.1
4
T
• — -j
c3 . Z
100.2
233 . i
102.5
37.2
74.5
95.5
100.2
125.8
195.1
186.4
116.5
186.4
181.8
88.5
144.5
149.1
132.8
191.1
114.2
167.8
144.5
139.8
95
-------
URINE -
! Grot
•j 3
(smokers) 1
112
Ml
IPO
142
ilji
l!.7
' 23*
1-iv'
j J7i'
| 600
f 139
j 2,0
204
210
098
122
(non
HI
311
133
203
297
080
161
177
110
224
129
296
222
094
167
41
277
53
7£
97
174
209
116
91
58
-:•£
197
174
83
233
smokers)
278
90
134
148
130
174
183
197
199
92
69
230
125
144
.4
. i
.0
.4
.0
.5
.2
.1
.1
.9
.0
.1
.5
.2
.6
.6
.8
.6
.7
.7
.1
.2
.5
.5
.8
.9
.7
.0
.4
.0
Te
2
150.2
loo. ^
212.7
217.4
^7.1
161.9
180.4
i78.6
277.5
30.9
141.0
2- 3.3
215.1
141.0
194.2
69.3
231.2
122.5
254.4
120.2
96.8
129.5
...
173.4
168.8
124.9
219.7
161.9
80.9
C r eati
nine
~
mg/100 ml
s t Group 3A
3
134.8
I ) ' . 5
162.2
258.6
1 j 3 . -1
139.0
231.7
75.8
159.2
37.9
252.8
160.1
158.0
111.6
126.4
111.6
88.4
80.0
126.4
153.8
126.4
103.2
111.6
103.2
210.6
179.0
115.8
4 (smokers) 1
273.9
1 7 A . <5
132.7
20S.5
134.8
....
84.2
71.6
195.9
9-1.6
168.5
269.6
179.0
255.0
252.8
139.0
130.6
210.6
109.5
120.0
153.8
168.5
69.1
187.4
252.8
273.9
42.9
130.6
091
131
227
2-15
r.'-.
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
169
{non
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
31
54
133
98
19
148
156
62
94
71
110
173
185
46
193
136
39
113
113
101
83
.3
.1
.9
.7
.9
.1
.7
.6
.0
.2
.9
.8
.2
.4
.7
.7
.8
.9
.1
.6
.1
—
Test
2
39.7
99.2
114.1
124.1
4.9
52.1
100.1
91.8
63.2
69.5
144.1
91.8
19.5
147.8
91.8
32.2
176.2
101.6
129.3
97.0
3
19.0
196.3
247.2
212.3
89.1
157.0
212.1
80.6
148.5
180.3
196.3
63.6
82.7
44.5
70.0
133.9
157.0
129.3
4
50.9
--_.
135.8
1 h 9 . -t
53.0
201.5
201.5
201.5
97.6
144.2
167.6
167.6
233.4
57.2
212.1
106.0
161.6
219.4
smokers )
136
162
151
156
196
79
170
133
105
79
48
99
56
207
64
.7
.4
.0
.7
.6
.7
.9
.9
.4
.7
.4
.7
.9
.8
.6
76.9
139.0
121.6
89.3
96.8
69.5
111.7
94.3
99.2
81.9
35.1
38.1
194.1
177.8
103.9
178.2
228.8
116.7
254.6
166.3
275.8
256.4
133.6
73.3
108.2
89.1
92.3
...
127.3
123.0
131.5
115.4
190.9
233.4
106.0
73.3
275.8
177.8
147.8
96
-------
- C :. -^ r o p orphyrin
Group 1
(s. -..•--
027,
054
"O'S
n?o
W fc- /
C30
07.0
033
016
G69
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non
046
035
024
013
019
015
049
055
034
045
067
070
U K !-••'• _;_—_---—------
Hg/lOO ml urir.
Test <
j, 7 3 4 '
3.5 4.5 2.3 LI
„ - , Q 77
— -j Q 1 "i.V — > '••
/ . s ^ . -J
2.5 1.1 1.3 2'°
7.0 6.6 4.1 LI
6 0 4.9 l.-i 1-t>
6.3 1.9 3.0 0.4
2.6 3.1 0.4 0.5
6.0 2.3 0.5 O.o
3.6 3.7 --- ":
3 1 3.5 0.2 0.,
2 3 5.9 2.0 1.0
5'.8 3.1 0.7 0.8
! 5 5.0 2.4 1.1
1.5 3.5 1.6 1-8
9 9 9.4 3.0 5.6
92'.4 1.5 2.0 08
8.7 0.8 2.3 0.8
4 7 3.4 1.8 1.1
8.1 2.9 2.2 2.2
1.3 5.0 0.8 1.2
1.8 3.4 0.8 2.1
2.5 5.9 0.9 2.2
0.4 5.7 1.8 0.9
5.2 7.4 0.2 1-2
smokers)
3.0 3.2 2.2 2.0
9 7 1.1 I-2 °'5
3.3 3.0 1.4 1.5
6.4 7.8 4.1 2.9
10.0 2.4 3.3 1.0
4.2 2.1 0.9 1.0
2.5 3.3 0.8 0.4
8.4 11.2 2.1 1.1
1.0 2.9 0.4 1-2
5.7 3.7 1.2 0.8
9.6 9.5 4.0 2.2
3.! 3.2 1.0 1.4
97
e
Tjroup 1A
smokers
350
348
347
329
336
321
313
284
320
340
253
318
339
283'
337
346
314
315
349
286
325
333
345
316
331
(non
323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
> JL- -
Te st
2 3 _
4
• i •
-> \ 4 .° 4-4 1>5
i'.O 4.5 1.9
_ * r\
2.5
1.3
7.9
9.4
1.0
5.6
4.3
3.0
1.3
4.0
4.2
6.1
1.1
2.5
2.8
3.8
1.2
3.0
2.2
8.1
2.1
1.8
3.3
smokers)
2.2
7.9
10.7
5.0
7.6
2.6
9.2
1.8
0.3
6.0
1.4
0.2
8.9
5.6
5.4
7 S
( • -?
4.4
3.3
4.4
1.3
6.1
7.1
7.1
8.5
2.8
5.0
2.5
0.3
4.5
4.5
6.3
2.8
7.4
1.3
6.1
8.9
5.6
4.0
4.5
9.4
3.0
4.2
9.2
3.5
0.4
6.1
3.4
8.9
4.4
8.1
1.7
2.2
1.3
4.4
0.9
5.3
4.7
2.6
2.0
1.1
1.5
2.7
2.7
3.7
1.2
1.9
1.5
5.3
3.9
2.6
1.4
1.1
l.S
-» *
i~- - -
4.8
3.6
6.°
0.9
1.6
3.2
3.9
3.3
2.2
2.3
5.7
2.6
1.8
0.8
6.8
1.1
1.8
4.7
1.5
5.5
1.9
1.8 2.0
1.3
12.8
0.8 4.0
1.2 3.3
0.4 3.9
1.1 2.7
0.9 3.9
0.9 1.3
3.7 5.4
4.6 2.2
0.8 2.0
0.9 2.3
n. / A 4
0.6 4.i
_ . A "7
3.4 4.1
-------
U RIN E - Cuproporphyrin
Group 2
(srrio
503
Z64
00!
273
2.-.:
50--
270
262
Z66
405
Ob6
058
002
275
061
(non
279
003
001
50Z
Z69
402
404
006
005
065
276
501
278
505
277
271
kers) 1
0.4
4.2
11 .1
1.4
5.6
2.7
7.0
16.6
6.0
2.4
23.3
4.3
smokers)
6.0
Z.8
9.7
6.9
9.4
14.0
6.3
5.5
0.4
2.2
5.2
4.3
6.5
4.9
2.9
Z.5
Te
2
0.4
2.5
8. '.
0.8
i.7
1.6
17.0
23.3
3.3
3.6
4.7
Z.O
16.3
5.4
f'S
st
3
1.3
2.6
9.5
1.6
2.9
5 . n
1.8
3.3
1.3
2.3
6.7
0.8
1.9
2.9
/ICQ ml
4
2.7
3.0
5.8
2.9
2.0
11.4
1.3
2.6
.__
3.6
1.5
0.6
2.5
urine
Group 2A
(smokers)
258
307
291
287
248
299
303
401
309
305
288
292
601 .
261
250
1
2.4
1.2
0.4
1.9
12.3
3.8
2.0
0.2
9.5
0-6
13.8
1.1
6.3
2.4
0.8
Tes
2
0.4
1.7
0.7
2.8
6.2
2.9
0.3
1.5
2.0
2.5
1.3
1.3
0.5
1.5
3.0
t
3
4.3
1.7
1.5
1.8
2.8
0.8
2.0
2.3
2.1
1.1
4.1
1.5
0.7
4.0
4.1
4
6.2
3.6
1.5
2.f>
2.1
4.7
3.5
3.3
2.7
3.8
7.1
6.3
2.2
3.0
(non smokers)
1.9
0.6
1.0
3.5
. Z.9
Z.O
8.8
7.7
6.7
2.6
4.3
8.6
2.3
6.8
3.5
0.8
0.9
Z.3
3.0
4.3
2.7
1.1
Z.O
1.5
1.3
0.8
Z.O
0.8
Z.6
1.6
1.2
1.1
3.4
4.0
3.9
2.9
2.6
4.4
0.8
1.5
2.3
1.1
Z.Z
1.9
2.0
246
259
304
249
257
400
251
255
290
301
6.5
9.4
3.7
4.4
10.8
4.5
8.6
6.6
4.5
1.2
3.3
5.2
3.9
1.1
1.3
2.0
4.4
5.2
0.5
1.8
2.0
0.8
3.1
1.1
3.3
1.8
2.3
0.8
2.2
2.1
3.8
7.3
1.6
3.2
4.1
3.2
1.6
1.0
1.7
98
-------
T ;; • i:,' z - c o p rope
r r, h v T i n
Group
\-' '"' -'•
11 Z
1-il
180
14Z
Z94
ZS5
ZZ1
187
Z36
149
176
600
139
Z30
Z04
Z10
098
1ZZ
(non
111
311
133
Z03
Z97
080
161
177
110
ZZ4
1Z9
Z96
ZZZ
094
3
ers) 1
1.2
1.7
9.5
2.Z
1 .7
7 c
1.4
4.5
4.1
6.9
1.1
1.2
1.1
0.5
2.4
2.1
3.0
smokers)
8.2
3.2
6.8
1.9
2.2
1.7
4.5
2.7
8.8
0.5
3.8
2.1
1.9
2.1
[•j/100 ml urir.o
Test £H::::LI±_
2 3 .4 (smokers) 1
2.2 1.6
1.4 1.0
2.7 1.1
5.1
-> O
3 . ?
1.5 3.6
3.5
1.2
1.4 5.0
5.8 10.3
2.2 7.7
1.9 2.2
4.3 1.6
6.2 2.7
3.9 5.4
2.1 5.9
1.5 2.2
3.2 3.2
3.2 1.2
2.5 2.2
1.9 1.8
7.0
1.1 8.5
3.6
4.3
1.7 6.4
0.7 0.8
3.0 3.2
3.7 3.5
4.8 5.8
2.5 2.7
4.5
2.2
3.9
6.4
1.6
2.9
5.7
0.9
3.2
4.8
5.5
11.8
3.9
3.5
4.6
2.3
2.3
1.6
3.0
1.9
0.5
6.8
6.8
2.3
3.9
091
131
227
Z45
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
* v /
169
(non
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
0.4
1.2
1.2
2.0
0.8
1.8
1.5
1.8
1.8
3.3
0.9
1.6
3.6
0.6
0.9
1.6
4.4
1.6
1.8
2.3
2.5
smokers)
2.3
2.0
5.7
2.2
2.0
1.2
1.5
2.7
1.6
1.5
3.6
1.1
0.5
3.4
0.8
Test
2 3
0.8
2.0
1.2
2.3
0.2
1.7
0.8
2.5
1.1
1.6
1.3
2.1
0.4
6.1
3.1
0.8
6.7
1.5
2.1
0.4
0.5
1.5
3.3
1.7
0.8
0.6
2.6
1.4
2.2
0.5
1.3
0.5
1.2
1.6
1.8
0.9
2.6
4.0
0.8
2.0
3.6
3.6
0.8
2.0
1.5
2.7
2.6
2.6
3.2
4.4
3.5
3.4
4.7
2.2
4.0
1.6
5.8
4.1
2.9
2.0
2.3
2.5
0.5
4
2.9
2.5
2.3
0.5
2.0
4.4
4.1
2.2
3.4
3.0
5.1
6.5
1.8
1.9
5.0
1.9
_ _ —
3.2
1.3
Z.9
z.o
5.8
5.1
Z.3
0.4
3.Z
1.7
_ _ -
99
-------
U Ps I N E
GROUP NO.
Volume
(ml)
Specific
Gravity
i. n.
Mo.
04b
A 1 '
036
n i i
U.I /
ni'i
o iu
'.'-0
033
015
' 1 J
069
036
IMO
049
008
039
OE7
055
032
042
034
023
045
026
053
01Z
047
014
017
067
071
070
1
til a
t (' O
773
•:.'. i
•197
(
639
13u<
-13")
578
c!9
•>.!•-,
657
614
6Q9
574
674
734
759
869
1131
971
1278
784
004
504
1028
15 54. _.
1417
978
907
834
162
712
T
r - •
•i:n
1 t-U
r t
•
111!
f , I > 1
! " "*
593
939
'?i.3
525
750
764
c99
641
644
485
1097
522
1535
1025
878
1 171
737
1602
1554
470
646
509
526
313
768
e s t
",
Orn
't i .-
603
831
77
t A|"M
30"
,
«.' '
670
127o
\°2
47o
5 6 '3
391
_
819
445
585
531
474
188
1332
4 60
1128
1261
1221
952
386
691
1329
1813
1602
399_ _,
992
600
435
1f>H3
*
984
1173
1 •,«.!
P71
419
•(••'',
583
793
194
402
519
1184
_
505
408
856
897
L 383
745
984
262
1381
664
1443
1 116
613
534
1030
?U
532
685
609
330
408
100
1
1.010
1 . ' i :
.021
.017
. o:i
. 019
.025
r\~> _)
. 021
. 015
1.022
1. 020
1. 022
1. 020
.
1.026
1.023
1.025
1.015
1.008
1.025
1.019
1.012
1.013
1.004
1.020
.017
.024
.018
._0 1 1 _
.005
.018
. 015
1.024
1.018
1. Oil
i
T e
?.
i.o.:;
i < -> -*
1.025
l.OH
.0?1
1.023
1.035
l."M
1.023
1.027
1.027
1.023
1.020
1.020
1.020
1.031
.024
.024
.021
.023
.028
.018
1.023
1.008
1.012
1.014
1.030
1.029
1.010
1.010
1.015
1.025
1. 024
1.031
1.030
1.013
s t
3
1.025
i f . ~* •
1.029
1.017
l.n->t
1.015
1.031
1.025
1.022
1.015
1.020
L_ 1.017
1.026
1.023
-
1.012
1.028
1. 025
1.017
1.020
1.016
1.013
1. 025
1. 008
1.005
1.011
1.025
1.033
1.018
.005
.011
.010
.023
.023
.007
1. 014
;-
1. 020
' . •' t r>
1.023
1.015
1. 025
1 . ?. i
1. C2o
1. 020
_
1. 023
1.026
1.035
1.032
1.015
-
1. 034
1.028
1.030
1.016
1. 032
1.023
1. 023
-
1.011
1.016
1.009
1.018
1.018
1.015
_
1. 025
1.030
.
1.025
1.026
1. 027
-------
iA I i t
GUO'JP NO. 3A
Volume
Specific
Gravity
" o
091
ib5
227
f1 ^ ^
245
215
0^7
22f.
21 3
!?.(->
229
1 at;
233
175
157
209
188
225
134
Ibb
125
170
123
182 j
214
186
172
244
234
118
109
169
1
1^53
i
737
'1
.i.tj.
308
? * 3
— 5
756
325
2400
2 1 1
533
? 11
°65
>04
724
397
224
507
452
1092
432
538
982
983
333
BOS
1492
898
965
315
749
477
174
T
*
I 74'^
570
650
^ - ^
802
307
2 A 7
45 *
696
301
2400
340
800
2-i2
4'»-
55^
812
445
—
471
537
551
887
835
343
1173
107
469
1593
126
576
254
629
437
774
c s t
3
K---1
315
->--."
'
4oo
209
'• T ~>
4^?.
375
130
2400
281
H29
-.< 1
.' v ',
726
536
298
163
607
240
1175
_
229
766
590
-
-
1787
925
376
520
-
384
389
4
292
v,-,-
240
7 f, 6
—
7G9
_
2400
447
509
IcO
I'"1 O,
934
1150
522
356
277
206
1298
_
546
399
475
418
-
1337
-
278
285
510
329
101
1
1 "*' 1 '
1.010
1.024
!.••:-
1.017
1. 025
1.023
1. 022
1.019
1.025
1.000
1. 026
1. 017
1. 21
1.021
1.010
1.015
1.019
1. 028
1.024
1.025
1.006
1.020
1. OOb
1.012
1.005
1. 027
1.015
1. 015
1.012
1.010
1.027
1.014
1.013
1.022
•
T €
2,
, - .
1.116
t . '" 2 0
< - - .
t . M 5
± . . — vr
1 . r 2 5
1.12-1-
1 . ' 1 5
1.G30
1.002
1 . '-• 2 9
1.016
. *•> 7 •>
1.023
1.014
1.012
1.022
-
1.024
1.01Q
1.020
1.015
1.010
1.028
1.010
1.025
1.025
1.010
1.026
1.011
1.030
1.010
1.022
1.011
: s t
3
1 . ' ^ 2
-
1.020
• -, •>
-
i _ A 2 2
1.014
« /--»->
1.02?
1.025 _j
1.001
1.028
1.010
1.011
-
1.011
1.015
1.028
1.010
1.016
1.018
1.015
-
1.015
1.015
1.009
-
-
1.010
1.011
1.014
1.019
-
1.017
1.025
»
*±
1 . r '• r
_
1.019
_
1.013
'. . 02
1.020
-
1.02 '"•
-
1.00?
1.02-
1.015
1.02B
_
1.008
1.014
1.030
-
1.026
1.025
1.009
-
1.00 -j
1.017
1,007
1. 029
-
1.011
-
1.014
1.029
_
1.025
_
-------
U R IN E
CROUP NO.
Volume
(nil)
Specific
Gravil y
I D.
T
Test
'» I
III
1 ' ~*
J 1
1-''
1
2T7
149
!7f'i
080
161
177
600
110
114
13?
.nn
129
204
296
222
094
210
098
122
i
325
T. n .-,
2 / ->
r~7^~
,
a'. ••
U2 '->
597
471
430
786
474
460
266
664
207
643
555
1093
760
. . 532
(.5.6
190
793
807
354
303
173
•>
353.
i m
. .-
-J • /
~ ' I
4'->(>
. ,
I t ')
3 : o
616
273
-
316
398
712
590
-
736
762
730
897
367
9o4
532
400
530
461
398
283
483
3
•> • :
^57
.
7 "r *
1710
•"V
r, < ',
760
_
i j -i
323
307
..23
-
813
1046
506
780
366
1617
701
S3 7
267
386
699
191
250
403
~
-:2
444
86
.•. ., i
r-jvv
MQ
< 30
_
25b
.
_
i -' 1
o52
872
728
365
395
391
84
523
479
927
575
286
109
568
861
3ol
228
220
102 j
i
! 1 } T 0
1 030
1. ^07
1.C.'0.
1 . C" ,-
,,!-025
1. 01 2
i. Uiv
1.017
1.010
1.018
] .021
1. 01°
1. 009
! . 027
' . 020
1.019
.
1.020
1.016
1 nt 4
i n 1 n
1 fll A
t n 1 5
1.020
1.012
1.015
1. 020
1. 005
1. 022
->
!. 017
1.030
1.013
1. G20
: . o i ;
1,02S
: . o 1 1
:.or
'..021
1.02?
1.027
-
1. 026
1. 023
1. 023
1.017
-
1.012
. 026
. 019
. 018
. 025
.022
1.025
1.030
1.022
1.019
1. 021
r i. 020
1.013
3
i^oj;
1.027
1.028
1.035
t , n \.\
1. 022
1. 030
_
1. 022
1.013
.
1.019
1.018
1.022
1.021
.
1. 026
1.015
.020
.017
.021
. 005
.016
.023
1. 021
1.019
1.011
1. 020
1.016
1.026
4
1.014
1. n27
1.031
\.r2.i>
t. ( V
1. o?n
1.014
_
1.022
-
-
1.017
1. 013
1. 016
1.016
1. 027
1. 020
1.019
1.021
-
1.016
_
1.020
1.026
1.02!
1.011
1.015
1. 008
1.016
1.016
-------
U K i
GROUP NO.
2 A
Volv.mc
(nil)
Specific
Gravitv
I.U.
No.
.- /O
1 - r\
T ;> —
1 - ~
248
I-),")
1
304
iC)
249
^T
305
2v ^
400
251
255
292
290
261
250
301
60 1
i
282
^t;?
i "> •> 1
6^2
70.1
TOO
...
j , '
815
934
"i(i 9
7°-0
690
:•-• t;
I2ti8
518
914
378
1925
501
631
474
1273
T
2
1300
•I'M
1 r • O
914
821
22 I
1
, 0
1137
7o2
1 127
?^OQ
476
— ' ' D
°22
044
738
869
2400
462
646
1258
888
e s t
3
i . . j
595
A. 10
^ » ,j
1-^6
j ">. ./. A
602
510
1
. -
704
368
4 •" 5
1325
585
• 4
1 196
760
812
278
955
584
439
608
539
1
4
~s , -J
252
_
1 ' "• -.
113
1011
1170
815
- -
- . -
487
253
70.-,
320
488
1 OR
968
581
617
989
1739
254
-
1440
584
103
1
i 1 -'2-i
1.010
1.022
i.nio
1. 006
1. 005
1.010
1 . •'" •
. 1.022
i . o : « •
1.021
1.026
1. 020
1.014
1.014
1. 023
1. 012
1.025
1.010
1. 027
1.024
1.022
1.009
1.027
1.013
i
T <
2
: . •„ _: j._.
1.006
1 . r> i 2 .
1 . ' '
1.003
1 . 0 1 8
1.015
1.' -7
1.020
1 . " '. -•
1.025
1.026
1.020
1. 012
1.028
1.022
1.016
1.023
1.022
1.010
1.025
1.010
1.017
1.034
1. 003
i S t
3
1 . '-• '. ~J
1.011
1.012
I.:.'.;
1.026
i . •: -i 3
1.020
'. . r"''7
1.018
! . i : -
1.020
1.029
1. 02 1
1.009
1.027
1.024
1.015
1.019
. 021
. 020
. 023
.016
. 029
1. 025
1. 010
4
-\
1.014
-
1.013
1.030
1.012
1.005
i . ono
1.016
i 0 7. ( !
1. 020
1. 024
1.01-
1.010
1.015
1.018
1.020
1. 021
1.016
1.010
1.025
1.017
-
1.016
-
-------
URINE
GROUP KO. I
Volume
(ml)
Specific
Gravity
I.D.
1 - f
264
U&4
•:--.
281
nn)
502
i(->")
270
li'l
Zoo
405
066
40 2
058
404
006
005
065
27b
002
501
275
27S
061
505
277
271
<
619
b2
-.">,
101=;
1 " , '
669
861
f ' . '"
522
4 A 5
926
b25
492
830
-
1496
537
467
162
1352
674
690
1251
749
MS
1263
529
671
T
->
• ~*
714
12-
:•••
17°^
ICC.
193
1473
1201
382
557
o99
-
359
1188
864
1K5
258
484
187
1256
1742
298
938
1479
fi9n
795
529
273
c s t
•>,
jl 1
( • i
812
IV?
_
1 V.Z
2"^
470
1 ' '- "i
842
4QT
260
957
95H
1137
141
757
395
1399
340
655
165
1197
1897
159
1014
535
712
648
407
81
4
443
-,o ,
591
77
-
1565
f--t7
190
l.'.oq
1010
445
361
-
774
401
-
535
645
535
161
-
81
-
1552
247
426
1350
476
330
1284
120
104 |
1
1. 035 .
, n,.,
1.020
1. 030
1.001.
1.07.2
1.023
1.023
< n i A
1. 040
1.030
1.023
.027
.012
.025
. 010
.019
-
1.018
1.020
.028
.005
.025
.027
.029
.015
.026
. 023
1.032
1.024
c (,t
T t
2
1.032
!LniO
1. 012
1.023
1. 003
1.013
1.035
1.027
1.013
i.(j- U
1.023
1. 027
1.026
-
-
1. 010
1.015
1.020
1.014
1.029
1.026
1. 007
1.014
1. 010
1.030
1.013
1.016
1. 024
1. 032
1.032
-
s t
3
_
1.006
1. OIL)
_
_
1.012
1.029
1.C23
1.006
1.026
1.022
1.026
1.012
1. 008
-
1.020
1.015
1.027
1.009
-
-
1.005
1.011
1. 008
1. 027
1.014
1.029
1.029
1.027
1.025
1.025
4
_
1.01 1
_
_
1 . 023
1. 027
1.022
.
1.022
-
1. 027
-
-
-
-
-
1.011
1.024
-
-
-
-
-
-
-
.1.008
l.Olc
-
I. 01?
-
-------
Spec itic
Gravity
^ * '
i
323
312
•-
• ;
3 . -
3? 6
'?.(•
i •> <
313
? -' -
-• w i_
MO
' " "t
318
»<»
258
143
233
527
no
nl
'37
m
H8
-1^
...M9
K4
^B
}4I
286
J25
133
145
116
MO
131
• T-
<
: .•
474
340
•• '"' 7
226
~ s *
7 ?( «
340
S 7 *
o <••••»
24UG
c •- .-•)
10 JO
589
533
1154
1068
622
553
355
756
254
491
491
1344
496
558
1386
705
362
295
1591
652
344
1047
594
V,T
b~?
- \
357
J75
< r ",
^V9
•
5M
1 1 Ui
(>7o
24UO
Z':^
790
380
_
917
716
534
594
294
755
71 1
284
557
847
-
5b4
1130
884
507
862
1284
268
460
1160
721
•5-1
1272
j
-•, i -s
391
2-1-0
. f ]
425
• - .
7 ' '~\
-1M
ti'.'O
llC'l "
1727
•' '-1
i b 7
631
581
1628
939
640
514
627
516
106
441
444
635
426
756
822
472
764
1000
1722
196
363
141 1
1 59
i-'21
1329
\
\ :• - ;
7 1" 3
435
41
17-'.
-
~ -". ">
170
-I '-I
•IOM
S-1S
1420
312
o'-,'0
780
794
1257
741
395
500
469
660
131
299
550
1029
485
614
1234
712
645
488
1331
421
553
1462
406
3 '•> 2
fl(/4
105
-i '
I i
1 . 0 I '»
1 I1 2 ' >
1.029
1. 034
1. -,.rt5
1.022
i _ n 7 -
1. 02-5
1 . (>.' «'
1 . 01 1
l.OOb
1. 003
1.021
1.015
1.019
1. 017
1. 020
1. 023
1.015
1.020
1.019
1.013
1. 003
1. 027
1. 025
1. 015
1. 021
1. 022
1. 035
1. 005
1. 019
1. 024
1. 009
1. 021
1. 025
1. 019 n
1.014
1.027
1.018
X
'\.\\\ C
S.-V.i
1.028
_
1 . 0 ? 2
1.030
1 O •> v
-
i . n.'i.
i. DI i
1.013
1. 005
1.033
1. 020
_
_
1.026
1.020
1.023
1.026
1.019
1. 018
1.019
1.026
1. 021
1. 020
_
1. 022
1. 038
1. 020
1. 030
1. 020
1. 010
1.026
1. 025
1.017
1 . 027
1 . f> >. ',
1.015
\ \
\ ._0 \ .».
1 . 'H '-
1.030
1.035
i . r: i r
1.017
* -NT —
1.01!
1 . il \'\
I . no i'
1.012
1.005
1.025
1.015
1.019
_
1.019
1.020
1.01 5
1. 01 1
1.020
1.026
1. 009
1. 020
1.014
1. 018
1. 027
1.016
1. 028
1.020
1. 020
1.012
1.003
^ 1. 025
1. 025
1.013
1 . 005
1.012
1 . 009
l.'M
1 . r' '*
i
I. '
-
i
1. • '
1;"''
1.0!
i. r;"
1. 02
1. • .L
1. 02
i . f -
1. C :
1.02
1. 02
1. C2
1. 02
1.01
1.05
1.01
1. ( ?
\.f l
1 . 0 ?.
1. 01
1.01
1.01
1. 02
1. 00
1.01
1. 00
1.02
L f"'-
1 . 01
. _
-------
BLOOD - Cadmium
Group 1
022
054
038
029
030
020
0?3
016
069
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non
046
035
024
013
019
015
049
055
034
045
067
070
\
1.
0.
0.
0.
0.
0.
0
0.
0.
0.
0.
0.
0.
0,
0.
0.
0.
c.
0.
0.
0.
6.
0.
smokers)
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
36
76
41
£0
63
68
7O
50
72
54
26
40
48
38
31 -
39
27
42
_ _
43
37
35
3
54
- -
60
82
37
36
32
51
36
21
27
56
75
Test
7
0.27
0.19
1. 1^
4.75
0.57
0. 64
0.21
0.31
0. 17
0.36
0. 18
0. 18
0. 57
0. 57
0. 33
n. 69
0.87
0.54
0. 62
0.75
0.46
0.23
0. 30
0.47
0.26
0. 63
0.46
0.46
0. 39
0.23
0.44
0. 57
0. 78
0.42
0.09
0. 13
Hg/100 ml Blood
Group 1A
3
0. 76
0.59
0.28
C.£4
0. 76
0.78
0. 35
0. 11
—
0. 78
0. 60
0. 33
0
0.70
0.25
0. 53
0. 18
0
0. 18
0. 63
0. 30
0
0. 33
0
—
0. 59
0.90
0.90
0.25
0. 14
0. 16
0.23
0.22
0
0.21
0
4
0.43
0.41
0. 32
0. 32
0.73
0.73
0
0.42
0. 30
0.39
0. 35
0. 50
—
0. 68
0.25
0. 37
0.25
0. 18
0. 17
1.45
0. 39
0. 10
_ _
0.49
0.27
0. 33
0.21
0. 56
0.97
0
0.26
0.21
0.21
0.27
0. 33
0. 10
(smokers)
350
348
347
329
336
321
313
2 £4
320
340
253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
352
(non
323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
0.
0.
2.
3.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1
99
47
97
08
21
—
42
61
11
18
08
14
96
44
24
64
36
65
- _
55
40
76
21
16
31
27
Test
2
0
1.00
0
0. 88
0
0.22
0. 31
0
0.41
0
0
0
0
1.70
0. 64
0.29
1.47
0.22
0.42
0.30
0.30
0.23
0.21
0
0.21
0. 35
3
0.29
2.39
0.38
0.49
0.41
0.27
0. 17
0. 15
0. 17
0. 14
0.41
0. 19
0.55
0. 31
0.21
- -
0.28
0.22
0.22
0.78
0.25
0. 33
0.25
0. 39
0. 32
_ -
4
~ ~ ~>
0.71
1.78
1. 33
1. 51
1.25
1. 11
0.80
1.70
1. 51
1.73
0. 68
1.41
0. 87
1. 55
—
1.03
2.25
1. 64
2.41
5.86
2.42
2.67
1.92
3. 10
—
smokers)
0.
0.
0.
0.
0.
0.
2.
0.
0.
0.
0.
0.
0.
42
_ _
21
38
46
38
63
47
41
17
08
19
36
13
0
0
0.47
0
0.35
2. 12
1.34
0
1. 60
0
0.35
—
0. 18
1. 35
0.27
0. 54
0
0.94
0.25
0. 56
0. 15
0.26
0. 30
0. 18
0.25
0.28
0.22
0.20
0
0. 30
0.25
0.91
1.77
0. 6?
0. 55
0. 61
1. 10
0.90
1.04
1.48
1.46
0.49
0. 81
1. 20
1. 71
107
-------
BLOOD - Cadmium
jig/100
G i -v
(: -
112
!••!
180
142
2'-M
295
221
1"7
23o
149
176
600
139
::o
20-i
210
098
122
(non
111
311
133
203
297
080
161
177
110
224
129
296
222
094
'> ^
'.-. f r s )
0
0
0
1
2
0
0
•J
0
0
0
0
0
0
0
0
0
0
smokers)
5
0
3
0
0
0
1
0
0
2
0
0
0
0
1
.22
. ic;
.29
.23
.00
. 1R
. 11
. 61
.24
.91
.97
. 30
.48
. 18
. 36
.30
.44
.50
.27
. 18
.71
.93
. 30
. 18
.27
.85
. 36
.84
. 24
.42
. 18
.42
Test
2
0. 17
0 . i "•"
0. 15
0.64
0.44
0. 32
2.48
0. Z*
0. 17
0. 14
1.47
0. 18
0. 18
0.49
3. 63
2.25
1.23
0.51
1. 18
0. 36
1.04
0.25
0.20
0. 39
0. 31
1.02
0. 14
0.49
3.02
0.66
8.70
0.77
ml Blood
Group 3 A
3
0. 66
n _ ' j
0.84
0.37
__
__
0.96
__
__
0.72
0.75
1.03
0. 56
0.49
0. 76
1.20
0. 89
0. 61
1.34
0.78
0.90
1.00
0. 74
1.02
0.89
0.77
1.47
0.69
0.78
1.03
1.03
1. 50
0
0
0
1
1
1
0
1
1
1
2
0
0
0
0
0
1
2
0
0
2
1
0
4
.72
. 46
.87
.79
__
.07
._
__
.22
.33
.92
.92
. 18
. 51
.26
.97
.24
.59
.94
. 18
. 11
.39
.61
0
0
0
0
0
. 51
.63
.37
(smokers) 1
091
131
227
245
206
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
169
(non
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
0. 86
0.30
0.93
0.63
1.86
0.29
0.33
2.04
0.79
9.31
0.69
2.20
0.26
2.56
1.70
0.34
0.59
0.32
0.59
0.98
0.20
0.43
smokers)
0.76
1.20
0. 33
14.63
9.31
0.43
0.08
0. 35
1.74
0.46
2. 56
1.00
0.38
0.21
2. 64
Test
2
0.25
0.58
0.24
3.02
0.30
0. 60
0.56
0.93
0.44
0.36
0.40
0. 73
1.09
0.59
0.50
0.23
--
0. 18
2. 52
0.32
0.34
0.46
0.22
0. 86
0. 33
0.53
0.71
0.47
0.30
0.52
0.41
0.29
3.58
0. 18
0.25
0.27
1. 71
3
0. 17
__
0.47
0.30
0.23
0
0.28
0
0.28
0.28
0.49
0
0.25
0.39
0. 16
0.20
0.62
0. 16
0. 35
0. 16
0. 11
0.21
0. 34
0. 57
0.30
_-
0.42
0. 34
0. 38
0.43
0.64
_.
0.27
0.23
0. 14
_.
.;
0. 14
o. !:-
0. 12
__
0.47
0.21
0. 16
0. 10
0. 16
0. 11
0. 13
0.21
0.40
0.27
0.62
--
0.24
0.27
0.24
0.31
--
0
0. 11
0.24
,-
--
0. 14
0. 12
0. 18
0
0.33
--
0.33
0
0. 60
0.22
108
-------
BLOOD - Copper
.-r.'lOQ ml whole blood
Group 1
Group 1A
(smokers)
n,8
72.0
0
4?. 9
I-
-J3.
S:!
51.0
:
047
f t 1 -1
I 1 4
017
071
(non
046
v rt \J
035
024
013
019
015
049
055
A-l A
\J J t
045
067
070
1 1U. 1
78.2
93.4
99.2
smokers)
107.0
70. 0
t \ a n
1 1 7. u
61.9
Cl~> ?
92. i.
108. 5
58.4
75.9
7 c Q
< b. 7
4 r\ *7 /I
10 < . 4
95.7
_^ A . 1 — ' *
51.7 46. 6
54.2 48.2
73.3 50.6
49. 9 38. 1
42.9 64.6
A 7 \ 505
4 £ . i JU.-'
77.1 79.0
47.3 57.2
65. 1 63.0
48.6 38.9
55.5 36.5
58.8 47.7
49. 8 42. 1
55 8 52. 3
J -J • *-*
53.3 43.3
60.0
51.0
75.0
40. 0
A / O
46. 0
40. 7
58.7
29.3
52.8
39.4
44.0
63.0
51. 0
40.0
47.0
347
313
284
320
283
337
346
314
315
349
-1 O L
286
325
333
345
316
331
(non smoke
323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
YU. i
65. 5
62. 3
85. 9
82.7
69 1
U 7 • A
62. 1
79.7
75.0
76.2
72.6
rs)
97.4
07 Q
o r . o
74.0
120.7
65.2
78.4
106. 1
62. 3
*7 n Q
/U . 7
67.7
78.4
97.7
83.2
69. 1
D U. 7
/ n ">
69. 2
- 4 n
si. 9
68.2
•-» i 1
f 3. 3
66. 1
42.0
54.0
72.0
56.0
61.0
75. 0
85. 3
75.7
81. 7
73.3
116. 5
72.0
63.4
52.9
73. 3
100 7
1 \j \s • i
61. 0
77.0
77. 0
58.0
59. 1
.
63.4 69.6
12. 0
65. 5
92. 4
62. 3
72. 0
66. 6
60. 1
68.7
70.0
55.9
65. 5
106. 2
68.9
64. 6
67.8
83. 8
67.7
67.7
83. 5
69.6
55.7
66. 1
63. 8
-
96.3
95.1
75. 8
42. 6
63.7
76.2
66.0
75. 1
74.2
94. 0
66. 1
71. 9
109
-------
Group 2
(smokers)
503
~> t- '
004
273
251
504
270
?62
266
405
Ob6
058
002
275
061
lig/100 ml
Test
1 J— -1- -
77~.3 -.3 ^.0 5
5:.0 71.2 41.0 5
143 5 102. a 67.8 t
67.2 65.1 53.5 !
77 3 60.0 57.1 (
62.1 — - 47.3 <
68.4 63.2 64.2
58.0 65.8 44.6
7.1 [ 44.1 ^--
56.3 80.5 55.3
77. 9 77.9 75. 0
68.4 91.8 68.7
105.1 58.0
60.0 58.0 53.2
81.4 87.9 69.4
whole blood
Group 2A
4 (smokers)
irTi 298
,0.8 307
,5.3 2^1
iO.8 287
iO.7 248
49. 8 299
77.9 303
401
309
58.0 305
288
63.2 292
49.3 601
51.7 26*
64.3 250
(non em
(non smokers)
279
003
001
502
269
500
402
404
006
005
065
276
501
J\I A
278
505
JUJ
Z77
tt 1 I
Z71
64.1
86.5
66.1
108.9
88.3
42.4
93.5
64.1
87.5
87.5
67.2
53.9
58.0
93.6
67.2
71.2
67.2
103.8
63.1
78.4
61.5
46.7
77.0
60.6
77.9
89.7
47.1
79.8
85.2
126.0
64.3
82.5
55.3
67.8
54.4
57.1
66.9
45.5
60.7
97.3
52.3
65.6
66.6
37.1
48.5
59.0
84.6
68.5
64.7
50.8
70.7
54.4
54.4
58.0
67.5
70.1
50.2
60.6
63.2
— - - —
41.5
38.4
51.7
57.2
65.8
246
259
304
249
257
400
251
255
290
301
1
67.9
44.7
51.4
43.9
39.8
67.1
55.5
47.2
71.3
50.5
46.4
44/
45.1
lokers)
Tc&t
_2__ 3 4
55.1 57.3 102.1
63.1 45.8 82.4
42.8 41.5 76.6
37.0 42.2 &0.0
38.4 43.0 60.3
54.4 53.0 88.2
47.1 51.6 91.6
49.3 58.0 89.3
66.0 60.8 H0.2
, 43.5 48.8 75.4
I 51.6 46.7 81.2
57.3 43.9 100.5
. 39.2 41.7 100.5
j 55.1 48.8 70.9
t, 45.7 50.9 98.0
53.0
49.7
69.6
48.1
48.9
46.4
44.7
55.5
47.4
52.2
43.5
39.9
50.0
49.3
54.5
40.6
39.9
42.1
50.8
39.9
41.
40.
48.
46.
45.
43
43
51
46
37
5
1
8
,0
.3
.1
.9
.6
.7
.5
71.9
67.3
89.3
82.4
80.0
68.4
68.4
76.6
104.4
82.5
110 I
-------
BLOOD - Lead
GrJ- -.-> !
(smokers)
022
054
03B
C 2V
030
020
033
016
069
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non smoker
046
035
024
013
019
015
049
055
034
045
067
070
1
i "—
26.7
22.8
26.7
20.3
23.1
20.8
24.4
25.3
38.9
IS. 3
21.7
30.6
30.3
32.8
2^..1
25.8
26.8
21.9
19.1
10.9
18.4
18.9
19.1
30.8
s)
24.7
19.2
24.4
26.7
23.3
19.6
22.1
26.3
26.6
56.6
30.8
P
Te s
2
40.2
39.1
1 ..', . -1
20.3
23.1
22.4
26.6
36.7
27.6
4 6 . 1
16.2
20.5
35.0
22.6
20.5
29.6
41.8
27.9
24.6
13.9
17.6
17.4
27.2
25.2
28.0
22.0
28.0
22.4
19.9
27.3
28.6
30.3
22.2
38.1
15.1
18.1
:;/'.! 00 n
t
3
23.2
17.9
16.9
15.6
13.8
20.7
12.0
9.3
IS.?
14.4
19.1
18.6
12.2
16.0
18.4
17.3
17.2
IS. 8
18.8
33.6
23.0
22.3
18.8
13.4
11.6
7.8
21.7
13.6
17.6
10.1
23.9
8.0
27.3
17.2
17.6
il \vhol'
4
35.5
29.3
23.4
15.7
13.7
lo . 2
16.7
15.3
9.3
15.7
17.7
11.3
16.2
21.6
16.7
14.1
17.8
15.0
46.0
48.8
40.8
66.7
35.7
23.0
16.0
19.5
32.5
26.3
24.6
11.8
24.6
24.9
13.1
24.4
23.5
G r o • -~J '" A
(smokers )
\ .
350
348
347
329
336
-~t •"> J
321
313
284
320
340
253
318
339
283
337
346
^314
315
*"> A C\
349
286
325
333
345
316
331
(non smi
323
O A ">
31
-------
; BLOOD - Copper
; ji^/lOO ml whole blood
Group 3
(smokers)
141
1.-0
{ 142
i 295
2?.l
187
! 236
1 :
-------
^g/100 ml w
hole blood
o \ Test
Group 2A 4
Group_2 _TeS% - | (smokers) _1_ _i_ -1- -
(i^ -'- ^
503
264
OOi
273
231
504
270
262
266
405
066
058
002
275
061
(non
279
003
001
502
269
500
402
404
006
005
n L C
ODD
276
501
278
505
~ i < / -_
7o~7 22.2 29.9 31.5
77 1 23 0 17.8 13.9
27' ,- --' 1 34.2
403 4 i . o - • - • a °
29.8 3E.O 27.2 ^.E
2°-! \\A "• :
£°, ».'o «•? "••
25.4 ?0.5 20. S
35 0 36.1 34.4
39.4 37.8 34.4 36.0
54 3 45.2 36.9
57 C 51.4 45.6 41.4
20.0 40.7
26~3 21.4 20.4 23.5
345 42.9 33.0 43.4
J •* • -' 1
1
smokers)
27.1 23.0 17.8 18.9
28 9 27.9 29.0 23.4
_ 31.2 27.2 19.8
21 9 19.7 21.8 19.8
27 ! 44.4 30.8 29.7
Z4'5 18.1
IS'.O 21.4 13.4 11.5
29 3 19.3 15.7 20.4
30.0 36.4 26.7 29.3
405 43.9 31.4 37.5
ll.3 66.4 37.7 43.9
24.8 32.1 21.2 ----
24 0 15.0 21.2 23.5
2l'.0 20.4 15.7 18.5
19.5 42.9 26.7 18.5
7-1 n 21.4 11-8 14.6
H'.S 26.8 20.4 30.5
298
307
291
7^7
£ O (
248
29°
303
401
309
305
288
292
601
-i / A
261
250
(non
246
259
304
249
257
400
251
255
290
301
1
26.1 31.7 24.2 30.V
4o a 20 -4 18.4 19. -
17'Q 19.7 15.0 17.7
47',9 28.2 20.7
13. S 20.4 17.3
17.2 2°. 6 24.7
Af - -> ^ 7 2 2 . 4
16.3 -»•-
17.9 30.4 15.5
16.5 22.4 15.0
16.9 30.4 16.1
11.5
"/.I". 46.4 56.0
36.8 20.4
74.0 21.6 80.0
24'.0 28.0 18.7
smokers)
21.3 25.4 17.3
9.6 19.0 17.8
11.0 39.2 12.7
16.5 25.6 15.0
13.8 19.2 9.2
14.1 23.2 29.3
12.7 17.6 29.3
21 1 18.4 21.3
19.2 24.0
16.9 20.0 8.0
23.2
13 ."-
26.7
14.9
24.2
14."'
22.9
19.3
29.1
27.7
19.?-
18.0
17.7
20.4
9.9
19.8
14.3
19.2
14.9
14 .3
18.6
8.5
113
-------
BLOOD - Lead
Gro-in 3
f;
112
141
180
142
?°4
£f t"
295
221
187
| 236
149
176
600
139
230
204
210
098
122
Givers) 1
19.
16.
14.
20.
1 7 .
10.
17.
20.
14.
6.
7.
4.
9.
18.
11.
12.
9.
10.
6
0
9
6
a
o
0
8
6
2
1
6
4
2
5
3
5
0
1
Jig/ 100
ml whole blood
Test
Z
16 2
10.1
10.8
25.2
1 7 ~<
J ' . j
12.6
19.8
19.8
12.7
10.5
14.5
11.9
11.1
16.3
16.3
7.7
9.6
8.1
3
10.0
7.7
9.2
9.2
_ . — -
10.0
....
6.7.
7.7
13.8
13.1
24.6
20.3
11.5
18.0
14.7
4
22.
14.
17.
15.
- * -
8.
...
12.
17.
16.
10.
15.
8.
8.
11.
10.
Group 3 A
8
.1
1
2
_
0
_
-
2
1
0
0
0
8
8
3
0
(non smokers)
111
311
133
203
297
080
161
110
224
129
296
222
094
SBwssrawB
14.
20.
17.
14.
10.
10.
8.
A -a
i j .
8.
10.
4.
7.
11.
9.
9
0
8
2
5
9
7
3
9
8
6
3
8
10.8
17.3
20.8
15.1
11.9
12.7
12.7
\ Q ft
J. 7 , O
11.1
13.7
11.9
13.2
15.8
9.6
8.1
8.1
10.6
7.3
9.6
13.1
13.8
?? Q
C.C. . 7
6.6
16.4
13.1
11.5
8.2
14.7
15.
15.
22.
15.
13.
15.
13.
4 ^
•t -> •
7.
7.
10.
8.
13.
5.
2
2
0
2
3
2
3
5
5
5
0
8
0
(binokers)
091
131
227
245
706
£>UU
226
126
229
195
233
175 .
157
209
188
123
182
214
186
172
244
109
169
Test
1
13.8
20.9
9.4
10.5
17. 1
12.1
9.4
14.3
13.6
16.0
13.6
17.6
14.4
13.6
16.0
16.0
5.6
12.8
21.6
19.2
12.6
9.1
2
14.9
28.6
11.4
8.0
11 .4
18.9
9.1
9.1
8.4
9.8
9.8
7.0
9.1
10.5
8.4
11.9
9.1
16.4
11.1
7.7
10.1
3
9.7
7.7
8.7
17.7
14.4
16.3
9.8
9.2
14.4
13.1
11.8
12.4
12.4
15.0
6.3
9.2
11.2
17.0
7.3
7.8
4
25.3
11.7
11.7
12.7
15.3
19.9
30.6
11.0
19.2
14.6
21.6
9.2
16.0
13.1
9.7
(non smokers)
165
083
136
215
i An
I D V
120
097
213
225
134
166
125
170
234
118
ff 4 ' ' '•
12.7
15.4
8.8
8.8
•(•in
JL 1 i \J
8.3
8.8
5.0
4.0
17.6
17.6
8.0
21.6
9.7
13.7
IE. 6
8.6
8.6
Q 7
7*1
10.3
12.0
7.7
11.9
9.8
4.9
18.9
11.6
10.6
9.7
9.2
12.1
9.2
6.7
8.7
-_-_
8.5
14.4
10.5
9.8
14.4
9.7
8.7
23,8
9.2
9.7
12.1
18.2
25.2
17.3
20.4
22.3
7.3
9.2
-------
BLOOD - Manganese
Group 1
(smokers) _ 1 _
022 4.3
054 1 • :-
03b 2.4
029 1-2
i "5 £.
f 3 ? - • -
020 12.7
033 1.4
016 1-4
,,/.-> -17
1)6 / * • '
, 0 - -IS
0 3 o 1.3
040 1.4
003 1 • 6
039 1-4
027 1.3
032 2.0
042 1.6
023 1 • 4
026 1.0
053
012 2.3
047 1.0
014 1.0
017 2.9
071 3.0
(non smokers)
046
V A \J
035 2.1
024 1 .6
013 1.7
019 1.7
v * /
015 1.6
049 1.8
055 2.2
034 4.8
045 1 • 7
067 3.0
070 1.3
Hg/ 100 nil Blood
Test Group 1A
234 (smokers) 1
3.2
4 7
L . L:
1.5
1.6
"s. 4
J> - -1
2.2
3.3
1.5
? ?
i> • i •
1 1
-i » •*
1.4
1.7
1.1
2.2
1.6
0.8
2.7
3.4
3.2
3.8
1.2
1.6
1.4
2.9
3.4
1.9
1.1
2.0
2.3
1.7
2.2
1.7
3.1
1.4
1.3
1.8
1.8 2.9
i ^ 12
± • ~J -* • *"•
1.3 1.3
1.3 0.7
23 1 -Q
L* * -J •* • '
1.6 1.7
1.7 0.9
1.4 1.1
0.7
1 . ?. 0.9
3.0 1.0
2.6 3.1
0.9
1.1 1.3
2.0 1.0
1.6 1.3
2.7 2.8
2.1 1.5
3.1
5.1 1.6
1.9 1.8
2.8 1.8
1.8 1.9
2.3 2.0
4.0 2.3
1.2 2.6
1.4 1.2
1.5 3.1
2.1 1.4
1.4 2.0
2.6 1.4
2.8 1.6
2.0 1.6
2.5 1.1
1.9 0.8
2.4 2.4
350
348
347
329
336
321
313
284
320
340
253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
(non
323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
1.6
2.5
1.0
3.6
3.4
2.5
9.4
2.2
4.2
2.0
2.2
2.5
1.4
3.4
2.8
1.5
4.0
7.2
3.2
3.1
1.4
1.8
5.3
smokers)
1.0
10.0
0.8
2.2
1.8
7.2
4.9
3.3
1.8
3.1
1.2
1.4
0.9
1.6
Test
2 3
3.3
0.8
2.2
2.9
0.9
6.4
4.5
6.4
1.9
2.2
2.6
1.3
5.8
1.4
2.4
1.8
3.7
1.4
1.1
1.4
1.5
1.0
1.0
1.8
3.4
2.1
10.8
6.4
2.2
2.8
1.7
2.5
1.5
1.9
1.9
- - -
2.2
1.7
6.1
2.0
2.8
1.4
7.9
0.9
1.1
1.5
1.5
1.9
2.2
1.5
2.1
7.9
3.7
1.2
2.1
1.2
3.5
5.9
1.6
1.4
3.6
3.7
3.1
4.8
0.5
1.5
1.2
1.7
0.8
4.7
2.3
4.0
1.3
1.5
3.0
1.9
4.8
1.9
0.8
1.8
1.3
6.3
1.4
2.2
2.0
3.7
4.3
IX
2.3
2.8
3..-'
3.0
2.0
3.6
2.4
1.6
1.4
1.9
1.7
2.3
1.9
2.6
2.9
0.6
1.8
2.0
3.7
2.5
2.9
4.8
2.0
4.1
2.2
3.2
2.6
1.8
2.9
-------
- M a ngane se
(ig/100ml Blond
G •-•<.-•
., ^
(smokers) 1
503
264
004
L. » J
281
504
Z70
262
266
405
066
058
002
275
061
(non
279
003
001
502
269
500
402
404
006
005
065
276
501
278
505
277
271
5.i
1.7
2.6
3.9
2.5
2.0
?..3 ,
1.6
1.1
1.4
2.4
2.0
...
1.8
1.6
smokers)
2.9
2.1
1.6
2.6
2.1
1.9
1.6
1.2
2.0
1.8
1.4
2.7
1.9
2.5
1.0
1.5
Tc
2
?.")
1.5
2.3
2.4
3.2
-.
. ?-.7
1.8
2.9
2.9
1.5
3.5
4.3
1.9
6.0
1.5
2.6
3.8
1.7
2.9
2.4
3.6
2.0
.9
0
1.9
2.7
1.6
3.1
2.8
1.4
st
3
4 -
1.3
4.4
1.7
1.9
2.3
2.4
3.0
2.6
1.7
1.9
2.7
1.2
1.8
3.7
1.9
1.1
Z.I
2.4
2.0
1.3
1.8
1.6
1.4
2.3
3.2
2.3
3.1
4.3
2.0
2.2
1.4
4
3.6
2.1
4.3
3.2
3.7
1.3
2.9
...
2.2
...
1.6
2.8
1.5
2.7
_ _^
3.3
2.1
1.5
2.3
1.9
2.4
6.3
2.9
3.3
3.4
1.5
2.5
1.6
2.6
Group
2A
(smoker;,) 1
298
307
291
287
Z48
299
303
•501
309
305
288
292
601
261
250
(non
246
259
304
249
257
400
251
255
290
301
1.9
3.7
3.4
4.9
1.9
3.2
2.6
2.4
2.7
2.4
...
2.8
6.2
smokers)
1.8
2.2
2.4
2.9
1.1
2.3
2.8
2.0
1.7
Test
7
2.7
3.7
2.2
2.4
2.6
2.2
2.8
2.6
1.9
1.6
1.1
1.5
1.6
1.3
2.2
2.2
2.2
3.9
1.3
2.6
1.5
1.7
1.4
1.3
3
1.1
2.1
5.3
1.5
2.1
1.8
2.4
3.1
1.4
2.0
2.0
.9
2.1
2.2
2.3
.8
2.9
1.6
1.2
1.3
2.4
2.1
1.8
1.7
1.8
1.7
1.5
1.5
2.1
2.3
1.1
1.8
1.4
1.4
1.8
1.7
1.3
1.8
1.5
2.2
1.9
2.9
1.1
2.3
1.6
2.0
1.6
1.9
1.8
1.0
116
-------
T
•*A
Test
Z 3_
V-i-""!' -L
(smokers)
4
1.1
0'
'
112 -,'c z 3 4.0
? 8 2.5 L.Z
414 7 q 1 7 2-0 3.0
180 2.7" • 9
142 2'9 V6, —
295 1-1 V3 : , 1.2
x 7 2 . J * • -
-571 *'
"" < " 13
. cv 1 • '*
lof _
236 2'4 ' i q ?.3
149 2'4 M 44 2.2
,/ 74 t . ^ t- • —
176 I'6 2'7 1-6 1.6
60°0 ~1~~9 z'-4 1.7 3.7
439 ,9 2.4 1.9 4.7
230 ; A 1 6 2.0 2.0
,0i 1.6 a-° . ,
204 ! z 1.0 1'4 ^
210 a-^ 2 8 4.1
093 3'° 4'9 13 1.6
122 1-6 2'2 1>3
(non smokers)
2 1 1-6 1-° 1>4
114 15 1.3 1-2 4'2
344 I'l 1.4 3.8 3.0
133 ^' . 7 A s 2.0
JB 1.7 i.o "
203 21 2.5 2.1 3.0
2W 15 1.6 1.4 1-9
080 15 2.2 1.0 3-3
161 !•= i d 5 2.5
177 2'5 ' 1<7 2.0
440 40 2 1 1-8 2'7
224 4.0 • Ii9
179 2'6 o L -\ 1
1^^ . / -17 2.6 3.1
296 4'° :\ i 3 1.8
0-77 2.1 2.3 1-^
222 5 1>4 1.6
094 1ft
2ZI 1 6 2.5 2.6 2.d
245 VQ 24
206 V! 16 2.0 2.3
2?^> 2'9 ]'* ! o 1-5
47- 1.9 1- ' o ,
420 \2 2.6 1.9 3'i
229 3'2 q 2.2 1.8
195 70 29 I'4 1>4
233 2'9 Z'l 4.8 2.3
175 I-7 3-3. 21 1.7
1Q / *± t- • *
M i- • ^ n
«• , 3 1-9 2.5 2.9
209 Vc 2 4 2.3 2.0
488 M 3'.3 L2 1-6
123 , X = 26 3.1
182 3'4 ^'' 20
t-4 2* 21 2.6
486 \\ 25 2.5 —
472 ^ q 2*8 1.4 2.3
244 1-9 2'° ___ 1.6
409 '^ 21 —
x£.a 3.1 2-1
169 J
(non smokers)
165 2.1 L6 4'°7 I'l
lO-1 ,1/1 7 ? £ • ^
70 4.1 c. . t.
f3 ;°5 2.4 1.1 4'2
436 I \ 1 4 1.8
215 2.1 I-"*
160 2'° 2'" 3 2 1.2
120 3.9 1-2 32
J 7 21 1 . t-
097 3*3 72 1.0 4'6
213 79 22 1-6 2'2
^4 16 23 2.7 2-6
7 A 1 2
166 32 29 2.7 3.0
125 3.2 4.? i<7
1*7 _^— J..L-
470 I -17 25 3.1
234 2.1 1-2 2.5
118 2.7 3.4 —
117
-------
Pt-ASMA - Zinc
Hg/100ml Plasma
Group 1
(smokers)
022
G:> ••
038
07.9
03'J
020
033
016
069
036
040
008
039
027
c:,?
04Z
CC.3
o^6
053
012
047
014
017
071
Test
1
310
~* f,f
316
34Z
_, •-, •
3ZO
398
378
•1C 8
374
312
336
308
378
3ZO
344
330
330
40Z
326
406
336
382
360
2
400
".'.0
432
372
• -,••)
302
400
492
4
-------
100 ml Plasma
Ci rouo 2
(smokers)
503
') .' «
* . • ~i
004
273
2b1
504
270
2t>2
266
405
066
058
002
275
061
1
549
?•' t
514
3'°0
214
197
184
211
218
327
169
335
--
297
282
" •;• s t
T
301
4 3 3
359
294
T -> -,
C ^ •>
290
425
379
332
298
356
298
--
433
i93
3
238
i ~> .'.
392
392
336
392
381
374
320
290
312
428
396
378
294
4
426
2C6
324
--
240
377
337
- _
_ _
318
_ _
378
318
382
378
Group 2A
(smoke r s )
298
307
291
287
248
299
303
401
309
305
288
292
601
261
250
1
492
282
279
322
358
311
337
442
400
374
m* _
345
180
242
337
Tes
1
»_
321
262
313
306
369
302
229
299
211
258
236
316
294
261
323
t
3
240
487
261
269
305
334
254
320
236
436
276
330
334
287
261
•I
356
385
301
293
367
400
282
257
148
278
326
347
286
265
278
(non smi
279
003
001
502
269
402
404
006
005
065
276
501
278
505
277
271
okers)
288
456
284
206
290
301
169
188
227
197
293
238
360
279
312
331
(non smokers)
240
414
209
329
290
278
433
313
247
259
286
182
348
321
240
329
320
284
296
340
356
385
414
305
312
428
370
294
352
341
254
290
350
434
270
327
340
326
333
300
551
285
326
326
292
318
296
246
259
304
249
257
400
251
255
290
301
232
326
337
323
297
396
312
290
_ _
370
358
391
261
316
349
280
378
312
316
225
280
338
276
254
391
240
425
280
298
290
319
286
274
381
378
278
274
290
257
294
119 .
-------
PLASMA - Zinc
p.g/100 ml Plasma
Group 3
(smokers)
112
141
180
142
221
187
236
149
176
600
139
230
204
210
098
122
1
22.1
390
217
241
241
2o9
315
222
256
252
253
335
324
364
324
200
Test
2
Z!9
172
143
210
210
224
239
283
201
239
250
210
216
335
227
301
3
"505
272
171
223
240
. .
_ _
223
204
223
232
309
260
208
230
208
4
256
311
226
286
306
_.
__
191
195
286
195
286
337
332
217
318
(non smokers)
111
311
133
203
297
080
161
177
110
224
129
296
222
094
221
277
241
322
298
210
214
319
277
315
284
297
333
390
243
214
219
291
196
201
201
294
288
283
250
199
238
233
232
7.68
203
223
171
250
213
223
232
213
299
234
252
291
151
216
341
306
271
243
248
238
248
338
235
295
281
281
Grouo 3 A
(smokers)
091
131
227
245
226
126
229
195
233
. 175
157
209
188
123
182
214
186
172
Z44
109
169
1
244
231
272
175
228
250
290
165
264
255
201
353
265
265
175
218
196
235
243
188
162
Test
->
254
168
281
177
241
178
173
197
216
277
164
244
192
220
352
230
253
220
173
220
220
3
212
—
249
221
286
304
328
268
314
231
291
309
314
248
248
296
276
253
191
234
253
4
286
—
240
324
274
247
277
290
412
243
316
321
433
244
220
--
267
--
403
267
--
(non smokers)
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
351
194
198
295
268
226
299
313
384
346
184
316
341
188
132
141
127
163
186
141
186
- .
202
216
253
234
183
21 1
277
183
194
217
221
217
__
249
295
226
295
272
-.
357
234
195
..
215
240
236
__
202
244
307
334
230
..
267
520
478
286
120
-------
HAIR - Cadmium
Hair
Group 1
(smokers)
022
054
038
029
030
020
033
016
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non smokers)
046
035
024
013
019
015
049
055
034
045
067
070
1
.2
.4
.1
3.9
.8
--
.2.
1.9
8.3
. 1
.3
.4
.8
1. 1
2.4
._
.7
.2
1.2
. 1
.7
. 5
.2
.2
4.3
. 5
. 3
.8
.2
1.4
1.0
.3
.7
.7
0
Test
2
.3
.7
.7
3.0
1.0
1. 1
. 1
2.0
9.1
. 1
.5
.5
.9
1.3
2.2
.3
.6
.3
.8
.3
.8
.3
.5
.2
.4
. 5
.3
.8
.4
1.9
.4
.7
1.2
1.2
0
3
0
.4
.2
2.4
.7
_.
0
1.2
15.2
0
0
.3
1.0
.5
2.7
__
.3
. 1
1. 1
.2
.6
.5
.5
0
0
. 3
. 3
. 5
0
1.0
.5
.4
1.2
.7
0
4
0
.3
.2
2.9
.6
1.0
0
2.8
12.1
0
0
.6
.7
.7
1.8
.3
.3
.1
.3
.2
.7
.3
.4
0
. 1
. 1
.3
.4
0
1.0
.5
.4
1.2
. 4
0
Group 1A
(smokers) 1
350
348 1.
347
329
336
321
313
284 15.
320
• 340 1.
253 1.
318
339 1.
283
337
314
315
349 1.
286 2.
325 1.
333
345
316
331
(non smokers)
323
312 2.
334
285 1.
326
258
343
327
330 0
351
338
324
328
341
319
2
7
9
6
5
8
5
0
4
3
7
2
1
3
1
4
2
7
0
i
4
2
1
6
0
8
1
6
$
3
3
6
4
7
8
3
3
Test
2
.1
1.8
.7
.6
.3
. 5
.2
13.5
.9
1.3
1.8
.2
1.0
.3
.1
.2
.2
3.6
2.0
1.0
.5
4.7
.3
.1
.7
2.2
1.0
.5
.6
.4
.2
.2
. 1
.6
.4
.7
.8
.3
.2
3
. 1
.9
.6
.5
.5
.5
.4
7.8
.5
1.4
. 1
1.3
.4
.2
. 1
.8
.3
7.0
2.4
.9
.6
_-
.3
. 1
. 6
2. 1
1.0
.5
.4
.2
1.3
. 1
.6
.4
.6
.4
.2
.3
i
i
4
0
1.2
.5
.5
.4
.5
.3
8.4
.4
.8
1.3
0
1.2
.3
. 1
.3
.3
5.7
3.6
1.0
.6
4.7
.3
.3
2. 2
2.2
1. 1
.4
.3
.5
.2
.2
. 1
. 6
. 6
. 6
.4
. 3
.3
122
-------
HAIR - Cadmium
Kg/g Hair
T ^ c f
Grou^J, Test 3
(smokers) |__ ?. —
503 -1 «4 '2
264 *4 -o 1*2
270 .? -9 1.2
405 2~0 2.6 1-7
OVJ 2.8 2.3 3.o
v 7 .8
OOZ ' u \
o— 5 -6 -o
2o • D ,
\ -> o .6
061 i-2 u
(non smokers)
279 -Z "4 "2
003 -- " ""
001 L9 -8 1-5
i 4 4
502 -3 '4
269 2.1 1.2 1.*
402 -5 .4 .6
404 -6 -5 -6
065 -- " "~
501 .8 LI 1-4
278 -3 "4 -
277 -3 "3 "
Group 2A ^
4 (smokers) 1
, — '•*
3 293 1-°
1 307 1C.1
l'.l 291 1-9
5.4 287 5-9
1.1 248 1.0
2.0 299 2.9
.6 303 -8
.7 401 !-4
1.4 309 2.0
305 I*7
ZBS . 5- 3
/
292 • b
601 5.1
.2 261 -6
2.2 250 2.9
1 ">
i . ^
.
< K
1 . 3
. 7 (non smokers)
.6 246 -2
.3 259 5'5
l' 6 304 I-6
.3 249 -3
3.0 257 I-6
.5 400 I-5
251 -2
255 -3
290 3.4
301 2.2
:e st
-> 1 4
2 -J ^
^ r. T
8.7 5.0 .3
8.4 5.2 5.4
3.7 1.6 2.1
5.6 6.5 6.1
r, 0 °
.9 • '
2.0 2.6 1.9
1.0 1.0 -5
.5 .6 -4
2.4 1.9 ?-.2
1 R 11
.. — 1«O i. • *
. o C ,1
5.5 4.8 b . 4
15 .4 1.1
1 * J *
3.1 1.6 1.5
. . Q
.7 1.1 -8
2.7 3.1 2.9
.1 -2 -2
4.9 2.5
1.4 2.3 1.5
.3 .2 -3
i 2 2.0 2. 1
.7 .7 .9
.2 .4 .2
. «
1.2 .1 • [
— /
2.7 2.0 5.6
_i-
2.2 1.6 2..o
123
-------
HAIR - Cadmium
jig/g Hair
j Group 3
,' (smokers)
112
' 141
180
i 142
; 295
236
1-19
600
! 139
; 230
Z04
! 210
098
122
(non smokers)
111
311
133
203
297
080
161
177
110
224
129
296
222
094
1
.4
.7
1.2
.4
__
--
. 5
.9
. 1
.8
.3
1.0
.7
.4
.3
.2
.8
1.7
.2
1.1
. 5
.5
.7
.6
.2
.9
.3
.2
Test
2
.4
.6
.8
.8
__
.5
* s
.4
.1
.4
.2
.6
.7
. 1
.2
.2
1.0
2.4
. 1
1.3
.4
.7
.8
1.0
.3
.8
0
. 1
3
.4
__
.7
.3
__
-_
Z
1.0
0
.8
1.0
.8
.6
.3
.4
.1
1. 1
1.2
.2
.8
.4
. 5
.6
.6
. 1
.4
0
.4
4
.5
.6
1.6
.7
.5
..
--
.6
.1
.2
.8
.9
.7
.3
.3
.1
.9
2.0
. 1
.9
.5
. 5
.4
.6
.2
.9
. 1
1. 1
Group 3A
(smokers)
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
186
172
244
109
1
.4
__
0
.3
.7
.8
1.0
1.2
.3
.3
.3
.5
0
0
1.8
.2
1.0
2.9
.8
Test
2
.2
__
0
.3
.6
1.1
.9
2.1
.2
.6
.2
.4
.9
0
.5
.2
.9
1.4
.9
3
.4
__
1.9
.3
.6
1.6
.9
1.9
.3
.6
. 1
.4
0
0
.6
.2
1.4
1.5
.9
4
.4
.5
1.8
.3
.8
.9
1. 1
1.7
.4
.4
0
.3
0
. 1
1.4
.1
1.1
2.3
--
(non smokers)
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
.8
1.0
. 3
.4
1.6
.5
. 1
.6
.2
0
__
.2
.9
1.6
. 1
.8
1.2
.2
.7
.9
.2
. 1
.5
.2
0
__
. 1
.2
1.5
.7
.9
.9
. 1
.4
.7
.5
__
.6
.2
0
__
.2
.8
1.2
.2
.9
.7
.2
. 3
.8
.3
._
. 5
.2
0
. 1
.2
.8
.9
..
124
-------
HA IR - Cop
G roun 2
' . '-..;--' '
503 5.0
" • ', " '"' - ?
270 10- 7
266
405 6.5
058 12.5
002 33.3
?,75 11. ^
061 2.0.2.
(non smokers)
279 7.1
nr, i q 7
001 - ^
502 5,9
269 13-°
402 !''•&
404 ''.°
065
501 7.6
278 11.0
505
277 12.7
HP^/p, Hair
Test
_ 2 _ 3 _.4_
5.5 3.5 5.0
4 /no 3r> . 5
12.') 15.9 13.2
11.6
6. b 5.7 7.2
10.8 14.3 10.2
35.3 38.4 34.0
i -\ -}
9,8 j U . o i <- .
-in " 1 U
j . 9 ' • '-
10.0 7.1 7.
10.
8. 6 10. 1 10.
5.8 5.4 6.
3.3 7.5 9.
16.1 16.7 18
11.5 10.0 10
13
7*6 7.:- 8
9.8 9.6 10
12.9 -- i2
13.5 -- 15
3
n
\J
0
8
5
, 0
. 6
. 6
. 0
. 2
. 3
. 5
. 3
.0
per
Group
2A
(smokers) 1 __
298 12.2
;v~>7 15.0
291 I0-b
^87 14.1
248
299
303
j
309
305
288
292
601
2 6 1
250
(non
246
259
304
249
257
400
251
255
290
301
11. 5
22. 5
8.0
17.2
14.4
17. 2
10. 2
11.8
18. 8
11.0
15.0
smokers)
1 1. 1
25.2
32.4
24. 4
9.3
19.7
41.4
9.2
10.7
11. 3
Test
2
— —
3.8
9.6
i 1.7
13. 3
10.0
20. 6
13.2
13. 6
17.
__
9.
10,
7.
10.
11.
8.
21,
28
8
6
13
41
8
12
5
6
3
8
3
4
, 5
.9
. 7
.9
. 5
. 1
.9
. 7
. 5
14. 6
3
— .. • —
8.4
13.5
13. 1
16.9
11. 5
25. 6
17.2
13. 5
13.7
18.4
7. 7
9. 9
9.0
11. 8
11. 5
8.7
26. 1
32.2
8.8
9.6
12. 5
46.2
10.0
12.4
14. 5
4
5. 4
13.2
1 1.
16. z
10. C
20. b
9.4
12. -
13.
14.
8.
12.
1 1.
12.
1 1 .
8,
15
30
9
9
15
36
10
10
1 2
-
^
n
0
i
5
, 1
. C
, I
. 9
. 3
. 1
. 0
i i ""*
125
-------
HAIR - Copper
Jig/g
Group 1
(rr-s?
022
054
038
029
030
020
033
016
03f>
0-10
008
039
O.'.V
03Z
042
023
026
053
012
047
014
017
071
(non
046
035
024
013
019
015
049
055
034
045
067
070
•-er.) 1
6.
17.
6.
8.
10.
--
6.
13.
19.
10.
7.
19.
11.
12.
9.
..
11.
13.
36.
9.
15.
8.
9.
smokers)
7.
5.
12.
8.
16.
6.
32.
37.
7.
11.
12.
13.
8
7
5
7
5
5
9
9
9
8
9
7
5
0
2
1
7
7
4
2
4
0
9
3
4
1
8
2
8
5
7
9
0
Te
2
8.3
7.4
8.9
8.6
11.8
13.0
7.6
14. 9
16.9
11.2
8.2
13.9
12.4
16.8
8. 1
6.8
11.4
11.3
13.9
10, 1
21.3
7. 6
10.6
7.4
9.3
14. 7
9.0
11. 1
7.6
31. 3
37. 1
7.6
20. 3
12. 1
12.9
st
3
9.2
16.6
17.0
7.5
12.7
__
7.3
12.6
21.0
13.3
8.5
17.7
13.0
12.3
9.0
- .
9.3
12.5
11.3
10.6
13.5
9.0
10.9
8.3
9.0
13.4
7.6
12. 1
7.7
21.3
34.8
7.9
20.2
13. 3
12.4
4
8.
12.
10.
9.
11.
13.
7.
28.
19.
10.
7.
12.
1 1.
12.
7.
7.
9.
11.
9.
10.
11.
7.
9.
9.
8.
11.
8.
9.
6.
20.
26.
7.
11.
11.
12.
Hair
2
2
4
0
5
0
8
7
1
9
9 '
3
5
5
7
4
3
2
9
2
9
4
3
2
4
8
0
5
9
5
2
4
2
5
9
Group 1A
(smokers)
350
348
347
329
336
321
313
284
320
3-10
253
318
339
283
337
314
315
349
286
325
333
345
316
331
Test
1
10.2
10.0
9.0
26.0
9.6
12. 0
14. 6
13.6
24.4
21. 5
13.7
7.0
29. 1
8.5
8.4
8.7
13.0
11. 6
8.7
13.4
12.7
__
18.9
10.3
2
7.3
8.9
6.3
29.8
8.1
7.6
7.6
11.7
38.7
21.0
11.3
24.6
24.6
10.0
7.6
8.0
16.4
10.9
11.3
12.5
13.2
13.5
20.1
6.9
3
8.5
8.7
9.3
21. 1
9.7
9.1
12. 1
11.2
26.6
22.4
7.7
26.8
21. 1
8.6
7.0
8. 5
28.4
10.2
8.7
14.6
11.9
__
15.9
6.8
4
8.0
8.^
8.9
23.5
9. ?
11. b
14. 6
12. 1
40. 1
12. 1
18. 9
7. 1
27. -I
9. ^
7. 9
1 ~
25.0
10. 1
10.0
13.0
11.4
12.4
14.3
6.0
(non smokers)
• 323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
11.8
12.0
42.7
9.3
14. 1
20.0
29.9
7.2
6.7
7.9
9.0
19. 8
10.7
7.7
16.3
13.4
13.6
35.2
8. 1
11.4
19.2
28.4
8.7
6.9
8.6
9.3
19.7
11.0
8.0
17.9
12. 0
13. 0
38.0
9. 3
12. 8
28. 5
26.8
__
6.2
7.7
8.6
18.0
9.7
7. 5
14. 4
6.7
13. (.
38.7
8.7
13. '•
20.;
27."
7. '
6.(
7.-
8..
19.
9.
7.
13.
126
-------
HAIR - Coppe
-, Test
j£_oup_3 ^ ,
11Z 13.1 12.9 13.1 11.3
i-1 32.4 31.4 -- '-_'
loO ';:)-7 '"'•
54. 2 6Z.7 Sl.l --
"> 0 C,
" .-125.!
o j 6 " " " " „ 0
, ... it). & !V- ' ; '
•>0 2 23. ^ 3o. b
139 U.5 lY.4 13.0 12.7
" , < < < 1 0 < 11°
( ' i 1 . -I ! . i J *
^ • u i < . t i .
,;M 5.7 5.9 5.0 ..i
M0 23.0 21.5 2'-. 1 :•-<•-
098 54.8 44.0 56.3 47.7
122 ^1.4 62.6 63.3 33. b
(non smokers) „ _
ui 13.1 15,2 14.5 ID.D
311 13.4 14.2 n.O 14.2
'33 18.9 21.7 22.4 231
203 35.8 44.5 22.2 432
,07 8.5 8.9 8.. 8.9
80 24.1 26.5 28.4 307
161 19-1 18.4 17. < IB. 6
177 32 i 34.4 30.6 32, <
110 101.5 120.7 92.0 113.5
!24 36.9 34.0 70,5 52.1
;29 11.0 9.9 H.4 H.3
296 66.2 66.2 40.6 b3. 3
2?Z 10-4 10.0 17.4 11.4
094 32.5 29.8 32.1 19.8
G r oujp__3A
(smokers)
091
1 3 '
' / "/
tw ... i
7 ' S
C,' •, J
lib
126
? ? Q
C . L.
195
233
175
( & 7
1 D *
0 0 Q
i— Lr
188
123
1 H '
i \J <•*>
186
172
244
109
1
19.5
2 ' j . 2
15. i
21.1
31. 2
:> o . 7
I ^ 6
1 _ . V-J
2 b . 6
91.4
3. 9
57 , 8
11.2
9. 3
27. 6
25. 6
45. 8
170. 7
13. 6
(non smokers)
165 23.1
083 9.7
136 14-2
215 29.3
160 70.8
120 16.1
097 21.0
213 20.0
225 12.1
134 32.8
166
125
170
234
118
— ~
23.2
26. 3
16.0
7. 4
Test
__2__ _J__ .
18.7 19.3
20.2 13. 1
14.5 12.1
20. 6 20. 6
37.4 27.0
35. 8 37. i
13/5 14.7
35.9 33.1
136.4 111.4
8. 1 7.9
41.5 42.2
14. 6 11.7
11.1 10.1
11,1 10.7
20.2 22.8
35.9 39.3
97.3 115.9
13.4 14.2
22.7 18.2
12.4 8.0
13.4 13.9
28.6 27.0
40.6 28.9
11.4 17.3
20. 5
17.5 16.7
10.9 10.3
12.0 11.9
24.4 21.2
25.0 21.6
13.3 11.7
8.4 H.2
4
19. 5
27. 4
1 ' . '
10. 4
19. 1
28. 5
10.2
40. 5
1 52. ?
7 . ~.
32. 5
10. 7
7. 0
17.2
20. 5
39. 3
118. 5
17. 8
6. 2
15.2
34. 1
39. o
15. 4
17. 4
11.0
9. 8
26.9
24. 1
22. 7
10 C
3. 5
"* ~"
127
-------
HAIR - Lead
jig/g Hair
Group 1
(smokers)
022
054
038
029
030
oau
033
016
036
040
008
039
027
033
042
023
026
053
012
047
014
017
071
1
8.8
19.1
13.2
37.3
26.8
35.7
2.5
56.0
76.4
68.9
85.5
79.4
54.4
77.0
376.9
4. 1
10.6
9. 1
20.5
2.4
19. 1
19.9
4.3
Test
2
8.4
23.0
20. 7
31. 3
21.0
37..0
2.6
21.6
89.4
4.4
14.0
22.4
22.0
41.7
34.7
3.9
22.8
12.0
34.8
6.0
37.2
16.4
13.6
3
8.7
19.6
50.7
27.8
21.1
2. 1
15.6
197.5
3.8
6.0
9.0
18. 1
7.9
24.6
..
6.2
11.4
15.6
3.5-
16.7
17.2
5.8
4
6.6
18.4
35.6
33. 3
19.4
- .
3.7
30.8
41.4
4.8
7.4
12.2
12.6
9.6
14.6
..
4.6
11.5
8.5
2.4
14.4
12.0
6.7
Group 1A
(smokers)
350
348
347
329
336
321
313
284
320
340
253
318
339
283
337
314
315
349
286
325
333
345
316
331
1
2.0
77.3
20.5
26.8
14.6
11.4
18.9
48.6
13.8
15.8
34.3
2.5
28.9
1.4
4.1
7.7
0.8
27.9
6.5
4.5
1. 1
76.6
1. 1
4.3
Tesi
2
0.2
57.3
20.5
28.9
17.5
8.4
8.0
0.2
14.4
16.2
34.9
5.0
18.3
0.2
2.0
5.7
1.0
23.8
7.3
3.3
0.8
62.2
1.0
2.2
t
3
1.7
32.5
12.9
24.8
20.8
18.0
9.1
22.9
12. 6
16.7
1.2
20.3
3. 1
0.6
2.8
3. 1
5.0
25.3
9.3
6.5
1.3
--
1.3
1.1
4
0.2
42.2
11.2
33.8
17.2
9.0
11.0
35.4
14.0
7.6
27.4
1.2
25. 6
1.0
1.8
5.3
3.9
23.7
11.0
4.3
2.8
-_
4.7
1.6
(non smokers)
046
035
024
013
019
015
049
055
034
045
067
070
3.0
9.4
11. 1
5.5
17.7
17.4
54.8
46.8
6. 1
43.3
23.8
2.4
3. 1
13.0
14.5
8. 1
17.0
27.0
31.4
35.7
9.6
7. 1
52.8
1.6
21.9
7.9
16.5
6.9
16.9
9.8
26.4
24.4
5.4
11.0
16.4
2.8
4.0
8.8
8.8
4.9
12.6
9.0
26.6
17.4
5.4
11.2
10.4
1.8
(non smokers)
323
312
334
285
326
258
343
327
330
351
324
328
341
319
9.7
59.3
16.9
10. 6
8. 5
4.3
8.9
3. 3
2.6
10. 6
5.6
14.2
0.5
0.9
10. 1
65.5
22.5
6.0
5.8
3.4
6.7
2.8
1.2
10.3
1.6
14.9
0.8
0.4
10. 3
59.3
21.7
5.8
6.0
5.3
16.5
3.7
1.9
10.0
4. 1
10. 5
5.8
1. 1
4.4
65.0
28.5
4.4
6.8
4.2
5.8
2.0
1.4
9.4
1.8
10.2
0
1.8
128
-------
Hair
Grou£_2 Tf^st _
f j - 1 — .— - - - - -
5.5 10.9 8.8 8.9
z.,4 i^ -"--0 ;•/•'; -":
266 19!-? r~% -~c. Cr8
10->. 2 c,' '. */ -• - ' -• °
, , j -3 7 / Q
i i V " < • , , . 1 1 1 -J ^ . - ' •
05B K'-,.- *-• '
nn7 31.7 19.8 2i.O -0.3
, -, T - 7 ion ? '•> . 7
; ' ' . . > ' » ' ' J ' "
L' ' J - < j < n < / ( 1 1 7
. , i ; o ;> I . 1 1 n * • h ill.'
(iion smoVrrs)
^,, 10 2.0 3.1 ,.5
003 1 - 4 . A - "
001 18.9 14.4 14.5 11.8
50 12.2 17.3 19.3 22,4
269 H4.2 99.0 102.3 111.5
402 10.4 ^-8 12-" IZ-;
404 31.9 22.4 20.0 22.6
065 26.7
,n1 48.8 64.7 66.4 69. b
2?1 ^-6 9'4 7"6 9"2
50S 74.3 71.4
T77 16.8 17.4 20.4 S7.8
l
Group
(<- nioki
Z^> Q
98
307
?9 i
Cj! / J-
287
248
299
^- i — J
401
300
Ju 3
288
"' 4 ;
j^ / *-•
AO 1
•> .'. i
^ O i
250
(non
246
259
304
249
257
400
251
2 5 5
290
30 1
2A
= «) _1_
13. 5
43, 0
94. 3
51.2
6. 6
21. 7
•> r,
14.2
81. 9
t1 - . -•
10. 3
16, 9
44. 3
12.8
18. 5
smokers)
4. 5
60. 9
41. i
8.8
18.7
32. 9
9.2
4. 7
104. 7
59. 3
Test
2___ 3
11. 6 9. 5
43.7 20. 4
S. 5 5.4
47.5 38.9
6.4 5.4
17.7 23.6
2 0.6 11.6
13.2 8.9
55. 7 67. 7
: .5 27.8
8.3 7.7
11.3 15. 1
57.1 51.5
8.5 18.4
lfa.5 19.5
2.2 2.8
79. 6 105. 6
45.8 41.7
9.6 2.2
19.8 22.6
12.7 10.7
9.4 5.0
2.9 5.0
92.4 115.5
13.4 25.6
4
12.4
21.4
17.7
37. 5
4.8
21.0
18. 6
4. 6
47. 4
64. 1
9. 3
20. -
22. 7
10.3
1 0 . V
2. S
71.2
47. 7
5.0
24. 2
22. •;
8. !
4. 2
119. 3
56. 7
129
-------
HAIR - Lead
H£/g Hair
Cro-ip 3
(smokers)
11Z
141
180
i4Z
295
236
149
600
139
230
204
210
098
122
(non smoKo
111
311
133
203
297
080
161
177
110
224
129
296
222
094
Test
1
4.7
44.0
20.9
4.6
8.2
--
4.6
12.3 "
1.0
8.2
17.8
2.2
5.7
4.7
rs)
8.6
1.8
1.2
11.3
2.9
17.1
8.9
4. 1
2.8
9.8
6.8
8.9
39.0
4.8
2
8. 1
85.8
?0. 1
2.4
_-
2.4
4.3
18.0
0.6
4.4
16. 1
3.8
5. 1
2.2
4.6
2.4
1.8
4.4
1.6
3.7
6.0
2.4
1.2
5.5
10. 1
4.6
17. 1
2.8
3
4. 3
4.3
6.1
5.0
--
--
2.7
6.3
1.0
3.0
12.9
4.7
3.5
2.2
6.3
0.9
2.4
3.3
2.8
6.4
4.8
2.0
0.7
3.0
5.4
0.5
6.6
1.8
4
4.7
17.8
18.2
2.6
--
._
2.4
8.7
0.4
3.6
14.3
4.9
6.7
2.5
4.1
2.4
1. 1
6.0
2.0
5.5
4.5
2.6
1.7
5.4
4.5
3.8
26.4
2.4
Grouo 3 A
(smokers) 1
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
186
172
244
109
(non
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
3.1
4.0
0
6.8
3.3
5.5
5.5
2.0
0.3
5.3
1.8
5.5
0
2.0
2.7
11.6
2.8
4. 1
5.2
smokers)
5. 5
19.3
10.7
3.6
12.8
11.9
7.6
1.2
1.6
3.9
0.8
9.5
1.4
11.2
1.0
Test
2
1.4
__
0
5.3
5.0
2.4
7.4
5.9
1.8
3.8
0.6
1.6
2.2
1.6
4.6
7.9
8.7
4.2
6.5
6.1
20.0
9.7
4.8
16.2
9.5
6.9
1.8
3.2
3.6
«*.
2.8
3.6
15.8
19.1
3
1.8
__
4.5
6.2
1.7
2.6
4.7
5. 1
2.0
2.8
0.6
2.6
0
1. 1
5.4
6.0
4.9
3.6
5.8
10.6
17.8
13.7
6.4
14.7
16. 1
__
1.7
3. 1
2.3
__
9.4
1. 1
10.6
0.8
4
2.7
—
4.2
6.7
3.3
2.7
5.8
2.4
1.2
6.3
0.9
2.2
0
3.6
2.6
6.6
6.6
4.2
--
10.8
40.4
10.2
7.3
5.4
11.4
__
1.2
4.6
2.2
_.
15.3
1. 3
11.4
__
130
-------
HAIR - >.'ar,0
348
347
329
336
321
313
284
320
340
253
318
339
283
3'37
314
315
349
286
325
333
345
316
331
1
.16
.40
1.29
.64
.20
.36
.22
1.34
.24
.14
.42
.21
.34
.04
.13
.17
.13
.28
.06
.18
.15
.10
.22
.06
T
2
.06
.28
1.29
.35
.12
.13
.02
1.73
.35
.14
.37
.12
.24
.04
.08
.22
.20
.39
0
.10
.08
.12
.10
.06
e st
3
.14
.25
1.19
.42
.17
.27
.17
.79
.23
.16
.12
.54
.29
.02
.15
.27
.44
.59
.04
.08
.15
_• •. _
.08
0
4
- — ..•.„
.12
.30
1.07
.03
1.12
.34
.38
.85
.32
.16
.38
.12
.46
0
.18
.34
.60
.70
0
.08
.07
.16
.10
(non smokers)
046
035
024
013
019
015
049
055
034
045
067
070
(non smokers)
.04
0
.12
0
.04
0
.33
.29
.04
3.04
.19
.04
.38
.31
.18
.02
.31
.18
.51
.18
.04
.61
.20
.04
.08
.14
.10
.73
.18
.05
.24
.37
.17
.63
.32
.07
.09
.17
.07
.04
.19
.13
.26
.21
.06
.51
.15
.04
323
312
334
• 285
326
258
343
327
330
351
338
324
328
341
319
.08
.42
.16
.16
1.44
.40
.14
.22
.06
.18
.15
.11
.24
.14
.09
0
.44
.15
.12
1.30
.20
.08
.12
.04
.25
.02
.06
.21
0
.06
.06
.38
.24
.12
1.04
.40
.54
.31
.04
.17
0
.08
.10
.06
.15
.02
.46
.37
.19
1.12
.27
.21
.27
.16
.10
.18
.02
.14
0
.06
131
-------
HAIR - Manganese
Hg/g hair
Group 2
(smokers)
503
2b4
270 1.
266 2.
405
058 2.
002
275
061 1.
(non smokers)
279
003 1.
001
502
269 7.
402
404
065
501
278
505 1.
277
Test
1
16
•M
7
40
82
69
40
42
34
12
84
33
20
7
34
63
59
38
50
14
23
2
.27
.70
1.37
.84
2.74
.42
.35
1.44
.18
.18
.22
.67
.34
.52
.30
.40
1.10
.23
3
.11
1.22
5.84
.56
2.39
.31
.36
1.22
.06
__-
.33
.19
.15
,29
.37
.43
.48
___
4
.17
.14
4.48
.49
3.00
.28
.06
...
.17
.32
0
.22
.46
Group 2A
(smokers)
298
307
2';i
287
248
299
303
401
309
305
288
292
601
261
250
Test
1
.54
0
.52
0
.03
2.66
.24
1.44
.86
1.05
.12
0
.28
0
.36
2
.24
0
1.06
.15
0
3.71
.99
.69
.92
0
.60
1.46
.09
.32
3
.41
.89
1.06
.51
0
2.36
.79
.95
1.03
1.30
.22
.89
.98
.24
.44
4
1.28
.87
1.09
.28
.12
2.94
.75
.72
1.12
1.46
.15
.71
.18
.16
.19
(non smokers)
246
259
304
249
257
400
251
255
290
301
.09
.95
.45
0
.06
.76
.30
0
.81
.88
.17
0
0
.28
.43
.22
0
1.44
.62
.03
1.59
0
.12
.25
.67
.22
.13
1.15
.47
.16
1.71
1.10
0
.41
1.19
.06
0
1.49
1.38
132
-------
ruur
(smokers)
"9
Z3t!
140 .28
Aon .''8
139 • J-*
Z .!'
204
Z 1 0
'b •- ' •• " — -" •- ^7 0
122 •• ' .: ••• ;•;
.,,, ..-> •''" '20
, " :• Q . 3 i
(r.on smokers) .|{-.o
1? o-i .IS .'2
1^4 • J Z • -; - „ ,.-,-,)•
• ?.7 -^
r O , i . J '
133
M4 .20 -^
jlj =» . \, -^ -1C' .._ ..- .ZP ,?.a
,n, «ZZ .-!^ — "L" .->,-, VI .04 .24
2°J o, 7> ,8Z .7?.
297 -8- • : .... ,7
06
15
OHO •' •;•; ':.., A, ;- -^
161
177
110 , , . ., ,.
2?4 .(-» .-^ •-' '-, .. , .8^, .4- .63
"4 •• "' -' )..f; 8,ZS 10.3.
296 -u"' -^ - ' ' •'•' jt) 'U< '10
-,.,..- . ;/, 24 -5 '•
094 •" ' ^ ': ;:,;, .30 .*
_;,- .40 -36
SO .'iO
-------
HAIR - Zinc
Hg/g Hair
f,ro-,-. 1
(smokers)
02Z
054
038
029
f-y.
020
033
016
03«>
0-10
008
039
027
032
042
023
026
053
012
047
014
017
071
1
MI. :•
161.2
128.3
325.2
19-1.1
116.0
135.8
14 n . 0
201.7
177.0
181.7
355.3
184.8
153.3
206.7
157.3
172.6
141.8
267.3
157.2
166.5
149.5
203.4
i.
i /, '
148
142
115
167
116
127
152
141
164
177
341
167
285
169
157
166
159
137
156
158
161
198
Tc
T|
.8
.6
.6
.8
.0
.8
.0
.5
.3
.5
.0
.9
.9
.1
.3
.3
.8
.2
.8
.2
.4
.5
st
3
i( ...
148.5
300.5
122.7
179.2
143.3
446.9
156.9
173.0
180.2
185.7
171 .6
212.6
186.6
156.3
145.5
170.1
151.7
172.7
220.6
Group 1A
4
? ' A . Q
Io2.2
137.8
152.1
180.5
149.9
156.0
159. 1
186.6
179.0
340.7
169.5
156.6
172.9
175.9
153.5
135.6
159.8
146.9
167.9
182.8
Te
(Muckers) 1 2
3-0
348
347
329
336
321
313
284
320
340
253
318
'339
283
337
314
315
349
286
325
333
345
316
331
147.
196.
206.
153.
156.
136.
101.
138.
166.
117.
165.
142.
188.
171.
150.
166.
172.
108.
132.
192.
164.
143.
214.
145.
0
6
2
3
7
7
7
3
J>
8
0
1
7
9
4
2
8
1
5
3
6
5
7
5
128.5
196.9
193.3
135.0
395.0
121.4
158.3
168.3
24S.3
120.8
376.6
127.0
169.5
171.6
168.2
160.0
174.3
138.8
127.5
182.4
164.8
138.5
228.2
147.9
st
3
147.4
173.3
195.4
151.8
140.6
134.9
108.4
133.2
183.1
120.1
125.5
184.6
228.5
173.5
176.7
165.0
240.0
135.0
148.3
195.0
165.0
201.7
148.3
4
148.6
157.8
200.1
146.4
161.1
151.0
105.7
136.°
190.3
116.0
188.7
131.8
183.8
178.2
168.6
15s.;
216.7
123.3
138.3
183.6
188.:!
198.:
180.1
(non smokers)
046
035
024
013
049
055
034
045
067
070
133.6
125.8
125.8
160.5
153.7
223.6
149.5
126.4
133.7
195.4
148
128
102
167
158
196
153
132
132
316
.8
.2
.9
.1
.3
.1
.3
.0
.4
.2
156.6
142.1
101.7
151.0
127.7
212.5
180.8
159.1
146.9
192.3
162.2
206.7
309.0
151.0
125.4
161.4
168.1
143.8
134.0
165.3
j 1
(non
323
312
334
285
3Z6
258
343
327
330
351
338
324
328
341
<-'- 319
smokers)
162.
152.
220.
278.
190.
246.
210.
162.
154.
154.
114.
236.
146.
155.
212.
2
5
2
7
0
7
0
1
9
1
6
4
9
4
0
168.3
151.7
200.4
155.0
178.3
220.4
349.9
321.2
145.3
162.6
109.7
221.1
134.9
148.3
213.7
165.3
144.6
211.2
145.7
164.3
213.5
189.6
167.4
163.3
160.3
126.9
2Z7.3
150.0
161.5
206.7
124.
149.
226.
163.
161.
235.
219.
163.
166.
171.
126.
Z15.
141.
150.
200
134
-------
HAIR - Zinc
Groi
(smokers) 1
503
270
il • ' !
405
058
r ". ">
275
0 6 1
(non
279
003
001
502
269
402
404
065
501
2 7 b
505
277
144.
; r
124.
*~ -: ' ,*
142.
1-10.
ivy.
218.
187.
smokers)
151.
124.
197.
126.
964.
142.
136.
144.
108.
173.
139.
186.
5
7
; .
3
8
5
2
1
6
4
1
6
6
8
4
9
4
2
8
3
T e s
2
140.
f
141.
—
181.
157.
loi .
1 55.
269.
159.
193.
119.
524.
146.
139.
__
95.
161.
136.
210.
t
c
^
3
5
r>
0
5
7
5
6
1
3
9
2
5
4
4
7
7
i.'-/g Hail-
Group 2A
3
148.
1 . .'.
ill.
—
133.
135.
171.
1 50.
122.
151.
200,
117.
199.
146.
166.
86.
163.
223.
4
b
V
0
7
•i
1
7
2
2
6
1
2
3
2
0
7
4
149.
161.
141.
—
112.
151.
loo.
2:6.
99.
146.
186.
124.
155.
166.
131.
95.
175.
(smokers) 1
3
?;
o
8
4
4
6
0
2
5
3
5
7
6
8
9
298
307
291
287
248
299
303
401
309
305
288
292
601
261
250
(non
246
259
304
249
257
400
251
255
290
301
1084.
169.
168.
100,
125.
240.
143.
193.
92.
128.
156.
234.
156.
117.
152.
smokers )
228.
179.
159.
141.
122.
98.
201.
1 54.
106.
92.
8
3
4
4
5
4
6
4
7
7
7
9
4
6
6
7
8
5
4
4
5
8
1
6
2
T e s
2
324.
245.
161.
88.
129.
251.
171.
179.
128.
—
161.
144.
141.
120.
101.
200.
185.
162.
1 50.
91.
132.
196.
158.
97.
444.
t
0
8
7
2
0
5
6
7
1
7
2
5
9
3
9
9
5
3
5
3
0
4
7
6
3
166.
162.
162.
106.
123.
24Q.
170.
187.
96.
147.
157.
141.
135.
105.
103.
191.
157.
156.
144.
116.
131.
200.
155.
89.
151.
5
o
1
5
9
5
7
5
4
6
3
3
3
5
3
0
5
6
6
0
9
2
7
7
1
4
271. i
1 " •" . '
1 - 1 . •
106. •
13.1. '
T - J -
158. 9
17t>. -.
v, "
118. 9
165. ',
147. 7
161.7
135. 1
109. o
190. 7
145. 2
160.0
14o. 2
1 1 o. 0
133. 5
205. 0
189. 1
98. 0
169. 3
135
-------
HAIR - Zinc
j
1
i
^ fid
(saic
< ,' T
141
180
147.
295
?."/.
14 q
600
139
Z30
204
210
098
12Z
(non
111
311
133
203
297
080
161
177
110
224
129
296
222
094
••> 3
kors)
If-?.
Ivfa
Z39
235
225
187
222
241
161
153
187
222
203
22Z
smokers)
159
148
82
159
184
178
no
201
358
264
357
225
227
186
Test
.7
.7
.4
.1
.3
.5
.5
.0
.2
.3
.8
.3
.4
.1
.6
.9
.9
.6
.6
.7
.3
.9
.5
.5
.2
.3
.2
.4
V
197.9
192.3
25Z.7
272.1
--,
2?-°. 6
237.9
165.3
163.7
187.5
419.9
244.7
2ZZ.5
165.3
157.7
316.2
174.8
184.3
230.7
165.4
212.9
367.1
223.7
381.4
ZZ2.5
210.3
189.9
3
162.
Z16.
230.
479.
21!&.
214.
170.
152.
195.
452.
222.
201.
153.
99.
321.
149.
181.
187.
184.
205.
315.
198.
337.
257.
242.
189.
f;g/g Hair
Group 3A
4 (smokers) 1
4
0
z
1
6
5
7
9
5
1
3
8
0
9
7
8
3
6
5
0
4
7
5
0
3
7
168.0
152.3
268.9
240.6
...
220.0
161.2
163.4
197.6
242.1
279.5
220.9
160.4
142.6
331.2
167.8
196.1
176.5
181.2
212.4
382.1
231.1
168.4
213.9
196.1
441.5
, 136
091
131
Z27
245
226
126
229
195
Z33
175
157
Z09
188
1Z3
182
186
172
244
109
(non
165
083
136
215
. 160
1ZO
097
Z13
225
134
166
125
170
234
118
1 ',/
206.4
326.8
Z51.4
195.4
334.7
387.6
247.0
73.7
137.1
212.7
229. 0
368.3
153.7
160.8
187.4
178.5
298.1
544.5
244.7
smokers)
175.7
361.9
262.6
484.0
283.1
174.5
169.8
156.9
265.6
179.4
187.7
166.6
145.7
384.0
128.7
•
Test
2
215.9
314.1
204.1
347.9
367.4
272.1
95.8
165.4
335.4
228.9
321.2
182.8
175.7
172.2
173.9
294.0
321.2
244.7
204.1
468.6
314.1
528.7
274.6
142.0
182.8
163.3
280.8
207.6
184.6
189.9
403.8
143.7
3
223.8
...
187.5
185.7
313.6
32-1.1
255.8
110.4
156.9
327.6
208.5
355.7
164.7
173.5
160.9
180.5
285.5
394.2
240.0
175.8
317.1
332.9
502.8
284.8
185.7
164.7
253.7
189.2
166.4
152.4
937.0
131.5
4
198.0
227. 0
189.4
345.9
3S2.5
121.8
95.2
166.1
362. -1
202.9
327.6
173.9
158.5
173.9
169.0
303.8
410.0
166.9
395.3
316.6
417.6
287.3
197.7
166.6
248.7
190.4
172.0
153.7
368.2
...
-------
URTNK - Cadmium
(jig/liter of urine
G rovip 1
(smokers)
022
054
038
029
030
0^0
033
Olb
069
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non smokers)
046
035
024
013
019
015
049
055
034
045
067
070
1
1. 3
2.6
1.4
4. 5
1.1
3. 1
3.3
2. 1
2.5
3. 1
2.4
2.3
3. 1
4. 5
2.7
9.6
1.7
1.7
1.6
0,9
1.4
1.6
1.9
2.7
Test
2
1.5
1.2
i. 3
0.6
0.9
0.9
1.5
1.4
1.5
1.2
0.9
0.4
0.8
1.8
1.5
2. 1
0.8
1.0
0.6
1.3
1.7
1.2
1.9
1.4
3
1. 7
0.7
1.2
1. 1
0.6
1.2
0.6
1.5
0.8
1.8
1.3
0.9
1.1
0.9
1.0
0.6
1.0
1.7
0.3
0.5
0.9
1.3
0.9
4
0.8
1.3
1.2
0.9
0.9
2.5
0.5
0.6
..
0.9
0.6
0.8
2.0
0.9
0.6
1.8
0.9
0.4
1.2
1.3
1.4
1.2
1.2
0.6
Group 1A
(smokers)
350
348
347
329
336
321
313
284
320
340
253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
352
1
0.4
0.4
0.2
0.3
0.6
0.6
0.5
0. 3
--
0.3
0. 3
2.0
0.9
0.6
1. 1
0.2
0.6
0.4
0.6
1. 1
1.9
1.6
1.2
0.8
0.7
0.6
Test
2
1.0
1.0
0.2
0.2
0.2
0.5
1.0
0.9
0.2
0.2
.-
1. 1
0.7
0.4
0.4
0.2
0.3
0.3
0.9
0.2
0.5
0.6
0.2
0.3
0.2
0.4
3
0. 1
0.9
0.2
0.2
0.8
0.4
0.2
0.7
0.2
0.7
0.2
0.4
0.6
0.8
1.0
.-
0.7
1.0
0.3
0.3
0.6
0.7
0.3
0.2
0.3
_.
4
0.6
0.6
0.4
0.6
0.7
2.2
0.3
1.8
2.2
0.7
0.5
0.9
1.3
1.4
0.8
--
1.8
0.5
0.7
0.9
0.8
0.6
1. 1
1.4
0.2
__
(non smokers)
2.6
2.0
2. 5
2. 5
2.2
3.6
2.7
.9
.9
.2
.9
.3
0.7
1.7
1.5
0. 7
1.4
1. 1
1.4
0.8
2.3
0.6
1.5
0.6
0.7
0.5
0.8
0.8
0.7
1.0
2.3
0.9
1.2
1.6
2.9
0.9
1.3
0.5
1.2
1. 1
1.2
0.3
0.9
0.7
0.5
0. 1
1. 1
0.6
1 '' '\
323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
1. 5
0. 5
0.6
0.2
0.8
0.4
0. 7
0.6
1.5
0.6
0.2
0.3
0.4
1. 1
1.0
0.4
0.4
0. 3
..
0.4
0.5
0.4
0.5
0.6
1.0
__
0.2
0.3
0. 1
0.3
0.5
0.9
0.2
0.2
0.3
0.3
0.5
0.4
0.3
0.7
0.8
0.2
0.2
0.3
0.2
1. 1
1. 1
._
0.4
0. 6
0.8
1.7
0.3
1. 5
0.9
0.3
0.4
0.5
0.9
0. 6
138
-------
U R I N
- ( '. a d in i u m
Group 2
( smoke rs)
* _-.-
5';} ' i-
264
004
273
; |
504
270
i, U~
?.66
-ID 5
066
0-', P,
— / *J
002
275
061
(non
279
003
001
502
269
402
404
006
005
065
276
501
278
505
277
271
0.
2.
0.
1.
1.
0.
1
6
7
3
2
(
1
5
i
Test
__2
0 . o
1.4
0.8
0. 3
>
4 , . -'
0.5
1. 1
0. b
1.0
0.3 ' --
0.
->
1. 2
1. 3
smokers)
4
0
0
0
1
1
0
0
0
1
0
0
1
1
0
0
.5
. 3
.6
. 5
.7
. i
.4
.9
. 5
. 3
. 8
. 5
. 3
.9
.4
. 2
2.4
0. 5
0. 5
0.4
0. 5
0.4
1.6
1.0
0.4
0. 5
i. 3
0. 7
2. 8
1. 7
0.4
0. 5
0. 8
0. 5
0.6
0.7
1. 6
jig/liter of urine
Group 2 A
3 4
0. 7
1.0
0.7
_ —
0 . i
0.7
1. 1
1. 0
0.9
0. 3
1.9
0.8
1.0
0. 7
1. 1
0.6
1.2
0. 5
1.2
0. 6
0.6
0.3
0.4
0. 5
0. 5
1.6
1.0
0. 8
1. 1
0.9
0. 7
0.
0.
0.
'•_
0.
1.
~t
6
3
. _
T
4
4
„ _
0.6
0. S
_ _
0.7
0.6
0.3
0.7
0
0
0
0
1
0
0
0
0
0
0
0
0
0
.7
. 3
.4
.4
.0
.4
.6
. 5
_ -
. 5
--
. 3
.3
. 8
.6
.4
(smokers) 1
2;3
307
291
287
?-'3
299
303
<\r--i
309
305
233
292
601
261
250
(non
246
259
304
249
257
400
251
255
290
301
0.4
0.3
0.2
0.8
0.3
0. 3
0. 5
0.7
0.2
0.4
1.0
0.8
1.4
0. 5
0. 3
smokers)
0.8
0.4
0.6
0.4
0. 3
0.4
0.4
0.6
0.6
0. 6
Test
2
0. 3
0. 3
0. 3
C. 9
0. 3
0.7
0.5
1.0
0.4
0.4
0.9
0.2
0. 7
0. 3
0. 3
0.7
0.3
1.0
0. 3
0.2
1. 1
0. 8
0. 3
0. 6
0. 7
3
0. 5
0.4
0. 5
0. 4
0. 5
0.4
0.2
0.9
0.4
0.4
0. 5
0. 5
0.4
0. 8
0.4
0.2
0. 3
0. 5
0.4
0.3
0.5
0.4
0.6
0.6
0. 6
4
C. 3
0. 6
0. 5
C . 7
0.4
0. 3
0. 3
0. 6
0. 4
0. 3
0. 8
0.4
0. 7
0. 6
0. 6
—
0. 6
0. 3
0. 3
0.4
0. 6
0. 5
0. 4
0. 5
139
-------
URINE - Cadmium
(smckei's)
112
141
180
142
221
IK"
2?>r,
149
176
600
139
230
204
210
098
122
(non smokers)
111
311
133
203
297
080
161
177
110
224
129
296
222
094
jig/liter of urine
1
O.o
0.3
0.5
0. 5
0.4
0. 4
0.4
0. 1
0. 1
0.2
0.2
0.2
0.2
0.4
0.3
0. 1
*** - f.
"»
t*
0. 8
'\ 5
0. 7
6. 1
1.3
1. 3
. 0.3
0.3
0.5
0.4
0.3
1.2
0.5
0.3
0.3
0.2
t
3
0. 3
0. 3
0. 6
1.2
0.4
__
__
0. 3
0.5
0. 7
0.5
1.8
0. 6
0. 6
0.3
0.4
•I
0.6
1.3
0.6
0.9
..
..
__
0.4
0.2
0.7
2.5
0.9
1. 3
0.6
0.9
0. 5
C:re".n 3 A
(smokers)
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
Tost
1
0.4
0.7
0.7
0.5
0.2
0.6
0.7
0. 5
0.6
0.4
0.4
1.0
0.4
0.4
0.9
0.7
1. 1
._
0.7
2
0.8
0.7
0.6
0.3
0.4
0.6
0.8
0.3
0. 5
0. 4
0.8
--
0.6
0.7
2.3
0.9
1.2
1.8
1.6
3
0.6
._
0.6
1.0
0.7
0.2
0.3
0.4
0.3
0.5
0.3
0.6
0.4
0.2
--
-_
1.8
0.4
0.8
4
1.8
—
0.6
1.0
0.4
0. 8
0.2
0.4
0.4
0. 3
0.8
0.8
0.7
0.2
0.4
--
0. 3
-_
1.3
:) (non smokers)
0. 6
0. 1
0. 3
0.2
0.2
0. 3
0.3
0. 5
0. 1
0.2
0. 1
0.4
0.2
0.3
1.9
1.6
0.6
0.2
_-
0.4
0.2
__
0.7
0.4
0.3
0.5
0.4
0.4
0.5
0.6
0.7
0. S
0.4
0.4
_.
0.4
0.4
0. 3
0. 6
0.4
0. 7
0.3
1.0
0.3
_.
0. 4
0. 3
0.7
1.2
0.3
1.0
1.2
0.7
0. 6
0.6
165
083
136
215
160
120
097
213
225
134
166
125
170
234
0.4
0.7
0.2
0.4
0.7
0.3
0. 5
0.2
0.3
0.3
0. 3
0. 8
_.
1.9
0.2
0.5
0.3
0.6
1.8
0.8
0.7
0.9
0.7
0.4
0.2
0.4
1.2
0.9
0.5
0.5
0.2
0.2
._
0.6
0.5
0.3
0.4
0. 3
__
0. 1
0.2
0. 6
0.7
0.7
0.4
..
_-
0. 3
--
0.3
0.6
0.2
-.
0.3
0.6
0.5
140
-------
U RINE - Copper
G roup _1_
KnT^k-rs) 1
\ -" ' • ^
02?.
U .1 -i
038
029
030
r '0
U «-• w
053
016
069
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non
046
035
024
013
019
v * /
015
049
055
034
045
067
070
5.4
12 0
i t-t t V
16.9
13.9
8.6
1 1. 5
12; 1
17.9
5. 5
9.6
10. 5
10. 6
7. 2
6.7
5.9
7.8
6.7
4.2
5.2
3.9
2. 5
3.6
4.9
25.0
smokers)
9.9
10.2
9.9
19.2
11. 8
16.2
9.3
4. 7
10. 2
2. 3
6.9
7. 9
Tc
?
10. 1
3 « *t
4.5
2.8
4.0
12. 5
3.7
9.2
4.2
11.7
4.7
14. 5
8.0
10. 1
7. 1
7. 5
7.5
4.7
1.5
7.8
19.0
5.7
12.3
23. 3
3.0
2.0
10. 9
6.7
4.2
5.0
11.7
6. 1
3.0
7.7
14. 5
4.8
jig/liter of urine
5 t H^lJA.
3 4 (smokers) _ 1 __
9.5
11.0
8.0
8.2
3. 1
16.3
5.9
17. 1
8.2
16.8
9. 5
11.0
8.4
25.9
2.5
3.3
10.0
11.7
1.9
3. 3
1.6
24. 1
0. 1
17. 9
5. 1
8.6
19.4
8. 3
13.7
11.4
6.9
1.6
10.4
9.3
6.4
5.2
f /
D. O
16.9
4.4
17.4
8.8
7.7
11.6
12.0
11.0
4. 1
27. 6
4. 3
13. 3
10.2
2.5
1.6
3.9
9. 1
10. 5
9.9
1.6
12.0
4. 1
1.6
8.0
6. 1
7.9
7. 5
10.4
8. 1
5.3
2.8
7.4
9.5
350
3-18
347
329
336
321
313
234
320
340
253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
(non
323
312
334
285
326
258
343
327
330
351
338
324
328
; 341
319
1.3
10.0
1. 1
8.4
8.0
2.9
1.6
7.4
9.3
7.2
17. 5
2.4
4.2
4.8
15.2
6.8
4.8
10.7
6.6
9. 1
12. 5
4.4
8.2
12.7
7. 8
smokers)
10. 1
10. 0
9.9
10. 7
3.0
7. 1
6.9
4.0
2. 5
14. 5
6. 1
6. 5
12.4
9.3
9.7
Te s t
2 3
10.6
6. 6
2.7
3.5
13.9
6.5
1.8
13.2
2.8
14.3
-
2. 6
3.7
3.0
6.1
1.9
1.7
14.8
1.7
3.4
7.3
7. 1
20.2
9.2
2.0
19.6
8.9
11.2
-
-
9.4
5.5
3.5
14. 1
18.0
-
5.8
10.4
2. 1
7. 3
3.3
2.9
3.3
7.0
11. 8
12.9
2.0
9.7
3. 5
8. 1
1. 7
1. 9
5.4
4.4
6. 1
3.6
5. 1
3.4
2. 1
12.0
19.2
22. 6
4.2
16. 1
11.8
17. 3
5. 5
3. 5
2. 6
2.2
4.2
7. 5
2.4
8.9
5. 1
8. 2
9.2
2.0
5. 1
4
5.5
5. 3
9.2
7.8
14. 5
3.8
0.9
10.4
11.9
1.6
2t
. 1
3. 7
6.8
8. 5
8.2
8.0
8.5
3. 5
20.4
6.4
9. 1
6.2
10. 5
1.8
25.3
11.0
5 A
. 4
1j
. 1
4.2
8. 5
3. 1
. /
11.6
14. 2
2. 1
11.1
9. 1
14. 1
9.0
-------
Gro'io 2
(smokers)
503
264
004
273
2M
504
270
262
266
405
066
058
002
275
061
1
-
?-. 3
17.4
5.5
8.6
1.2
14. 5
7. 3
-
14. 3
8.0
-
14.5
9.2
8.6
Te
2
6.9
3.0
18. 1
2.3
5.8
24.6 •
10. 1
9.3
7.3
.
2.3
11.7
2.4
2.4
6.9
URI
[-' o
st
3
S. 5
2. 1
8.4
.
1.4
1.0
12. 1
3.5
2.6
2.5
15. 1
10. 1
1.9
2.2
6.6
NE - Copper
:'. '-' -' " of urine
4
7.6
8.3
11.9
_
3.9
1. 1
10.4
_
.
15.0
.
2.8
1.7
1.4
1.7
(non smokers)
279
003
001
502
269
402
404
006
005
065
276
501
278
505
277
271
3.7
3.2
8.9
13.4
15.6
2. 1
9.8
10.7
3.9
1.9
3.7
14. 5
3.7
16.5
5.9
9.0
3.0
8.3
11.5
4. 1
5.0
4.2
4.2
11.7
7.8
1.8
1.9
16.6
3.2
19.9
7. 5
49. 6
1. 1
6.0
9.8
13.4
6.9
2.5
1.4
3. 2
1. 7
1.9
2. 1
9.5
9. 1
16.0
7.8
4.3
1.5
4.4
11.7
5.5
14.4
2.0
7. 6
7. 1
_
6.0
_
6.2
1. 1
14.4
1.6
2.6
Group 2A
(smokers)
298
307
291
287
248
299
303
401
309
305
288
292
601
261
250
Test
1
1.8
2.2
2.3
3. 3
1.9
5.2
6.4
4.0
6.9
9.8
2.5
4.9
1.4
9.0
0.9
2
1.4
2.2
0.7
1.4
3.2
6.7
8.7
13.3
12.4
19.0
24.8
4.6
6.4
5.9
15.9
3
8.2
4.8
10.6
8.8
5.7
13.9
14.2
12. 5
8.5
9. 1
14.4
8.7
9.4
18.7
9.8
4
12.4
6.8
15.0
5.7
2.6
30.2
8.6
11.7
18.8
12.0
17.4
3.3
15.6
8.5
-
(non smokers)
246
259
304
249
257
400
251
255
290
301
2.7
6.3
7.2
6.3
8.0
1.6
5.3
8. 1
2.8
23.5
*3.3
3.7
5.9
15.7
9.8
5.6
8.4
3.2
9.2
18.1
6.3
4. 1
8.3
19.3
8.4
6.7
4.7
4.9
9.1
14.4
7.0
.
10.6
15.4
8.1
14. 1
5.3
6.1
9.7
6.5
142
-------
URINE - Coppe r
Group 3
(r:..t
112
141
180
142
221
187
236
149
176
600
139
230
204
210
098
122
(non
111
311
133
203
297
080
161
177
110
224
129
296
222
094
-.'-or-) 1
12.
9.
17.
7.
4.
13.
7.
5.
3.
29.
8.
3.
11.
13.
4.
9.
smokers)
13.
8.
6.
8.
1 1.
35.
13.
7.
14.
11.
6.
11.
2.
6.
8
6
5
3
8
0
3
3
4
0
3
0
0
3
0
7
^ig/liter of urine
Test Group 3A
7
10. 5
4. 3
15.8
13.0
3.4
12.2
17.0 '
25.4
12.0
6.0
7.8
4. 1
24.8
14.3.
24.3
8.8
3
16.0
24. 1
19.2
35.3
19. 8
_
-
8.4
15.9
6.3
17. 5
20.9
15.8
12.9
15. 1
11.0
4
33. 6
45.3
-
35. 1
37.2
_
_
4.9
8.0
11.2
9.2
5.0
21.7
6.5
14.9
35.7
(smoker
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
169
s) 1
7.
3.
7.
21.
5.
12.
19.
5.
3.
5.
6.
15.
5.
9.
8.
7.
7.
11.
9.
11.
6.
9
5
6
1
0
4
8
0
6
0
8
6
8
9
6
7
8
i
5
5
9
Te
2
6.3
6.7
8.4
19.9
3.0
8.2
26.0
11.0
6.0
7.2
11.9
-
29.7
5.0
25.0
14.7
5.0
28.8
7.4
16.4
7.2
st
3
2.9
-
17.0
17.4
8.4
4.2
7.5
19. 1
24.8
10.7
8.9
33.9
8.9
9.8
-
-
11.0
8.9
16. 1
17.0
11.6
4
3.5
_
6.3
21.7
4.0
13.2
29.9
17.0
32.2
11. 6
13.7
14.9
27.1
40.0
10.8
_
5.5
_
20. 1
12. 8
-
(non smokers)
1
3
5
9
4
7
5
2
0
6
2
3
0
0
10. 3
8. 1
16.7
10.2
-
12. 8
9.0
-
18. 1
13. 6
3.9
14. 5
14. 1
7.4
12.3
10. 9
9.6
11. 1
12. 5
13.3
-
17. 6
9.9
6.0
5.3
11.7
10. 8
4.8
HI
5. 1
40. 3
-
4.5
15. 3
9.7
12.9
10.2
35.4
6.0
23. 1
16. 1
6.6
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
6.
7.
6.
5.
10.
6.
7.
6.
17.
9.
6.
18.
«
19.
6.
2
9
1
9
3
1
2
2
1
4
9
3
5
1
9.3
12.8
12. 1
8.4
11.3
7.5
10. 8
7.0
9.9
11.9
8.5
8.4
24.2
15. 1
6.7
11.2
13. 0
7.8
12.0
_
14.2
15.4
16.8
13.9
38.4
_
17. 7
7. 1
11.4
—
7.4
9.6
8. 6
_
_
9.7
-
15.3
18.0
7.7
-
18. 3
11.2
26. 3
13. 7
143
-------
URINE - Lead
[ig /liter
Group 1
(.. .0"
022
051
038
029
OiO
020
033
016
069
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non
-•---) J'
18
41
48
63
51
92
4-1.
81
14
32
28
12
48
88
32
16
48
72
36
12
0
20
12
40
smokers)
.5
.1
.2
.0
_ 9
.6
..5
.5
.8
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
.0
of urine
Test
2
40.0
16.7
26.7
85.4
80.8
46.2
53.9
42.3
92.3
53.9
3.9
27.7
40.1
38.9
7.7
0.0
0.0
53.3
0.0
0.0
36.4
37.7
24.7
39.0
3
42.1
33.0
25.0
21.6
17.1
13.7
34.1
28.4
15.9
26. 2
23.5
29.8
18.5
23.5
7.4
9.9
40.8
11.1
7.4
11.1
9.9
24.7
19.8
4
14
9
8
0
8
0
6
0
--
14
6
4
47
1
18
9
10
0
7
0
9
4
9
1
.5
.7
.1
.0
.1
.0
.5
.0
-
.5
.5
.5
.0
.5
.2
.1
.6
.0
.6
.0
.1
.6
.1
.5
Group 1A
(rmokcrs)
350
348
347
329
336
321
313
284
320
340
253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
1
0.0
18.6
0.0
20.9
45.3
2.7
0.0
13.3
11.9
13.3
85.3
12.2
21.9
9.8
109.7
29.2
14.6
37.5
46.8
9.4
12.5
0.0
25.0
34.4
Te
2
0.0
0.0
76.6
0.0
0.0
3.3
0.0
36.6
0.0
46.6
0.0
23.8
0.0
23.8
0.0
0.0
28.5
0.0
4.7
70.3
45.3
26.6
43.8
26.6
st
3
19.2
11.5
44.9
51.3
25.6
2.6
38.5
14.1
29.5
1.3
18.2
22.7
30.7
36.6
21.6
21.6
26.1
0.0
15.8
28.9
3.9
0.0
6.6
4
21.6
8.3
38.3
24.9
44. ^
19.9
3.3
46.6
28.3
4.9
28.3
14.9
20.9
8.0
9.7
6.5
6.5
0.0
16.1
0.0
1.6
0.0
(non smokers)
046
035
024
013
019
015
049
055
034
045
067
070
41
62
44
41
63
51
24
48
24
24
24
8
.1
.9
.5
.1
.0
.9
.0
.0
.0
.0
.0
.0
46.7
29.9
36.7
46.7
46.2
57.7
12.3
7.7
0.0
6.1
37.7
5.2
21.6
19.3
17.1
50.0
22.8
13.7
23.5
13.6
0.0
18.5
8.7
17.3
0
0
1
9
6
24
1
12
12
1
0
0
.0
.0
.6
.7
.5
.2
.5
.1
. 1
.5
.0
.0
1 , (
3E3
312
334
285
326
258
343
327
330
351
338
324
' 328
341
319
0.0
56.9
26.6
28.9
19.9
0.0
12.2
21.9
7.3
39.0
0.0
0.0
25.0
12.5
0.0
23.3
0.0
3.3
0.0
4.7
0.0
33.3
19.0
18.7
70.3
31.3
64.1
66.7
51.3
30.8
21.8
19.2
15.9
12.5
31.8
0.0
26.1
35.2
15.8
36.8
14.5
14.5
31.7
43.3
48.3
8.3
3.2
12.9
8.0
3.2
32.3
1.6
19.4
22.6
19.4
12.9
144
-------
URINE - Lead
fig /liter of urine
Group 2
(smokers)
503
264
004
273
281
504
270
262
266
405
066
058
002
275
061
Test
1
29.7
8.1
5.4
0.0
2.7
0.0
9.5
0.0
____
0.0
0.0
2.9
0.0
23.5
2
53.0
3.0
59.1
4.5
31.8
13.6
53.0
48.5
24.2
_ _-
1.5
52.9
15.3
19.9
65.8
3
64.5
8.6
52.7
9.7
4.3
51.6
20.4
16.1
12.9
49.4
106.0
12.0
16.9
56.6
4
30.3
3.0
51.5
33.3
0.0
60.6
21.2
52.5
49.1
32.4
25.9
37.9
(non smokers)
279
003
001
502
269
402
404
006
005
065
276
501
278
505
277
271
6.8
13.5
2.7
1.3
41.9
11.7
17.6
41.1
38.2
5.8
97.1
2.9
0.0
5.8
0.0
0.0
4.5
48.5
83.3
45.4
37.9
12.9
18.8
68.2
88.2
0.0
7.0
47.1
21.1
51.7
88.2
78.8
1.1
37.6
35.5
52.7
67.7
16.8
15.6
19.2
36.1
0.0
24.1
22.9
16.9
28.9
18.0
15.7
10.1
50.5
90.9
25.3
52.5
17.6
24.9
32.4
29.6
34.2
0.9
52.7
13.8
42.6
Group 2A
(smokers)
298
307
291
287
248
299
303
401
309
305
288
292
601
261
250
Test
1
27.9
4.9
21.3
0.0
13.1
32.8
54.1
26.9
20.5
46.2
62.8
43.6
0.0
32.1
0.0
2
10.0
15.0
0.0
52.5
30.0
1.3
39.9
34.7
19.9
37.3
49.3
19.9
9.3
0.0
26.7
3
1.6
32.3
46.7
0.0
37.1
1.6
17.7
33.9
20.9
33.9
24.1
49.0
58.8
47.1
17.6
4
10.5
15.8
33.3
24.6
0.0
0.0
43.1
62.7
60.1
44.4
63.9
20.9
54.8
41.8
(non smokers)
246
259
304
249
257
400
251
255
290
301
96.7
98.4
32.1
32.1
20.5
7.7
25.6
16.7
46.2
48.8
50.0
30.0
38.7
22.7
17.3
18.6
19.9
23.9
31.9
38.7
14.5
11.3
14.5
17.7
8.0
5.9
21.6
29.4
11.7
11.7
24.6
26.1
20.9
20.9
43. 1
32.6
45.7
40.5
31.3
145
-------
URINE - Lead
Group 3
(smokers)
112
141
1BO
142
221
187
23o
176
600
139
230
204
210
098
122
(non smokers)
111
311
133
203
297
080
161
177
110
224
129
296
222
094
1
49. 3
33.3
51.9
7.9
23.9
43.9
21.3
13. 3
13.3
71.9
25.7
10.0
7. 1
22.8
0.0
20.0
')
42.7
53.3
30.7
21. 3
53.3
63.9
47. 9
29.3
15.9
18. 6
12.8
24.2
0.0
18.5
Test
2
73.6
5.2
66. 6
17.5
8.7
54.3
43.8
36.8
61.4
10. 8
19.9
49.9
28.3
24.9
83.3
33.3
36.8
21.0
47. 3
57.8
--
47. 3
37. 8
--
2Q. 7
19. 9
11. 6
36.6
26. 6
19.9
|i£/J of urine
Grour> 3A
3
32.7
3V. -i
56. 3
25.4
83.8
__
--
9.6
58.0
9.6
66. 1
24.1
46.7
69.3
20.9
35.4
10.9
36.3
51.6
0.0
9.6
24. 1
__
61.2
20. 9
17.7
90. 3
85.4
69. 3
33.8
>
4
38
66
_
64
9
-
-
8
11
149
19
21
60
2
41
10
-
16
61
-
13
21
46
58
39
36
8
21
0
60
.3
. 6
_
.9
.9
_
_
. 3
.6
.9
.5
.7
.8
. 1
.3
.8
_
.6
.6
.
. 3
.6
.6
. 3
. 1
.9
. 6
.7
.0
. 8
I • >
(smokers) 1
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
169
• (non
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
17.
5.
31.
41.
0.
8.
38.
S.
5.
0.
4.
34.
14.
0.
84.
23.
6.
17.
5.
15.
35.
smokers)
14.
1.
21.
8.
10.
0.
66.
47.
30.
3.
15.
21.
_.
53.
15.
8
3
4
0
0
3
8
5
5
9
6
2
8
0
7
8
6
1
7
2
2
2
7
4
9
7
0
6
2
5
7
2
9
3
2
Test
2
15. 5
20. 6
16.3
22.4
9.4
9.4
13.7
2.2
8.8
0.0
9.9
--
23.3
0.0
37.9
5.7
0.0
9. 1
0.0
3.4
0.0
13.7
15.5
9.4
15.5
25.8
13. 7
22.4
19.8
17.7
7.7
0.0
2.2
35.5
4. 5
0.0
3
0
-
28
73
0
-
29
49
6
3L
48
57
21
7
-
_
12
30
25
37
53
11
28
38
69
--
28
64
51
21
26
_
43
12
57
-
.0
-
. 5
.8
.0
-
.2
.9
.0
.7
.7
.3
.9
.3
_
-
. 1
.4
.6
.8
.6
.9
. 5
.0
.0
• -
.0
. 6
. 2
. 9
. 8
.
.9
. 1
. 3
-
4
0.0
25.7
142.4
0.0
15.8
43.9
21.9
1.2
2.4
42.6.
14.6
34.3
5.9
37.3
_-
14.9
--
32.8
20.8
--
31.8
13.6
31.8
--
-_
.-
__
31. 7
25.3
0.0
__
28.3
31.3
56.7
14.9
-------
C-ioir.__
/ -,-,-, -'• 'i
(:-,] n .-.-
022
054
033
029
030
020
033
016
069
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
(non
046
035
024
013
019
015
049
055
034
045
067
070
y
7s) i
3.3
3.2
3.0
6.3
&.b
3.1
2.5
2.4
3.9
3.8
13.3
1.6
5.4
6.6
4.8
3.0
6.4
3.4
7.3
2.5
4.5
3.0
14.1
5.1
smokers)
2.9
3.1
5.2
7.8
4.4
4.9
2.2
5.6
3.1
6.4
4.3
9.1
W i.\ .*.
T e s •
2
4.4
2.8
3.4
2.1
•1.2
2.1
3.3
3.4
3.1
8.4
5.5
10.1
8.1
5.0
15.6
3.1
6.1
9.3
4.6
6.2
6.0
8.7
5.8
13.0
4.3
3.2
2.8
3.8
11.1
7.5
14.2
9.4
3.6
7.2
6.4
6.2
|ig/ liter of urine
I Gro-T>_lA_
3
2.9
11.2
3.6
6.3
*? n
_> . /
-4.8
5 . o
4.3
1.4
9.0
2.5
3.9
2.3
5.3
9.2
4.1
7.9
1.4
9.0
4.6
8.3
5.6
2.0
4.2
6.9
1.4
3.0
2.5
3.9
3.1
4.8
2.3
1.9
2.8
4.1
4
—
25.1
7.8
11.0
6.1
* > /
1 1 . o
* ~> \
j. LJ • '*•
-^ -* Q
L j . 0
6.1
12.2
10. 1
13.6
18.5
6.5
10.2
11.0
7.4
2.8
5.9
12.1
6.1
5.3
16.2
13.2
5.3
18.6
9.1
8.0
20.7
6.3
11.6
7.2
8.5
4.8
8,6
9.6
,
i
(smokers)
350
348
347
329
3V-
•~* -' -*
3?1
313
~J •*• — *
284
320
340
•253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
(non
323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
1
9.8
4.2
9.1
7.9
9.8
47.4
8.0
19.1
6.1
5.4
8.9
10.7
4.0
9.1
10.2
7.2
24.2
8.0
4.1
15.6
8.0
8.8
22.3
6.2
19.1
smokers)
5.6
8.5
10.0
10.0
2.2
12.8
13.1
6.4
12.4
9.1
7.1
6.4
86.2
9.3
11.3
Test
— . i — —
7.2
12.0
6.0
22.4
8.9
8.1
3.4
21.5
5.8
10.3
15.9
13.0
13.4
2.4
5.2
7.4
7.6
13.2
7.5
10.6
5.8
6.2
13.0
4.5
7.1
11.1
15.5
6.2
7.9
8.4
4.4
16.0
14.2
7.7
35.9
3.3
7
_>
— — -
4.8
2.9
2.7
3.5
2.6
1.1
0.5
1.7
2.4
2.8
1.9
1.9
2.4
1.8
7.3
0.9
1.6
3.8
3.5
2.9
1.5
1.7
0.3
10.6
1.9
3.4
7.8
5.6
3.3
1.9
8.9
3.5
2.7
2.7
7.2
2.3
2.3
0.6
2.5
*t
1.3
16.9
4.2
2.2
7.?
2.6
4.3
7.4
4.9
3.5
4.9
3.7
10.2
8.b
3.6
14.4
6.9
9.3
4.2
3.6
4.3
1.3
8.9
3.6
2.7
4.0
3.1
2.7
6.0
2.5
2.1
1.2
6.1
3.4
4.8
5.1
5.0
11.2
1U7
-------
URINE - Manganese
Group 2
(smc
503
264
004
2V3
2ol
504
Z70
262
266
<:os
066
058
002
275
061
(non
279
003
001
502
269
402
404
006
005
065
276
501
278
505
277
271
\^rr) 1
2.3
4.6
4.3
9.5
o.9
5.1
7.6
8.6
9.8
4.3
1.5
2.4
4.7
smokers)
1Z.7
5.7
2.5
7.5
3.8
2.0
11.9
4,2
9.4
2.4
6.7
5.0
2.5
6.2
8.5
2.5
1 e
2
5.4
4.6
19.9
0.2
2.3
1.1
6.6
9.3
4.6
5.9
2.2
1.2
3.7
2.2
3.4
3.2
4.2
4.4
6.1
3.0
2.4
2.0
2.0
4.2
2.8
8.4
2.0
8.4
2.3
3.8
\ig /liter of urine
s t Group ZA
3
25.3
1.2
47.6
6.5
2.4
2.0
1.3
2.6
1.5
2.5
1.7
3.2
5.1
1.5
2.7
3.4
3.5
1.5
6.6
11 .0
2.3
2.6
3.2
0.4
4.3
2.0
5.4
4.1
4.5
8.8
4
11.
1.
2.
3.
4.
3.
--
2.
3.
2.
5.
4.
1.
4.
3.
3.
12.
9.
4.
2.
5.
23.
3.
1.
17.
2.
6.
(smokers) 1
3
9
5
-
3
4
2
-.
6
5
-
7
2
6
5
1
1
6
7
3
6
0
6
-
7
-
3
5
1
6
8
298
307
291
287
248
299
303
401
309
305
288
292
261
250
601
(non
246
259
304
249
257
400
251
255
290
301
4
5
2
2
4
5
3
4
13
1
4
2
26
6
5
.8
.4
.9
.7
.1
.3
.1
.3
.2
.6
.7
.7
.4
.1
.2
Test
2
1.5
12.2
1.5
2.2
2.1
2.7
11.0
3.2
7.7
13.7
39.8
7.3
16.8
10.6
4.4
3
12.6
13.2
18.1
4.8
34.4
8.2
8.2
17.3
12.7
31.3
10.3
11.6
5.8
13.1
5.3
4
8.5
4.9
9.2
4 .5
6.1
5.C
21.7
13.:
9.0
17.5
7.1
12.6
21.2
3.2
smokers)
2
2
3
1
2
4
6
2
4
2
.5
.7
.5
.3
.1
.5
.7
.2
.5
.5
1.4
7.1
1.9
9.0
5.4
6.6
32.3
7.5
9.3
15.8
12.4
11.5
7.2
6.5
11.5
10.9
14.0
65.0
6.8
7.4
10.5
11.2
5.6
7.2
7.:
12.9
42.4
13 .2.
1S.C
148
-------
U R IN E - Man g a n e s e
jig/liter of urine
(~~ — • v . • ••» ">
ti O'in _>
(smokers)
112
1-H
iro
142
?.?1
•* R7
J v' (
£ j O
149
176
600
139
230
204
210
098
122
(non smokers)
111
311
133
203
297
080
161
177
110
Test
1
19.2
14.2
?.7.5
12.1
14.9
8/
• O
R A
v/ • \J
2.0
47.7
18.8
13.5
8.5
10.3
9.3
6.8
13.5
19.5
6.6
10.6
5.8
8.2
10.0
20.4
16.5
10.4
224 45.0
129
296
222
094
4.0
11.5
5.1
12.1
2
30.4
5.3
5.9
2.0
3.8
? s
t* • --J
44 Q
i^E . /
14.9
6.8
8.7
8.2
11.8
14.7
12.6
8.2
3.5
9.9
23.1
12.9
12.9
2.9
2.3
7.0
3.7
12.0
10.7
6.5
4.0
_3
5.9
6.8
9.8
2.8
4.5
5.9
7.4
6.6
9.9
5.0
8.8
10.3
26.9
7.9
10.2
6.5
21.1
4.9
10.4
18.4
2.6
5.0
4.6
4.7
6.5
14.7
9.3
4
4.6
4.0
10.8
8.5
3.6
7.8
8.6
89.1
11.4
39.3
5.2
3.7
4.4
_ — _
8.7
58.5
44.8
6.7
10.9
6.9
21.1
13.4
4.8
35.8
6.6
7.3
Group 3A
(smokers) 1
091
131
227
245
226
126
J- t-*\J
7/9
L* L+ /
195
233
175
157
209
188
123
182
214
186
172
244
(non
165
083
136
215
160
120
097
213
225
134
166
125
170
234
52.9
9.7
6.7
7.0
12.2
4.0
5 1
+s * J~
6.1
10.7
15.0
6.6
24.0
19.1
15.9
2.0
3.3
5.2
11.9
2.5
smokers)
20.9
17.4
4.2
69.6
6.6
21.6
11.6
7.0
3.6
3.1
3.0
24.1
_ _ _ _
68.8
Te
2
1.0
9 4
7 • A
2.4
1.9
2.6
3.3
5.7
5.2
2.2
2.3
3.4
3.7
3.7
1.2
4 5
* • J
2.4
2.8
6.6
0.9
1.7
7.4
2 4
t-* * *
2.6
4.0
6.5
2.6
4.1
3 5
-------
URINE - Zinc
Group 1
(s'nokcrs) 1
022 153.
054 158.
038 124.
029 • 110.
030 113.
020 230.
033 241.
Olo 269.
069 263.
036 115.
040 67.
008 249.
039 168.
027 334.
032 252.
042 188.
023 308.
026 84.
053 53.
012 216.
047 87.
014 126.
017 182.
071 631.
(non smokers)
046 153.
035 198.
024 90.
013 173.
019 167.
015 308.
049 188.
055 297.
034 109.
045 160.
067 224.
070 252.
^ig/liter of urine
2
170
133
90
173
1 il
193
210
144
462
119
360
377
351
363
336
102
207
105
21
237
126
180
404
463
Test
3
. 466.
437.
. 239.
288.
260.
592.
221.
. , 423.
10-1.
. 346.
638.
749.
558.
491.
189.
568.
437. "
279.
354.
419.
354.
. 1085.
518.
4
218.
235.
410.
335.
427.
680.
559.
241.
298.
261.
593.
255.
627.
235.
221.
403.
153.
261.
122.
153.
479.
667.
421.
Group 1A
(smokers)
350
348
347
329
336
321
313
284
320
340
253
318
339
283
337
346
314
315
349
286
325
333
345
316
331
1
215.
393.
77.
261.
358.
143.
235.
126.
163.
189.
175.
88.
143.
71.
458.
264.
198.
194.
445.
224.
316.
397.
150,
185.
217.
Te
2
358.
606.
744.
141.
342.
169. .
405.
138.
694.
505.
612.
237.
232.
603.
277.
214.
201.
201.
432.
128.
356.
171.
204.
115.
Bt
3
224.
272.
227.
164.
977.
164.
164.
346.
312.
249.
45.
167.
269.
82.
229.
171.
203.
707.
145.
191.
272.
29.
78.
168.
4
106.
465.
575.
267.
695.
204.
730.
634.
344.
587.
135.
67.
408.
115.
357.
381.
186.
634.
412.
169.
499.
534.
219.
514.
(non smokers)
116
82
90
278
210
261
263
180
148
153
503
175
. 592.
334.
184.
502.
. 423.
460.
620.
577.
239.
453.
964.
552.
252.
129.
381.
476.
461.
680.
114.
426.
__
224.
482.
278.
323
312
334
285
326
258
343
327
330
351
338
324
328
341
319
341.
530.
146.
430.
131.
111.
278.
352.
243.
366.
475.
224.
465.
399.
226.
556.
339.
295.
--
113.
395.
138.
50.
132.
564.
198.
613.
389.
412.
269.
542.
153.
181.
90.
184.
173.
490.
92.
287.
510.
307.
330
205.
156.
383.
361.
767.
175.
196.
608.
710.
244.
647.
254.
186.
352.
646.
129.
150
-------
URINE - Zinc
Hg/liter of urine
Group 2
(smokers)
503
264
004
273
281
504
270
262
266
405
066
058
002
275
061
1
461.
473.
648.
395.
563.
202.
705.
793.
711.
637.
570.
189.
582.
508.
Te
2
492.
167.
1032.
320.
527.
493.
543.
1245.
550.
222.
257.
458.
182.
652.
684.
st
3
496.
361.
1361.
103.
491.
334.
587.
642.
192.
551.
540.
4
505.
110.
480.
154. .
129.
537.
393.
303.
449.
199
228.
290.
(non smokers)
279
003
001
502
269
402
404
006
005
065
2.76
501
278
505
277
271
444.
457.
775.
632.
1250.
260.
450.
231.
376.
378.
594.
181.
194.
319.
876.
505.
300.
596.
540.
400.
477.
497.
236.
102.
503.
278.
1307.
352.
272.
408.
746.
317.
767.
318.
295.
248.
253.
417.
414.
294.
519.
561.
745.
554.
177.
189.
522.
445.
471.
423.
162.
334.
353.
181.
__-
312.
55.
71.
_ _ _
Group 2A
(smokers)
298
307
291
287
248
299
303
401
309
305
288
- 292
601
261
250
1
174.
122.
174.
61.
165.
174.
227.
337.
249.
223.
260.
355.
289.
295.
34.
Tes
2
t
141.
93.
25.
115.
122.
117.
209.
321.
347.
515.
167.
177 .
160.
83.
t
3
174.
275.
447 .
95.
301.
340.
194.
596.
485.
713.
470.
457.
204.
243.
4
184.
165.
511.
85.
79.
247.
181.
485.
250.
287.
718.
367.
477.
284.
(non smokers)
246
259
304
249
257
400
251
255
290
301
92.
150.
204.
135.
141.
150.
91.
100.
204.
355.
138.
103.
235.
103.
96.
215.
160.
86.
222.
392.
113.
158.
200. *
226.
121.
217.
97.
108.
230.
220.
118.
155.
167.
73.
280.
40.
157.
180.
143.
151
-------
URINE - Zinc
Hg/liter of urine
Group 3
(smokers)
112
141
180
142
221
1ST
336
149
176
600
139
230
204
210
098
122
!
2°f,.
65.
29.
127.
172.
277.
29.
62.
11.
297.
101.
175.
198.
153.
35.
237.
Te
•>
L,
419.
74.
21.
213.
91.
186.
118.
112.
204.
132.
122.
445.
312.
254.
289.
199.
st
3
465.
382.
99.
755.
168.
79.
104.
152.
248.
101.
276.
203.
159.
184.
4
467.
171.
82.
505.
133.
28.
31.
302.
178.
200.
260.
123.
156.
153.
(non smokers)
111
311
133
203
297
080
161
177
110
224
129
296
222
094
68.
87.
136.
110.
217.
184.
92.
132.
132.
235.
143.
117.
87.
234.
77.
152.
240
115.
52.
66.
—
207.
217.
196.
122.
109.
305.
92.
82.
155.
118.
125.
76.
124.
184.
124.
108.
127.
162.
184.
82.
73.
187.
Group 3A
(smokers)
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
169
1
42.
168.
402.
653.
63.
225.
222.
139.
152.
225.
206.
458.
276.
232.
355.
78.
201.
158.
220.
360.
77.
Te
2
53.
244.
198.
252.
26.
72.
74.
421.
110.
244.
153.
200.
122.
428.
102.
118.
334.
193.
311.
49.
st
3
14.
215.
211.
45.
47.
85.
254.
82.
108.
79.
448.
133.
170.
90.
183.
186.
189.
131.
4
52.
108.
372.
59.
104.
286.
100.
50.
83.
215.
275.
162.
291.
98.
311.
(non smokers)
127.
92.
66.
213.
162.
184.
98.
133.
45.
140.
165
083
136
215
160
120
097
213
225
134
166
125
170
234
118
227.
208.
104.
208.
144.
110.
203.
219.
235.
207.
81.
301.
282.
90.
149.
334.
145.
126.
169.
99.
149.
91.
157.
275.
39.
137.
216.
137.
107.
97.
260.
19.
120.
81.
224.
216.
308.
119.
228.
90.
96.
138.
91.
104.
191.
291.
84.
177.
93.
213.
142.
152
-------
FECES - Cadmium
|ig/g Feces
Group i
(smokers)
022
054
o:-s
029
030
020
033
016
069
036
040
008
039
027
032
042
023
026
053
012
047
014
017
071
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
.20
.25
--
. 30
--
. 1 5
.20
.20
. 15
. 10
. 15
. 15
. 15
. 15
. 10
. 10
.20
. 11
.06
. 13
. 14
. 14
.21
Test
2
0. 12
0. 19
0. 16
0. 19
0. )3
0. IS
0. 19 '
0. 17
0. 18
0. 13
0. 16
0. 13
0. 15
0. 19
0. 19
0. 19
0. 12
0.22
0. 19
0.06
0. 12
0. 19
0. 19
0. 13
3
0. 18
0.20
0.27
0. 14
o.ao
0.21
0.7.6
0.21
0. 16
0.27
0.07
O.Z3
0.21
0.24
0. 17
0. 14
0. 19
0.20
0.24
0.20
0.31
0.20
0. 28
0.27
4
0.22
0. 17
0.30
0.27
0.20
0. 13
0. 19
0. 18
0. 13
0. 17
0. 14
0. 18
0.38
0.30
0. 11
0. 13
0. 14
0.33
0.37
0.05
0.36
0. 13
0.24
0. 15
(non smokers)
046
035
024
013
019
015
049
055
034
045
067
070
0
0
0
0
0
0
0
0
0
0
0
0
. 15
.28
. 25
. 35
. 20
. 15
. 10
. 15
.25
. 10
.20
. 04
0. 17
0. 33
0. 18
0.30
0. 16
0.20
0.23
0. 12
0.41
0.05
0.25
0.08
0. 13
0. 13
0.21
0. 19
0. 11
0. 10
0. 14
0. 12
0. 15
0. 19
0.22
0. 15
0.22
0.21
0.28
0. 18
0.25
0.20
0.26
0.08
0.26
0.08
0.26
0. 15
Group 1A
(smokers)
350
348
329
336
321
313
284
320
340
318
339
283
337
346
352
314
315
349
286
325
345
316
331
Test
1
0. 11
0. 13
0. 13
0.21
0. 1 1
0. 14
0. 16
0. 26
0.09
0.30
0. 16
..
0.24
0.37
0. 11
0.21
0. 13
0. 17
0.27
0.20
0.36
0. 57
0.40
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
2
. 15
.36
--
.21
.03
. 15
.20
. 32
.-
.45
. 19
. 14
. 17
.24
.09
.20
. 15
. 18
. 21
.32
.30
.24
.28
3
0.15
0. 14
--
0.24
.-
0. 12
0. 15
-.
-_
0. 50
0. 14
--
0. 68
--
-_
0. 14
0. 14
0. 14
0. 10
0. 13
0.73
--
0. 19
4
0. 15
0. 18
0. 15
0. 02
0.01
0.04
0. M
0. 44
0. 14
0. 19
0. 13
0.09
0. 12
--
-_
0. 18
0.09
0.26
0. 10
0. 18
0. 28
0. 08
0. 12
(non smokers)
323
312
285
326
258
343
327
330
351
338
324
328
341
319
0.28
0.28
0. 14
0.23
0. 16
0. 10
0. 19
0. 18
0.23
_ _
0.20
0. 34
0. 17
0. 16
0
0
0
0
0
0
0
0
0
0
0
0
0
0
.09
. 43
. 15
.21
. 12
. 19
. 31
.24
.22
. 17
.26
.28
.28
. 13
0. 17
0.21
0.09
0. 11
__
0. 12
0. 11
0. 16
-.
0. 15
0. 18
0, 16
..
0. 11
0.26
0.07
0. 10
0. 20
0. 12
0. 17
0. 15
0. 17
0.32
0. 18
0.25
0.22
0. 10
'.154
-------
FECES - Cadmium
Rg/g
Group 2
(smokers)
503
264
004
281
504
262
405
066
058
002
275
061
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1
2?
22
26
21
20
15
1-1-
C'j
29
16
17
18
Te s
2
0. 19
0. 12
0.29
0.24
—
0.41
0. 15
_ -
0. 14
0.20
0. 41
0.28
t
3
0.41
0. 36
0.08
0.25
0. 36
1. 78
0. 38
_ _
0. 35
0.20
0. 36
0.48
0
0
0
0
0
0
0
0
Feces
4
.39
. 19
.06
.20
.02
—
_ _
. 37
. 32
.23
(non smokers)
279
003
001
502
269
402
404
006
005
065
276
501
278
505
277
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
-
0.
13
14
38
14
27
30
30
33
23
15
21
13
21
-
90
0. 16
0.08
0. 34
0.39
0. 33
0.28
0.25
0. 19
0. 10
0. 22
0.22
0. 17
- -
0. 17
0. 38
0.23
0.25
0. 59
0. 35
0. 37
1. 02
0. 34
0.41
0. 32
0. 32
0. 38
0.53
0
0
0
0
0
0
0
0
0
0
0
0
.26
.22
.20
. 31
.24
. 28
. 36
. 21
—
. 38
. 45
. 31
. 38
Group 2 A
(smokers)
298
307
291
287
248
299
303
401
309
305
288
292
601
261
250
1
0. 33
0.29
0. 28
0.41
0. 19
0. 14
0.26
0. 14
0. 26
0. 28
0. 18
0. 01
0. 18
0.04
0.27
Test
2
0. 33
0.26
0. 37
0. 33
0.07
0.43
0. 23
0. 13
0. 15
0. 02
0. 09
0.07
0. 15
0. 34
0. 51
3
0. 19
0.22
0.42
0. 38
0.29
0.22
0. 14
0.24
0. 16
0. 17
0.24
0. 95
0. 18
0. 1 1
0.29
4
0. 39
0.27
0.28
0. 38
0.25
0. 12
0.21
0. 23
0. 19
0.07
0. 34
0.00
0. 07
0.20
--
(non smokers)
246
259
304
249
257
400
251
255
"290
301
0.22
0.24
0.20
0. 25
0. 30
0. 30
0. 37
0. 10
0. 18
0.28
0. 18
0.08
0. 09
0. 62
0. 17
0. 21
0. 23
0. 06
0. 15
0. 31
0.24
0. 16
0. 16
0. 17
0.28
0.40
0. 30
0.27
0. 31
0.27
0.25
—
0. 19
0. 31
0.24
0.05
0.27
0. 18
0. 30
0.25
155
-------
FECES - Cadmium
Group 3
(smokers)
1 12
141
ItiO
142
231
167
236
1 i}
176
600
139
230
204
210
098
122
(non smokers)
111
311
133
203
297
080
161
177
224
129
296
222
094
1
0. 38
0. 2?
0.41
0. 17
0. 17
0. 10
0.22
0. 21
0. 35
0.27
0.28
0. 13
0. 31
0.31
0.42
0.41
i)
0. 17
0.24
0.40
0.42
0.21
0.29
1.45
0. 34
0. 13
0. 38
0. 18
0.22
Test
2
U.24
0.27
0.22
0.29
0.06
0. 1 1
0.23
0.22
--
0.24
..
0.07
0.29
0.26
0. 11
0. 14
0.26
0. 14
--
0.25
0.23
0. 12
0.25
0. 52
0. 18
0.27
0.28
0.39
0. 34
Hg/g Feces
Group 3 A
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
3
. 27
. 16
.40
.26
.41
--
_-
.35
.23
.26
.42
. 25
.24
. 15
.07
.06
. 30
.34
. 14
. 30
.20
. 12
. 53
. 21
.29
.28
. 18
. 17
. 33
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
.23
.48
.29
. 13
_.
_-
_.
. 12
.49
.25
._
.35
.20
.37
. 14
. 13
.25
. 10
__
.24
.40
.08
.25
.24
. 20
. 32
.22
.47
.30
(smokers) 1
091
131
227
245
226
126
229
195
253
175
157
209
1S8
123'
182
214
186
172
244
109
169
{non
165
083
136
215
loO
120
097
213
225
134
Io6
125
170
234
118
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
smokers)
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
I
27
17
25
28
26
22
19
26
14
15
18
31
19
15
15
24
14
14
10
03
34
11
33
26
31
27
17
54
24
22
23
30
04
27
24
17
Test
2
0.21
0. 15
0.03
0. 17
0.20
0.21
0. 13
0.25
0.02
0. 12
0.21
0. 31
0.23
0. 26
0. 12
__
0. 10
0. 18
..
0.30
0.35
0. 17
0.30
0.05
0.25
0. 30
0. 16
0. 17
..
0. 14
0. 15
0.01
0.05
0. 35
0.26
0.28
3
0.31
--
0.20
0.44
0. 19
0.21
0.41
1.20
0.08
0. 15
0. 13
0.24
0.20
0.40
0. 15
-_
0. 16
0. 13
0.21
0.37
0.30
0.24
0.29
0. 24
0.31
_.
0.28
0.25
0.29
0.37
0.22
__
0. 04
0.21
0.23
..
4
0.28
._
0.24
0. 17
0.24
0.41
0.28
0. 12
0.27
-_
0.20
0. 17
0.21
0.22
..
0.20
..
-.
0.21
--
0. 11
0.35
0. 17
..
0.27
0.32
--
--
0.24
0.26
--
0. 18
0.28
0.27
--
156
-------
FECES - Cadmium
Group 3
(smokers)
1 12
141
180
142
221
187
236
i-19
176
600
139
230
204
210
098
122
(non smokers)
111
311
133
203
297
080
161
177
224
129
296
222
094
1
0. 38
0. 23
0.41
0. 17
0. 17
0. 10
0.22
0.21
0. 35 '
0.27
0.28
0. 13
0. 31
0. 31
0.42
0.41
')
*• _
0. 17
0.24
0.40
0.42
0.21
0.29
1.45
0. 34
0. 13
0. 38
0. 18
0.22
Test
2
0.24
0. 27
0. 22
0.29
0.06
0. 11
0. 23
0.22
—
0.24
- -
0.07
0.29
0.26
0. 11
0. 14
0.26
0. 14
--
0.25
0.23
0. 12
0.25
0. 52
0. 18
0.27
0.28
0.39
0. 34
[j.g/g Fcces
Group 3A
3
0.27
0. 16
0.40
0.26
0.41
—
0. 35
0.23
0.26
0.42
0.25
0. 24
0. 15
0.07
0.06
0. 30
0. 34
0. 14
0. 30
0. 20
0. 12
0. 53
0. 21
0. 29
0.28
0. 18
0. 17
0. 33
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
4
.23
.48
.29
. 13
_ _
- -
. 12
.49
.25
_ -
. 35
.20
.37
. 14
. 13
.25
. 10
--
.24
.40
.08
.25
.24
.20
.32
.22
.47
.30
(smokers) 1
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
169
(non
165
083 .
136
215
160
120
097
213
225
134
166
125
170
234
118
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
smokers)
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
[
27
17
25
28
26
22
19
26
14
15
18
31
19
15
15
24
14
14
10
03
34
11
33
26
31
27
17
54
24
22
23
30
04
27
24
17
T
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
e s t
2
.21
. 15
.03
. 17
.20
.21
. 13
.25
.02
. 12
.21
. 31
.23
.26
. 12
- -
. 10
. 18
- _
. 30
. 35
. 17
.30
.05
.25
. 30
. 16
. 17
—
. 14
. 15
.01
.05
. 35
.26
.28
3
0.31
--
0.20
0.44
0. 19
0.21
0.41
1.20
0.08
0. 15
0. 13
0.24
0.20
0.40
0. 15
_ -
0. 16
0. 13
0.21
0.37
0.30
0.24
0.29
0.24
0.31
_ _
0.28
0.25
0.29
0.37
0.22
.- ..
0.04
0.21
0.23
.. «
_4
0.23
_ _
—
0.24
0. 17
0.24
0.41
0.28
0. 12
0.27
0.20
0. 17
0.21
0.22
—
0.20
_ _
_ _
0.21
--
0. 11
0.35
0. 17
0.27
0. 32
- -
0.24
0.26
_ -
0. 18
0.28
0.27
_ _
157
-------
FECES - Lead
Group 1
(smokers)
022
054
033
029
030
020
0:3
016
069
036
0-10
00<5
039
027
032
042
023
026
053
012
047
014
017
071
1
1.1
2.2
8.6
1.4
...
2-5
0.5
2.2
_ - -
1.3
1.0
1.3
2.2
1.2
1.2
1.2
1.1
19.4
2.8
1.2
2.0
4.3
6.2
2.1
Te
2
2Z. 1
2.1
2.0
3.2
7.5
1.7
2.8
1.5
3.1
4.9
2.6
4.4
2.8
0.8
2.9
2.4
1.7
3.4
3.0
0.9
2.2
1.9
4.7
0.6
st
3
1.3
2.2
3.0
5.1
2.3
2.2
4.3
2.8
1.0
2.5
0.6
1.5
2.9
0.6
1.1
0.7
1.3
1.8
2.8
2.8
2.3
2.2
2.5
2.2
4
1.1
16.7
1.3
1.0
2.5
2.2
1.2
1.5
4.9
1.4
1.2
2.2
2.8
2.0
1.3
1.0
1.3
3.2
3.1
0.9
2.3
0.9
1.6
1.4
(non smokers)
046
035
024
013
019
015
049
055
034
045
067
070
0.6
0.9
0.7
1.0
0.7
1.8
1.0
2.9
1.9
1.0
5.2
0.3
2.1
1.6
4.1
- --
0.2
1.6
1.4
2.1
5.5
1.1
2.6
1.1
1.2
2.4
3.2
2.6
1.9
1.0
0.7
0.9
2.0
1.6
2.1
1.2
1.2
1.4
0.9
2.4
1.4
4.6
0.8
1.5
4.8
0.7
3.5
1.9
Group 1A
(smokers)
350
348
329
336
321
313
284
320
340
318
339
283
337
346
314
315
349
286
325
345
316
331
1
0.7
0.3
0.8
2.3
0.4
2.5
0.9
4.3
0.8
4.9
4.2
4.1
2.5
26.0
2.7
0.7
1.3
0.9
2.6
0.6
1.5
Te
2
1.3
1.5
1.2
0
1.0
0.9
1.8
6.3
13.1
1.6
1.6
1.4
1.5
2.0
1.4
3.8
2.0
1.6
0.8
3.2
st
3
1.3
0.7
2.9
3.5
2.0
2.8
2.5
2.4
4.1
1.6
5.8
1.8
1.7
2.8
4
0.5
2.1
2.2
7.8
0.2
1.3
0.7
2.2
0.4
1.8
3.7
0.6
1.3
4.6
2.0
2.5
0.5
3.7
2,5
0.6
2.0
(non smokers)
323
312
285
326
258
343
327
330
351
338
324
328
341
319
1.6
1.8
0.7
4.8
1.3
1.2
1.0
2.3
4.8
1.2
1.0
1.2
0.9
0.7
2.9
0.6
2.0
0.1
3.3
1.6
2.3
2.4
0.9
2.2
2.5
0.9
0.4
1.6
3.1
0.5
4.7
0.6
0.7
1.9
2.5
4.1
1.3
3.4
1.2
3.5
2.5
2.2
2.2
1.1
4.0
1.2
1.3
1.3
0.9
1.9
158
-------
FECES - Lead
-------
FECES - Lead
Group 3
(smokers)
112
141
180
142
?~M
187
z?-j
149
176
600
139
230
204
210
098
122
(non
111
311
133
203
297
080
161
177
224
129
296
222
094
2
4
4
1
?,
Z
0
3
7
3
3
2
2
2
0
0
smokers)
-
1
7
3
5
1
16
6
3
3
2
1
2
1
.9
.7
.0
.0
.0
.1
.9
.2
.0
.0
.3
.4
.0
.4
.7
.7
_-
.8
.3
.9
.7
.5
.1
.4
.7
.0
.6
.4
.5
Te st
2
2.1
4.3
2.8
2.5
1.4
2.0
2.0
3.2
2.1
0.5
0.7
3.1
1.8
2.6
2.1
1.0
3.4
3.8
2.8
6.0
9.7
1.5
2.5
2.9
1.5
2.5
3
1.3
2.4
1.9
1.4
2.3
1.8
2.6
2.1
4.3
1.8
1.5
2.5
2.1
2.3
1.1
2.9
2.4
8.5
3.0
1.1
2.5
1.5
4.3
3.2
2.2
1.4
2.1
0
1
7
0
-
-
_
1
2
1
_
4
0
2
1
2
1
0
-
3
2
4
3
5
1
2
4
5
6
4
.8
.3
.5
.8
--
_-
_-
.4
.6
.6
-_
.0
.9
.4
.5
.5
.4
.3
-_
.4
.3
.6
.4
.5
.9
.5
.9
.4
.4
Group 3 A
Ismokers)
091
131
227
245
226
126
229
195
233
175
157
209
188
123
182
214
186
172
244
109
169
Test
1
3.6
0.6
0.5
0.1
3.2
11.7
1.4
1.1
1.4
1.1
0.1
2.2
0.6
0.6
0.6
3.1
2.4
1.1
2.0
12.0
3.6
2
15.9
0.6
1.3
1.2
1.4
4.8
3.3
0.5
1.4
1.4
1.1
1.4
2.0
1.7
0.6
0.1
0.6
1.8
7.6
3
3.9
1.2
3.2
1.6
2.4
1.5
2.5
0.9
2.4
2.4
2.9
1.8
0.7
2.0
0.0
0.5
0.7
6.8
4.2
4
2.1
0.7
1.6
1.1
2.6
1.5
0.2
1.1
0.1
1.8
30.4
2.0
1.9
0.9
4.0
(non smokers)
165
083
136
215
160
120
097
213
225
134
166
125
170
234
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Report on
"Design of Procedures for Monitoring
Platinum and Palladium"
Contract No. 68-02-1274
SwRI Project No. 01-3881-000
Author:
Donald E. Johnson, Manager
Analytical & Biochemistry Section
Department of Chemistry & Chemical Engineering
Prepared for:
Dr. Douglas L. Worf
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
by
Southwest Research Institute
P. O. Drawer 28510
San Antonio, Texas 78284
April 12, 1974
; 165
-------
The objectives of this phase of the study were to determine the
existence of industrial point sources for survey of workers occupationally
exposed to platinum and palladium metals and to design procedures for
surveying populations for baseline levels of these metals. The literature
search conducted on platinum and palladium under a portion of this
investigation was utilized as a source of information to guide the selection
of sites and for the design of sample collections required to conduct a proper
survey. The review of the literature and documentation of data are
found in the report for that portion of the study and need not be repeated
here. The results did indicate that there have been some toxic effects
indicated for the soluble forms of platinum. These effects occurred
primarily in refining operations where a soluble form of platinum was
found. No health effects for palladium were noted.
This report is designed to provide procedures for the determination
of absorption, retention, rate and route of elimination, and possibly
deposition of platinum and palladium compounds in humans. The data that
would be developed utilizing these procedures -would provide the EPA with
guidelines for assessing the potential health effects of platinum and
palladium attrition products from the catalytic muffler.
Selection of Sites
Information obtained from the literature indicates that the
industrial point sources for possible exposure to platinum and palladium
166
-------
compounds would be found in three major categories:
1. mining
2. refining
3. processors
Very little mining of platinum or palladium takes places in the United States.
The Sudbury area cf Canada has a substantial mining operation. The mining
processes produce a concentrate of platinum and palladium. The metals
are apparently in an insoluble form at this stage as the noble metal or as
the metal oxide. There are probably measurable quantities of platinum
and palladium dust in and around the mining operation; however, it is
unlikely that these insoluble forms of the two metals are absorbed into
humans. It has been shown that the allergic reactions to platinum, for
example, occur only with the soluble platinum salts and not the insoluble
forms.
The refining processes for platinum and palladium have in the past
shown measurable quantities of the two metals in the air. During the
refining process, the concentrates are converted to a soluble form using
aqua regia, and they are further processed to various forms of quite pure
platinum and palladium. During these processes, there is ample
opportunity for particles of platinum and palladium to exist in the air
either in the form of mists or dusts. There are two primary refineries
located in the United States, with a number of much smaller operations.
Both of the larger refineries are located in New Jersey.
The users of platinum and palladium are quite varied. These
sites are spread throughout the United States and are not considered
167 , ,
-------
likely sources of a sufficient number of workers (in central locations)
exposed to attrition products from platinum and palladium. It would
require much more investigation to determine optimum locations
within this category.
From the above study, it is concluded that the most likely
place to conduct an epidemiologic survey for exposure to platinum and
palladium would be in the refining industry, with the secondary source
in the mining of platinum and palladium. As stated above, there are two
primary refineries, both located in New Jersey, each with a sufficient
number of workers in the plant to provide the necessary data base for
platinum and palladium levels. Both of the refining companies have been
contacted and supplied with information regarding the proposed investigation.
It is possible there will be some difficulties in obtaining permission from
these companies to conduct these surveys.
As stated above, it is probable that the insoluble form of
platinum and palladium is not readily absorbed by humans; however, this
has not been documented. It may be important to determine whether or
not this is true in an actual epidemiologic study in the mining area. The
catalytic muffler may emit both the soluble and insoluble forms of
platinum and palladium, and it is important to know whether or not the
insoluble form is absorbed to any extent. No contacts have been made as
yet with the mining companies; however, the preliminary contacts with
the refining companies may provide these contacts. Each of the two
refining companies is the parent company of mining operations in the
Sudbury area of Canada.
168
-------
It is proposed that baseline studies be conducted in the Los Angeles
basin area and in a rural suburb of San Antonio. The first area is suggested
because of the high density of automobiles in that area and because it has
one of the more severe air pollution problems resulting primarily from
auto exhaust. It is proposed that a survey be conducted in this area near a
heavily trafficked freeway. The survey would center on a large apartment
complex in which data from humans, air and soil samples would be
collected. Platinum, palladium and lead would be analyzed in all samples.
Lead is included because the catalytic muffler will require the use of
low or non-leaded gasoline to prevent poisoning of the catalyst. These
baseline studies would provide data for comparison purposes for future
epidemiologic surveys and presumably would show an increase in
platinum and palladium with a reduction in lead.
The second baseline survey would be conducted in a rural
community near San Antonio with the identical sampling protocol to that
of the Los Angeles basin. The objectives would be to provide data on an
area relatively free of air pollution from any source. These data would
be very useful for comparison purposes with other areas more heavily
polluted and for future comparisons. The suggested areas are Fredericksburg
or Boerne, Texas. Each of these locations is ideal for baseline studies,
and there is sufficient population to provide the necessary human
subjects.
169
-------
Design of Questionnaire
A trace metal questionnaire has been developed and is shown in
the appendix. This questionnaire has been designed specifically for
survey of industrial point sources and conduct of baseline surveys for
platinum, palladium and lead. The questionnaire is designed such that
keypunching of the relevant data can be readily performed. The
questionnaire will collect information regarding smoking habits, age,
sex, ethnic background, hair color, occupation, and other covariate
information. Since little information is available regarding platinum
and palladium, the questionnaire has intentionally been designed to
collect more information than may be required.
Design of Surveys
It is proposed that five separate sites be surveyed for body burdens
of platinum and palladium in individuals and for collection of air and soil
samples in the environments of these sources. The five sources are:
two refineries, one mining operation, the Los Angeles basin area, and
a rural suburb of San Antonio, Texas. It is proposed that at least 40
subjects be examined in the two refining operations for urine, blood, hair
and fecal samples. Approximately 20 of these will be from one of the
refineries and 20 from the other. The subjects selected for study will be
those individuals working regularly in the immediate vicinity of the
refining processes. Those subjects selected for study will have worked
at least 6 months in the plant. It is likely that subjects selected for the
refineries will be males. Each subject will be sampled twice during a
170
-------
five-day week. The schedule will provide for sampling on a Tuesday and
a Friday. During this five-day week, a high volume portable air sampler
will be used to collect air samples within the plant environment. Samples
will be collected over an eight-hour period covering the work schedule of
the workers to be studied. Three of these portable air samplers will be
utilized with the collection of approximately 15 air samples for each of
the two refineries. Approximately 10 soil samples will be taken around
the refinery, and if a pond or lake is located in the immediate vicinity
of these refineries, water samples will also be taken.
Arrangements will be made with the local medical examiner's
office in which the two refineries are located to collect any available
autopsy samples from workers from these two plants. The medical
examiner will be instructed to collect portions of lung, liver, kidney,
hair, and spleen in suitable containers which will be rapidly frozen and
shipped to SwRI laboratories.
The design of the survey for the mining operation will be
similar to that for the refineries. A total of 40 workers will be surveyed;
each subject will be sampled twice during a five-day period for blood,
urine, hair and feces. A high volume air sampler will be used in the
immediate vicinity of the mining operation. If the mining is conducted
in confined areas such as in a tunnel, then a high volume portable air
sampler will be used. A total of approximately 15 air samples will be
collected to describe the concentration of platinum and palladium in
the environment of the miners. It is probable that the subjects selected
171
-------
in the mining areas will be males. No attempts will be made to exclude
workers on the basis of age.
For the baseline studies in the Los Angeles area and the rural
community near San Antonio, an age group study will be conducted. Three
age groups are suggested: pre-school, young adults, and aged. Approxi-
mately 40 subjects will be utilized for each of the three age groups.
Ambient air measurements will be made for platinum, palladium and lead.
These samples will be collected using high volume samplers operated in
the immediate vicinity of the areas to be studied. The samplers will be
located at ground level and will be operated for 24-hour periods. Two
high volume samplers will be used, and there will be approximately 10
air samples collected for each of the two sites during the sampling
period.
The urine samples collected for all subjects will be overnight
specimens in which the total urine voided will be measured and an aliquot
taken for analysis of the metals. The results will be reported as
quantities of trace metals per liter -with an estimate of the quantities
excreted per day. 20 ml of blood will be taken from each subject except
young children, from which 10 ml will be taken. Results for blood will
be reported on whole blood for quantities per 100 ml. Some studies -will
be made on fractionated blood, particularly from refinery workers and
miners as to where in the blood the platinum and palladium compounds
are located. Two to three grams of scalp hair will be collected from
each subject twice during the sampling period. These samples will be
172
-------
collected at regular haircut or from comb or brush collected daily.
If there is insufficient quantity of hair available at these intervals, then
small quantities of hair will be clipped from the backs of the subjects'
heads. Overnight fecal samples will be collected from the subjects at the
same time urine samples are collected. The total fecal output will be
collected and measured. The results of the metal analyses will be
reported as quantities per gram of feces with an estimate of the total
fecal output for each subject on a daily basis. Quantities of the metals in
air -will be quoted as quantities per cubic meter of air. Soil samples will
be reported as quantities per gram of soil.
Autopsy samples will be reported as quantities per gram of wet
tissue. The number of autopsy samples to be studied will obviously
depend on the availability of samples, but it is likely that the total
numbers of occupationally exposed will be five or less, and in the baseline
studies five to ten may be available.
Contacts have been made with the Committee of the Academy of
Sciences concerned with attrition products from the catalytic muffler.
Dr. Joe Hightower of Rice University is the head of this committee, and
Dr. Barney Rosenburg of Michigan State University is a member of the
committee. They are gathering information on the possible health effects
of platinum and palladium. The general design of this project was
discussed with both of these individuals. It is proposed that a close liaison
be maintained with this committee and that we exchange reports.
173
-------
Palladium" - EPA Contract No. 68-02-1274 - SwRI Project 01-3881-000
APPROVED:
John T. Goodwin
Vice President and Director
DEJ: pb
174
-------
TRACE METAL QUESTIONNAIRE
STAF
ID*
F USE ONLY
Cob 1-3
II II
1. Nam (In Full).
2. Address: Street.
City-
Postal Code.
Telephone.
3. How many years have you lived in your present city or town?
4. Is your residence located:
1—In the central portion of a city
2—In a suburban community or residential area
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:
1—Employed fulltime (including ;pl* employed) 4—Housewife
2-Employed part-time 5-Student
3-Urwmployed 6-Pre-school age
3—In a rural town or community
4—In a rural setting some distance from any town.
Cols 4 24
Coh2&44
Cols 45 59
Cote 60 64
Cols 65^1
Col 80
Cols 4 5
OH
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 8
D
Col 9
D
Col 10
coin
7-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 12-13
9. How long have you worked for your present employer?.
10. What is your job title?
Cols 16-17
Col 18
11. Your work Is primarily? 1-Inside
12. If you work inside, do you perform:
2-Oirtside
1-Off ice work
2—Production or manufacturing
CoM 9
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
175
-------
15. If you are a current or an ex cigarette smoker:
a. How many cigarettes do (did) you smoke per day
1—Less than 1/2 pack per day (1-5 cigarettes per day)
2—About 1/2 pack per day (6-14 cigarettes per day)
3-About 1 pack per day (15-25 cigarettes per day)
b. How old were you when you first started smoking?
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)
Years
c. How old were you when you last gave up smoking, if you no longer smoke?.
_Years
16. What is your marital status?
1-Single
2-Married
3-Separated
4-Divorced
5-Wktowed
17. How many times have you and your family changed living quarters 0—None
1-One time
2—Two times
18. What educational level has been completed by the head of your household:
3-Three times
4—Four times
5—Five or more
1-Lea than 8th grade
2-8th grade
3-High School-Incomplete
4-High School-Completed
19. What was your age in years on your last birthday?.
5—College—Incomplete
6-College-Completed
7-Graduate School
20. What is the natural color of your hair?
21. What is your sex?
1-Male
22. Females Only:
a. What is your horrnbnal status?
b. Do you use ora I contraceptives?
1—Brown
2-Black
3-Red
2-Female
1—Pre-puberty
2—Menstrual
3—Menopause
1-Yes
2-No
JVears
4-Blond
5-Gray
6-Bronchiolitis
7-Bronchitis
8—Tumor or Cancer
9-Other (Please Specify)
23. Have you ever experienced any of the lung related 0-None
problems listed here: 1 -Asthma
2—Emphysema
3—Tuberculosis
4-Histoplasmosis
5—Bronchieclasis
24. Are 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
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appendix
TRACE METALS IN OCCUPATIONALLY AND
NON-OCCUPATIONALLY EXPOSED INDIVIDUALS
Authors:
D. E. Johnson
J. B. Tillery
R . J. Prevost
To be presented at the conference on:
The Health Consequences of Environmental Controls:
Impact of Mobile Source Emissions Controls
April 16-19, 1974
Durham, North Carolina
c
Southwest Research Institute
P. O. Drawer 28510
San Antonio, Texas 78284
reprints to be submitted to
D. E. Johnson
Department of Chemistry and Chemical Engineering
Southwest Research Institute
177 l I i
-------
ABSTRACT
An epidemiological survey was conducted in Houston, Texas
on five trace metals in policemen, parking garage attendants, women
living near freeways arid three control groups of subjects. The controls
were matched with the exposed groups for covariate information such
as age, sex, smoking habits, ethnic background, socioeconomic status,
hair color and education. Each subject was sampled four times for blood,
urine, hair and feces, and these samples were analyzed for lead,
cadmium, zinc, manganese and copper. Lead and cadmium were
correlated with airborne exposures but zinc, manganese and copper were
not.
The second part of this paper deals with a market study of
platinum and palladium markets and a design of an epidemiology survey
of individuals occupationally and non-occupationally exposed to these two
metals. The market survey shows that although the catalytic muffler
will have a major impact on the market, it is predicted that producers
can meet these demands.
178
-------
"TRACE MKTALS IN OCCUPATIONSLLY AND NON-OCCUPATIONALLY
EXPOSED INDIVIDUALS" - Presented by D. E. Johnson
Part I. Measurement of Human Exposure
to Fuel Additives
The most commonly used fuel additive in gasoline powered engines
in the United States is tetraethyl lead. There are, however, a number of
other fuel additives which may be used in greater quantities in the future
that contain a variety of trace metals such as manganese, copper and zinc.
Other trace elements such as cadmium are present as impurities* It ha.s
been shown that trace metals such as these may accumulate in various
tissues and possibly contribute to the incidence of carcinogenic, mutagenic
or teratogenic processes.
The objective of this investigation has been to develop methodologies
for monitoring free-living populations for their exposure to trace elements
that arise from automobile exhaust emissions. A large number of studies
have been conducted similar to these for lead, but there have been relatively
few involving the assay of other trace metals in free-living populations.
Methods
The monitoring program was conducted in the metropolitan area of
Houston, Texas. Six groups of individuals were monitored as shown below.
179
IT-
-------
Group 1 - Policemen on fool patrol
Group 1A - Office workers in downtown Houston which
served as controls for Group i
Group Z - Garage Attendants
Group 2A - Orderlies and custodians which served as
controls for Group Z
Group 3 - Females living within Z blocks of a freeway
Group 3A - Females living away from a. freeway; served
as controls for Group 3
Thirty-six individuals were selected for study in each of these
groups. Policemen, garage attendants and females living near freeways
were selected first, and then the control subjects were selected to match
the appropriate group as closely as possible for covariate data such as.age,
sex, smoking habits, hair color, ethnic background, socio economic status,
and education. Figure 1 shows the comparison of these groups for the
variables mentioned. This type of matching is essential to make valid
comparisons between groups of individuals for these trace metals. The
data illustrates that the groups were relatively well matched except for the
education of the policemen vs their controls and a difference in age between
the parking garage attendants and their controls.
Each subject was sampled four separate times for blood, urine,
hair and feces. Blood, urine and hair were analyzed for all five metals ,
whereas feces was monitored for lead and cadmium only. Hematocrits
and urinary coproporphyrin were monitored in each subject four times.
All samples were analyzed by atomic absorption spectrophotometry
utilising a deuterium arc background corrector. Each metal in each
180
-------
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181
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sample matrix (i.e. blood, hair, urine, etc) was analyzed by one of the
fol.lov/ing atomic absorption techniques:
(1) aspiration into an air-acetylene flame
(2) micro-sampling using the Delves cup method, or
(3) graphite tube furnace.
Hair samples were washed and then digested with nitric-perchloric
acid mixture. (1, 2) The digest solution was then aspirated into an
air-acetylene flame to analyze for each metal. (3)
Blood samples were diluted with deionized water and allowed to
hemolyze. Cadmium and lead were then determined by the miciro-sampling
%
(Delves cup) technique .(4, 5) Copper and manganese were analyzed with
the graphite furnace(6, 7) and zinc by aspiration into an air-acetylene
flame (8,9).
Urine was either analyzed without dilution or diluted with 0. IN HC1
or deionized water. Cadmium was determined by the micro-sampling
technique. (10,11,12) Lead, copper and manganese were determined by
the graphite furnace (7,12), and zinc by aspirating into a flame . (8)
Feces samples were digested with a nitric-perchloric acid
mixture. (13) The digest was analyzed for lead and cadmium with the graphite
furnace.
Results
All of the data obtained were examined statistically by use of a
t-test using paired comparisons. The data for coppei', manganese and x,inc
182
-------
indicated that the values were not related to exposure to exhaust products.
The median values were within normal for the groups of subjects. The
results did indicate that there were larger quantities of copper in the
blood, urine and hair of females versus male subjects. It has been reported
previously that females have higher levels of copper than males. Also,
there were lower levels of zinc in blood and urine for females while higher
levels were found in hair.
A summary of the data obtained for cadmium is shown in Table 1.
Levels of cadmium are low in all specimens. These low levels pushed
the analytical methods to the limit of effectiveness. In addition, there
appear to be rather wide individual variations in cadmium content,
particularly in hair samples. Statistical comparison of the data indicates
that there are significant differences in cadmium levels in urine between
Group 1 and 1A and 2 and ZA at the 95% confidence limits. No differences
were seen in the female subjects. The values reported here are consistent
with data reported by others in non-occupationally exposed individuals.
It is possible that the levels of cadmium in urine are related to the exposure
ale i) to air pollutants .
Table 2 presents the comparison between groups for lead values.
There are significant differences (at the 95% confidence limit) for the male
volunteers (policemen versus control and garage attendants versus control)
in blood and hair. There were slightly higher levels, although not significant,
in females living near freeways versus their matched controls in blood.
183
-------
For urine, Ihi.rr. we,-<- .-i^j.'. .,: <', -.1T.J r oncer; between the policemen and
their controls ;md worncm };-/;:••• m--:1- freeways and their controls.
Hematocrit d-ttM for l^c ji". - -.;.••• <->.? individuals \vere normal for their
ages. There \veve ro ••"o^" •.:-.* n'T/crejicct. between the groups for the
hematocrits. For the ur; . • ,- coi.- -.;l:orphy?-ins there were no statistical
differences between jioJice- >'*-. ai:cl ,'Jieir controls and garage attendants
and their controls; how ever 5 (liere wei'e significantly higher values for
) the females living near frce-./v/s versus their controls.
DiscuKsio7i
Comparison botweei' I^e exposed groups and controls showed, as
%
expected, that policemen unn garage attendants had significantly higher
blood and hair lead level s. Fecal lead measurements were included in
this study to obtain data regarding the dietary consumption of lead. Fecal
lead is a good indicator for d'.etary consumptions, since 95% of orally
ingested lead is not absorbed and is eliminated via feces. There were no
statistically significant differences in fecal lead between any of the groups
studied. From these resulLs, it is concluded that the differences seen
in body burdens of lead between the exposed and control groups are related
to airborne exposures, probably from auto exhaust. For females living
near freeways, there were higher levels than their control subjects for
lead in blood, urine arid hair, although only urine was statistically
significant at the 95% confidence limit.
184
-------
In a recent position paper by thu Environmental Protection Agency
(14)
on Health Effects of Lead from Automobile Emissions, results of
several studies on exposed population were summarized. It was
concluded that blood-lead levels of 40 |j.g per 100ml or above existed to
a small but significant extent in the general adult population. The level of
40 ug of lead in blood has been used by many agencies as the level in which
some concern for health effects from lead is warranted. The results from
this study show the following percentage of blood leads of 40 [j.g or higher:
policemen 6%, controls for policemen 2%, garage attendant lb%, controls
for garage attendants 3%. The females, both exposed and control, had
no blood lead values of 40 \s.g .
\
The Seven City Lead Study included a study of females in Houston,
(.0
Texas. Their blood-lead values compared closely with values obtained in
this study. Their data were 12.5 ug per 100ml of whole blood, whereas
we obtained 12.9 and 11.9 ug. The lead values found in this study indicate
that females may metabolize lead differently than do males. Thus, males
had blood-lead levels between 28.3 and 18.4, while females were 12.9 and
11.9 for whole blood, and in hair, males' values ranged from 47.6 to 13.1,
while female hair lead levels were 7.4 and 6.0. All of the females
utilized in this study were employed in the metropolitan area of Houston.
The control group of male subjects for the garage attendants worked in the
same building as did the females utilized for this study. It is unlikely that
exposure to different lead levels in the air or from dietary sources produced
these significant differences in blood and hair lead levels. The values for
185 ,
-------
fecal lead of females versus males are sliijblly higher feu f^mal >•;.-,.
If the observations in this paper arc correct, it could explain so^o nf
the lower lead values in blood of subjects examined in iho Seven City Sti'Oy
because their subjects were predominantly women.
Market Study of Platinum and Palladium
and Design of Monitoring System
The catalytic muffler shows considerable promise for reduction of
carbon monoxide, oxides of nitrogen and hydrocarbons in the emission of
automobiles. These muffler systems utilize platinum and palladium a§
the catalyst. Recent data indicate that these mufflers emit particles of
platinum and palladium as well as sulfates. This project was designed to
determine what effects the introduction of the catalytic muffler would have
on the world market for platinum and palladium and to develop
epidemiological procedures for use in monitoring body burdens of the
general population for platinum and palladium.
Methods
A thorough review of the literature was made for identification of
industrial uses of platinum and palladium to include production figures in
the United States and foreign countries and the known reserves. The
literature survey also included the documentation of human, exposure c.i:,o
and the toxicological information available for animals and man. The
review covered the open literature through the end of 1973, and Ll also
186
-------
TABLE 3. WORLD PRODUCTION OF PLATINUM
AND PALLADIUM
Average Annual, 1969-1972
(Thousands of Troy Ounces)
1969-1972 Average
Source
Canada
Columbia
Ethiopia
Finland
Japan
Philippine s
Republic of South Africa
U.S.S.R.
United States
TOTAL
Platinum
188
26
0.3
0.2
3
0.6
909
665
9
1801
Palladium
187
--
--
0.3
5
1
321
1339
13
1866
Total
375
26
0.3
0.5
8
1.6
1230
2004
22
3667
Sources: Minerals Yearbook and Engineering and Mining Journal
187
-------
TABLK 4. WORLD CONSUMPTION OF
1971
(Thous.'inds of Troy Ounces)
Nation
United States
Japan
U.S.S.R.
West Germany
France
Italy
Canada
United Kingdom
Netherlands
Sweden
Switzerland
TOTAL
Consumption
1376
758
589
451
313
74
68
49
33
17
12
3740
Source: Minerals Yearbook
188
-------
i.j.K ;,. .KSTJMATED FUTUKE WORLD DEMAND
PLATINUM AND PALLADIUM
(Thousands of Troy Ounces per Year)
Total Demand
United L'tr Lcs;
biise platinum
automotive catalysts
total platinum
base palladium
automotive catalysts
total palladium
total base
total automotive
Total
1971
541
541
760
760
1301
1301
1980
734
774
1508
898
33Z
1Z30
1632
1106
2738
1990
1044
866
1910
1095
371
1466
2139
1237
33-76
Rest of WorH: platinum
palladium
Total
Grand Total
platinum
palladium
Total
1283
1163
2446
1824
1923
3747
1826
1655
3481
3334
2885
6219
2703
2450
5153
4613
3916
8529
Source: Mineral Facts & Problems, 1970; A Look at Business in
1990 (a Summary of the White House Conference on the Industrial
World Ahead, February 7-9, 1972); and SwRI
189
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included contact,:; with various government and industrial concerns for
additional information. Information obtained from the literature was
used to assist in identifying industrial point sources of platinum and
palladium and the design of analytical methods for assay of platinum and
palladium in various media. An epidemiology survey was designed to
determine the relationship between airborne concentrations of platinum
and palladium and levels in various tissues of individuals occupationally
exposed. The procedures developed will be used to monitor the general
population for baseline levels prior to introduction of the catalytic muffler.
Results
Table 3 shows the world production of platinum and palladium.
The data show that half of the world platinum and 1/6 of palladium
production comes from the Union of South Africa, while 1/3 of platinum and
2/3 of palladium is from theUSSR. Canada produces about 10% of both
platinum and palladium, while the United States produces less than 1% of
(Table 3) each.
Table 4 shows the world consumption of platinum and palladium as
.>
of 1971. The United States uses 37% of the total, while Japan uses 20%,
Russia 16% and West Germany 12%. The data in these two tables point
out clearly that the United States is heavily dependent on foreign sources
(Table
-------
This table does not include a possible increase in consumption of
platinum and palladium if countries other than the United States adopt
the catalytic muffler for use in their countries. The data indicate that
the use of the automotive catalyst will provide considerable increase in
the consumption of platinum and palladium; however, a detailed analysis
of the reserve situation and the potential of producers to meet these
demands indicates that this production can be increased as the demand
Le 5) increases.
Platinum was considered harmless until the report published by
Hunter, Hilton and Perry in 1945 (16) which documented an investigation
»
of exposure among workers in four refineries. It was found that the
complex salt? of platinum produced various symptoms such as asthma,
eczemateous lesions and dermatitis in a high percentage of workers
exposed. It was found that exposure to metallic platinum or palladium or
the complex salts of palladium produced no apparent similar effects.
. Similar studies to those of Hunter, et. al., have confirmed that the soluble
forms of platinum are toxic when the dosage is sufficiently high. Little
' information is available regarding assay of platinum levels in the work
environment, although one report of Fothergill, et. al., 1945, (17) reported
values of 5 to 70 |^g of platinum per cubic meter of air. It is likely that
refineries in plants of this type have significantly reduced these levels.
Very little information is in the literature regarding toxicity studies
in animals for palladium, although one report did indicate that palladium
193
-------
salts administered to animals showed damage to heart, kidneys, liver and
bone marrow. Studies are currently underway within the EPA in
Cincinnati, Ohio to develop detailed lovicological data on platinum and
palladium.
The review of the literature indicated that there are three primary
categories of industrial point sources for possible exposure to platinum
and palladium compounds: major categories are mining, refining and
processing. The data indicate that the highest concentrations of exposure
to significant number of individuals would occur in the refining and mining
operations. The refining operation provides the possible exposure of
predominantly the soluble forms of platinum and palladium following
treatment with aqua regea, while in the mining operation the metals are
found in the insoluble form as the free metal or other forms which are
very insoluble. The data indicate that the insoluble form of platinum and
palladium may be poorly absorbed. Thus, it has been demonstrated that
the allergenic reactions are not produced by the insoluble forms in the
human exposures.
There are two primary refineries located in the United States,
with a number of much smaller operations. A follow on study is planned to
survey thet,e refineries for platinum and palladium in air, soil and refinery
workers. Blood, urine, hair and feces samples will be collected from
these individuals. Air samples will be taken in the plant environment, and
correlations will be made between levels of platinum and palladium seen
in the air versus levels produced in the tissues. A smaller study is pl.inm-d
194
-------
for the mining operation to determine whether or not significant
quantities of the insoluble form of platinum or palladium are absorbed
into the miners. This is important because the catalytic muffler may
under different circumstances produce soluble and/or insoluble forms of
platinum and palladium.
A baseline survey is to be conducted in the Los Angeles basin
prior to the introduction of the catalytic muffler and in a rural community
relatively free of any source of air pollutants. The data from these
surveys will provide a basis for comparison of future studies following
the introduction of the catalytic muffler. Three age groups will be studied:
*
young children, adults and aged. Both male and female subjects will be
examined.
Very few methods are available for measuring platinum and palladium
in biological tissues. This study has included the development of
procedures for monitoring these two metals in urine, blood, hair, fsces
and autopsy tissues. The procedures developed are based on atomic
absorption spectrophotometry using an extraction procedure and the graphite
furnace. It is likely that the quantities of these two metals in various
tissues will be very low; thus, the assay methods must be extremely
sensitive/ The graphite furnace procedure offers an advance in sensitivity
over the conventional flame techniques. The procedure developed thus
far is able to detect 0.88 jig of platinum per 100 ml of blood and 1.2 ug of
palladium per 100 ml of blood.
195
-------
References
1. Hammer, 1). 1. ct al. Trace Metals in Human Hair as a
Simple Epidcmiologic Monitor of Environmental Exposure.
In; Trace Substance in Environmental Health V, (1972). A
Symposium, D. D. Hnmphill, ed. University of Missoviri,
Columbia.
2. Harrison, W. W. , Vurachek, J. P. and Benson, C. A. The
Determination of Trace Elements in Human Hair by Atomic
Absorption Spectroscopy. In: Clin. Chim. Acta, 23, 83-91(1969).
3. "Analytical Methods for Atomic Absorption Spectrophotometry",
Perkin-Elmer Corp. , Norwalk, Conn. , March 1973.
4. Ediger, R. D. , and Coleman, R. L. Determination of Cadmium
in Blood by a Delves Cup Technique. In; Atomic Absorption
Newsletter, Vol. 12, No. 1, (1973).
5. Ediger, R. D. and Coleman, R. L. A Modified Delves Cup
Atomic Absorption Procedure for the Determination of Lead in
Blood. In: Atomic Absorption Newsletter, Vol. 11, No. 2 (1972).
6. Matousek, J. P. and Stevens, B. J. Biological Application of
the Carbon Rod Atomizer in Atomic Absorption Spectroscopy, 1.
Prelimirary Studies on Mg, Fe, Cu, Pb, and Zn in Blood and
Plasma. In: Clin. Chem. , 17, No. 5 (1971).
7. Amos, M. D. , et al. Carbon Rod Atomizer in Atomic Absorption
and Fluorescence Spectrometry and its Clinical Applications.
In: Anal.- Chem. , 43. No. 2 (1971). ','<
8. Dawson, J. B. and Walker, B. E. Direct Determination of Zinc
in Whole Blood, Plasma and Urine by Atomic Absorption Spectroscopy.
In: Clin. Chem. Acta. 26, 465-475(1969).
9. Sprague, S. and Slavin, W. Determination of Ion, Copper, and
Zinc in Blood Serum by an Atomic Absorption Method Requiring
Only Dilution. In: Atomic Absorption Newsletter, Vol. 4, (1965).
10. Hauser, T. R. , Hinners, T. A. , and Kent, J. L. Atomic Absorption
Determination of Cadmium and Lead in Whole Blood by a Reagent-
Free Method. In: Anal. Chem. , 44, No. 11 (1972).
196
-------
11. Kahn, H. L. , and Sebestyen, J. S. The Determination of Lead
in Blood and Urine by Atomic Absorption Spectrophotometry
with the Sampling Boat System. In: Atomic Absorption Newsletter,
Vol. 9, No. 2 (1970).
12. Davidson, I. W. F. , and Secrest, W. L. Determination of
Chromium in Biological Materials by Atomic Absorption
Spectrometry Using a Graphite Furnace Atomizer. In: Anal.
Chem. . 44, No. 11 (1972).
13. Adrian, W. J. A New Wet Digestion Method for Biological
Materials Utilizing Pressure. In: Atomic Absorption Newsletter,
Vol. 10, No. 4 (1971).
x
14. ' EPA's Position on the Health Implications of Airborne Lead,
November 28, 1973.
15. Tepper, A. Survey of Air and Population Lead-Levels in Selected
American Communities. In: Seven City Study (testimony) presented
at EPA Public Hearings in Los Angeles, May 3, 1972. -
16. Hunter, D. , Hilton, R. , Perry, K. M. A. Asthma Caused by
the Complex Salts of Platinum. In; Brit. J. Indust. Med., 2,
92(1945).
17. Forthergill, S. G. R. , Withers, D. F. and Clement, F. S.
Determination of Traces of Platinum and Palladium in Atmosphere
of a Platinum Refinery. In: Brit. _J. Indus t. Med. , 2_, 99(1945).
- 197
t
i t '
-------
Appendix B9.5
Report on
"Evaluation of Methods for Platinum and Palladium"
Contract No. 68-02-1274
SwRI Project No. 01-3881-000
Authors:
John B. Tillery and Donald E. Johnson
Analytical & Biochemistry Section
Department of Chemistry & Chemical Engineering
Prepared for:
Dr. Douglas L. Worf
Environmental Protection Agency
Research Triangle Park, North Carolina 27711
by
Southwest Research Institute
P. O. Drawer 28510
San Antonio, Texas 78284
April 25, 1974
198
-------
"Evaluation of Methods for Platinum and Palladium"
Introduction
The objective of this portion of the study has been to evaluate
the "flameless" carbon furnace technique of atomic absorption for
assaying tissue samples for platinum and palladium. This methodology
is needed for the conduct of epidemiology surveys of populations for
body burdens of these two metals.
The literature survey by Bumgarner and Yoakum provides an
excellent review of the current analytical methodology for platinum and
palladium through September, 1973. There have been a few papers
(2) (3)
published since that review which provide information on the analysis
of platinum using the "flameless" carbon furnace technique of atomic
absorption spectrophotometry.
Following the suggestion of the above mentioned reviewers, a
preliminary evaluation has been made of the "flameless" technique of
atomic absorption spectrophotometry for the analysis of platinum and
palladium in biological samples using a separation and concentration scheme.
The evaluation problem was approached from the standpoint of using
the "flameless" technique for analyzing a large number of biological
samples collected from a live population. Whole blood and urine were
selected as representative of the type of samples which may be collected
from a live population. These two sample matrices will provide
concentrations of substances (salts, proteins, etc.) which would be likely
to interfere with platinum and palladium analysis by atomic absorption.
Procedures worked out for these types of samples should be applicable,
with minor modification, to other types of biological samples.
199
-------
There are several separation-concentration methods which may
(1)
be applied to biological samples. A chelate-solvent extraction method
was selected, since there are extensive reports in the literature on the
use of this method for a variety of trace elements. It also affords a
very rapid and efficient method to preconcentrate the analyte in a large
number of samples.
A Perkin-Elmer Model 306 Atomic Absorption Spectrophotometer
was used in this study. The optics and photomultiplier were modified
(Perkin Elmer Part No. 040-0286) to reduce the "light scattering"
interferences caused by the heated graphite tube. A Perkin-Elmer Hitachi
Recorder Model 0^6 was used to record absorption peak heights. A
Deuterium-arc background corrector was also utilized. The graphite
furnace was a Perkin-Elmer HGA-ZOOO using a "regular" graphite tube.
Standard metal solutions used for spiking were Alfa Inorganics,
Ventron, chloroplatinic acid (1000 ppm metal) and palladous chloride
(1000 ppm metal).
Aqueous Sample Analysis
Analysis of spiked aqueous solutions of platinum gave detection
limits and sensitivities similar to those reported previously (e.g. 1.1 ng
(3)
detection limit and 1 ng for 1% absorption).
Palladium analysis of spiked aqueous solutions gave a detection
limit of 0.5 ng (signal to noise ratio 2:1) and a sensitivity of 0.06|ag for
1% absorption.
200
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Four-milliliter aliquots of spiked aqueous solutions were
treated with a combined complexing reagent, Stannous Chloride:Ammonium
Pyrrolidine Dithiocarbamate (SnCl^: APDC) (1:1), after their pH had been
adjusted to 3-4 with HC1 (IN). Methyl isobutyl ketone (MIBK) (0.5 ml)
was used to extract the metal-chelates. It was necessary to centrifuge
the solution to separate the aqueous-organic layers. The organic layer
was removed for analysis of platinum and palladium in the graphite
furnace using the instrumental conditions listed in Table I.
Platinum at the O.Z jig/ml and 0.05 ug/ml spiked levels gave
recoveries of 91 to 105% based on aqueous standards made at the
concentration levels of the extract solutions.
Detection limit and sensitivity (1% absorption) for platinum
extracts were 1.37 ng and 0.13 ng, respectively. Palladium recovery
was 105% with a detection limit of 0.54 ng and a sensitivity of 0.06 ng
for 1% absorption.
This extraction was also performed with ethyl acetate. A small
improvement in extraction efficiency was offset by the fact that the ethyl
acetate was more difficult to pipet into the furnace than the MIBK.
Cursory extractions with chloroform and carbon tetrachloride also showed
some improvement but were not examined further.
Blood Analysis
A 5-ml aliquot of spiked whole blood was digested with HNO~:HC1O4
(70:30) in a Vycor beaker at 200°C. A nitrogen stream was used to help
201
-------
evaporate the digest to near dryness. This remaining solution was
taken up in 2ml of concentrated hydrochloric acid and evaporated twice
more to near dryness. This evaporation and hydrochloric acid treatment
is necessary to remove the HC1CK, HNO and to convert to the chloride
any nitrosoplatinic acid which may be present. One milliliter of stannous
chloride solution (35%) was added to complex the platinum
( PtCl2(SnCl3) 1 . Then 0.5 ml of MIBK was added and the solution
shaken vigorously for 1 minute. It was necessary to centrifuge the
solution (15 min. at 2600 RPM) to recover the organic phase. The MIBK
layer was separated from the aqueous phase and analyzed for platinum
using the instrument parameters given in Table I.
The calculated detection limit for platinum in blood is 0.5 jjLg/100 ml,
and the sensitivity is 0.1 ng for 1% absorption.
Another 5 ml of spiked blood was digested by the procedure given
above. After reconstituting with hydrochloric acid, the pH was adjusted to
4-5 with sodium hydroxide, and 1 ml of APDC (2%) solution was added to
complex the palladium. The palladium complex was extracted into 0.5 ml
of MIBK/ Centrifuging (15 min. at 2600 RPM) was needed to recover the
organic solvent. The organic phase was separated from the aqueous phase
and analyzed for palladium using the conditions given in Table I.
The detection limit for palladium in whole blood by this procedure
is 0.12 |j.g/100 ml, and the sensitivity is 0.04 ng for 1% absorption.
202
-------
Recoveries of platinum and palladium from whole blood were
determined by comparing the organic extract concentrations with aqueous
standards made to the concentration of the organic extract, assuming
all the metal had been extracted. Recoveries ranged from 90-96% for
both platinum and palladium at the 4 jj.g/100 ml spike level.
Urine Analysis
Attempts were made to extract both platinum and palladium from
a spiked urine sample. Ten ml of the spiked urine was pipetted into a
small separatory funnel. The pH was adjusted to 4-5 with sodium
hydroxide, and 1 ml of APDC solution (Z%) was added. Then 1 ml of
MIBK was added, and the sample was shaken vigorously for 30 seconds.
The aqueous phase was removed from the funnel and the organic phase
washed twice with several milliliters of deionized water. These washings
were added to the aqueous phase. The organic phase was transferred to
a small screw-cap vial for analysis of palladium.
The aqueous phase was transferred to a micro-extraction vessel,
the pH adjusted to 1-Z with HC1, and 1 ml of stannous chloride (35%)
solution added. One milliliter of MIBK was then added, and the solution
shaken vigorously for 1 minute. Good recovery of the organic phase was
obtained, without centrifuging, by passing the organic phase through a
glass-wool plug in the extraction arm. The organic phase was then
analyzed for platinum.
203
-------
Initial attempts at this extraction have not proven effective for
platinum. Recoveries of palladium have also been low. The problem
is thought to be improper pH adjustment prior to extraction.
Conclusion
Atomic absorption spectrophotometry using the "flameless"
graphite furnace technique combined with an extraction-concentration
scheme provides sufficient sensitivity to determine platinum and palladium
in biological samples. Instrument operating parameters must be set
very carefully to obtain maximum sensitivity for these metals. Also,
extreme care must be used in making pH adjustments on the sample
solution, since the formation and extraction of the metal complex is
dependent upon a specific pH range. These procedures can be refined and
developed into an efficient and accurate method for analyzing a large
number of biological samples on a routine basis for platinum and palladium.
Investigating means of improving this analytical procedure may
follow two routes: (1) improvement in instrumental techniques to achieve
greater sensitivity and (2) investigation of other solvent-extraction schemes
Improving the analytical performance of the atomic absorption
instrument will require evaluation of newer and more sophisticated
instruments and improved spectral sources such as Electrodeless
(4)
Discharge Devices.
Evaluation of more effective solvent-extraction systems will require
a survey of the literature to discover new and exotic systems which may be
204
-------
applied to platinum and palladium. Other systems which have been
(5) (6)
used for these metals wiU also require investigation.
Investigation of other separation and concentration techniques
should also be carried out, specifically, ion exchange methods and
chromatography. These methods would favor the speed and accuracy
needed to analyze a large number of samples on a routine basis.
APPROVED:
J6hn T. Goodwin
Vice President and Director
— 205
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TABLE I. ATOMIC ABSORPTION INSTRUMENT PARAMETERS
Slit Ashing Ashing
Element Wavelength Setting Time Temp.
(nm) (nm) (sec) ~PQ
Atomization
Temp.
Platinum
Palladium
265.9
247.6
0.7
0.2
70
70
1500
1500
2700
2700
206
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REFERENCES
1. Bumgarner, J. and Yoakum, A., "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., Sept. 1973.
V /*
2. Janouskova, J., Nehosilova, M. , and Sychra, V., "The
Determination of Platinum with the HGA-70 Graphite Furnace",
' Atomic Absorption Newsletter, Vol. 12, No. 6 (1973) pp 161-162.
3. Adriaenssens, E., and Knoop, P., "A Study of the Optimal
Conditions for Flameless Atomic Absorption Spectrometry of
Iridium, Platinum and Rhodium", Analytica Chimica Acta,
6_8 (1973).
4. Aldcus, K.M., Dagnall, R.M., and West, T.S., "Preparation
and Spectral Characteristics of Microwave-excited Electrodeless
Discharge Tubes for Palladium, Silver, Platinum and Gold",
Analyst, Vol. 94, (1969) 11 347-353.
5. Khattak, M. A., and Magee, R.J., "Spectrophotometric
Determination of Platinum after Extraction of the Stannous-Chloro
Complex by High Molecular Weight Amines", Talanta, Vol. 12,
(1965), pp 733-741.
6. Briscoe, C.G., and Humphries, S., "An Investigation of the
Diethyldithiocarbamates of Palladium Including the Determination
of their Stability Constants"-, Talanta, Vol. 16 , (1969), pp 1403-1419,
207
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Appendix B9.6
A LITERATURE SEARCH AND ANALYSIS OF INFORMATION
REGARDING SOURCES, USES, PRODUCTION,
CONSUMPTION, REPORTED MEDICAL CASES,
AND TOXICOLOGY OF PLATINUM AND PALLADIUM
by
Richard A. Mayer, W. Lawrence Prehn, Jr., and Domald E. Johnson
Contract No. 68-02-1274
SwRI Project No. 01-3881
Prepared for:
THE ENVIRONMENTAL PROTECTION AGENCY
Research Triangle Park, North Carolina 27711
208
-------
EXECUTIVE SUMMARY
An inlemlve ncarch of the literature provides the basis for the
following conclusion* concerning platinum and palladium.
Supply and Demand. An average of 3.7 million troy ounces of
platinum and palladium were produced in the world in the four-year
1969-1972 period. The United States consumed about a third of this. The
proved world reserves amount to some 394 million troy ounces, with con-
siderable promise of increasing these reserves through new explorations.
Half of the proved reserves are in the Republic of South Africa and 45 per-
cent in the Soviet Union. Projected 1980 and 1990 world demands are 6.2
and 8.5 million troy ounces per year, respectively. The introduction of a
new demand for automotive emission control catalyst purposes (18 per-
cent of the total in 1980 and 15 percent in 1990) is not expected to upset
the world supply/demand situation.
This assumption does not consider the possibility that other
countries may adopt the catalytic muffler for their use. If this occurs,
there will be a larger demand on platinum and palladium resources.
Although it appears that the projected demands on platinum and palla-
dium reserves can be met with known sources, it should be pointed out
that the United States is almost completely dependent upon foreign
sources. The United States currently consumes nearly 40 percent of the
world production, but it produces less than 1 percent.
Health Hazards. No data exist by which an estimate can be made of
transfer of platinum and palladium to the environment. Investigations
show that only the salts of platinum present human health hazards. Indus-
trial exposure to these is limited to the mining and refining of platinum
ores and the preparation of catalysts for the chemical and petroleum
refining industries.
209
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NARRATIVE SUMMARY
Present World Supply and Demand
Based on reasonably reliable estimates from
foreign sources, world production of platinum and
palladium is estimated to have increased from a total
of 3.12 million troy ounces in 1969 to 3.90 million
troy ounces in 1972, a four-year increase of 25 per-
cent. World production by source is summarized in
the table below.
WORLD PRODUCTION OF PLATINUM
& PALLADIUM
Average Annual, 1969-1972
(Thousands of Troy Ounces)
Source
Canada
Colombia
Ethiopia
Finland
Japan
Philippines
Republic of South Africa
U.S.S.R.
United States
TOTAL
1969-1972 Average
Platinum
188
26
0.3
0.2
3
0.6
909
665
9
1801
Palladium
187
—
—
0.3
5
1
321
1339
13
1866
Total
375
26
0.3
0.5
8
1.6
1230
2004
22
3667
Sources: Minerals Yearbook and Engineering and
Mining Journal.
Half of world platinum and one-sixth of world
palladium production comes from the Union of
South Africa. One-third of platinum and over two-
thirds of palladium production is from the U.S.S.R.
Canada produces about ten percent of both platinum
and palladium, while the United States produces less
than one percent of each. South Africa, U.S.S.R., and
Canada combined produce 98 percent of the world's
platinum and palladium.
Consumption of the two metals in 1971 is
estimated to have been 3.7 million troy ounces, with
the United States using 37 percent of the total, as
shown in the following table. Japan used 20 percent,
Russia 16 percent, and West Germany 12 percent. All
other consumption totaled 15 percent of the world
total.
Sales to United States users in the five-year
1967-1971 period averaged slightly less than 1.3 mil-
lion troy ounces per year. Sales to specific industrial
categories are shown in the following table.
WORLD CONSUMPTION OF PLATINUM
& PALLADIUM
1971
(Thousands of Troy Ounces)
Nation
United States
Japan
U.S.S.R.
West Germany
France
Italy
Canada
United Kingdom
Netherlands
Sweden
Switzerland
TOTAL
Consumption
1376
758
589
451
313
74
68
49
33
17
12
3740
Source: Minerals Yearbook.
PLATINUM AND PALLADIUM SALES TO
U.S. INDUSTRY
1967-1971 Averages
(Thousands of Troy Ounces per Year)
Industry Category
Electrical
Chemical
Petroleum Refining
Dental and Medical
Glass
Jewelry and Decorative
Miscellaneous
TOTAL
Five- Year Average
Annual Sates
Platinum
97
155
184
23
49
31
29
568
Palladium
389
208
9
56
5
19
35
721
Total
486
363
193
79
54
50
64
1289
Source: Minerals Yearbook.
Some 38 percent of total sales were to the
electrical industry, the palladium (over half) being
used chiefly in telephonic equipment and the plati-
num being used chiefly for switch gear manufacture.
The chemical industry purchased 28 percent of the
total during the 1967-1971 period, chiefly for,sul-
furic and nitric acid manufacture. The petroleum
refining industry purchased 15 percent of the total,
mostly platinum, for use in the refining processes.
These three industry groups purchased 81 percent of
the platinum and palladium sales during the five-year
period. World reserves of platinum and palladium
were estimated in the 1970 Mineral Facts and Prob-
lems to be about 394 million troy ounces. These
reserves are equivalent to 105 years of supply at the
210
-------
1971 rate of 3.7 million troy ounces per year. Proved
reserve figures are given in the table below. There are
extensive exploration and investigation of other
prospective producing areas which are not included in
these totals.
WORLD RESERVES PLATINUM & PALLADIUM
1970 Estimates
(Thousands of Troy Ounces
ESTIMATED FUTURE WORLD DEMAND
PLATINUM & PALLADIUM
(Thousands of Troy Ounces per Year)
Nation
Republic of South Africa
U.S.S.R.
Canada
Colombia
United States
TOTAL
Reserves
Platinum
142,400
60,000
6,940
5,000
950
215,290
Palladium
50,200
120,000
6,860
-
1,960
179,020
Total
192,600
180,000
13,800
5,000
2,910
394,310
Source: Mineral Facts and Problems, 1970.
Nearly half of total estimated reserves are in
South Africa, with another 45 percent in the Soviet
Union. Canada, Columbia, and the United States
account for only 5.5 percent.
Future World Demand
A series of estimates has been made for future
demand for platinum and palladium on the part of
major consuming industries, both in the United States
and elsewhere. High, low, and median estimates were
made for consumption in 1980 and 1990. The follow-
ing table gives the median value of projected demands
and reflects the impact of new demands for automotive
exhaust emissions control catalysts. The 1971 sales to
industry figure is included for comparison. This figure
is some 5 percent lower than the U.S. consumption fig-
ure shown earlier, reflecting transfers to small coun-
tries, chiefly for trading and speculation.
Catalyst use for automotive emissions control,
40 percent of the United States demand in 1980 and
37 percent in 1990, is not expected to impose a
supply hardship in the foreseeable future. The addi-
tional needs amount to 18 percent of total world
demand in 1980 and 15 percent in 1990. Producer
indications are that production can be increased as
the demand increases. The 1970 proved reserves of
394 million troy ounces are equivalent to 46 years of
supply at the estimated 1990 annual consumption
rate of 8.5 million troy ounces.
United States: base platinum
automotive catalysts
total platinum
base palladium
automotive catalysts
total palladium
total base
total automotive
Total
Rest of world: platinum
palladium
Total
Grand total: platinum
palladium
Total
Total Demand
1971
541
-
541
760
-
760
1301
_
1301
1283
1163
2446
1824
1923
3747
1980
734
774
1508
898
332
1230
1632
1106
2738
1826
1655
3481
3334
2885
6219
1990
1044
866
1910
1095
371
1466
2139
1237
3376
2703
2450
5153
4613
3916
8529
Source: Mineral Facts & Problems, 1970; A Look at
Business in 1990 (a Summary of the White House Con-
ference on the Industrial World Ahead, February 7-9,
1972); and SwRI.
Environmental Considerations
Losses to the Environment. Essentially, no data
were found in published sources covering industrial
rates of transfer of platinum and palladium to the
environment. If such transfer is labeled as "unac-
countable losses" versus attrition (that known loss
from catalyst poisoning, handling and the like), then
some speculation may be made as to (I) the probable
sources of unaccountable losses, and (2) some feel for
the relative importance of these.
Most platinum or palladium is used by industry
in two forms: (l)as a metal, pure or in alloy, fabri-
cated, melted and cast, or used directly; or (2) as a
platinum or palladium compound either in solution
or not and applied, as for catalyst preparation, to a
carrier or matrix.
While process losses certainly occur among the
industries using metallic platinum and palladium,
there should be little or no loss entering the environ-
ment in the sense of a potential health hazard. These
industries include the electrical industry where
precious metals are used for switch contacts, dental
211
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work, the glass industry where precious metal spin-
erettes are used in the production of glass fibers, and
the jewelry and decorative industries.
In the chemical and petroleum refining indus-
tries, there is probably some transfer of platinum or
palladium to the product. However, the most prob-
able site of potential loss of platinum and palladium
to the environment, in one form or another in the
chemical and petroleum refining industries, is at the
point of preparation of catalysts rather than at the
chemical plant itself. As an example, mineral carriers
are impregnated with a platinum compound such as
chloroplatinate in manufacturing the catalyst for
producing nitric acid. The catalyst is then further
processed in order to render the platinum elemental
in form. In these processes, there are opportunities
for spillage, vapor entrainment, or other mechanisms
for loss. Of the 354 thousand troy ounces of plati-
num and palladium consumed in the chemical indus-
try in 1971, the Bureau of Mines estimates an attri-
tion rate of some 49 thousand ounces of platinum.
There are no data published with which this attrition
can be apportioned to the categories of transfer to
product, transfer to the environment, or other source
of loss.
In summary, with respect to industrial losses of
platinum and palladium to the environment, it is felt
that two groups can be identified as having the work
potential for such losses which may become matters
of health concern: first, the obvious group including
mining, processing, and refining of platinum and
palladium; and second, those firms engaged in the
preparation, regeneration, and recovery of platinum
and palladium catalysts for use in the chemical and
petroleum refining industries. Estimates of the
amount or concentrations of losses to the environ-
ment cannot be made on the basis of data currently
available from the literature.
Human Exposure Cases. Platinum was felt to be
relatively harmless until a report published by Hun-
ter, Milton, and Perry in 1945 in which was docu-
mented an investigation of exposure among workers
in four refineries. In essence, it was found that the
complex salts of platinum produced various symp-
toms in a high percentage of workers exposed. These
symptoms include asthma, eczematous lesions, and
dermatitis. On the other hand, exposure to metallic
platinum or palladium, or the complex salts of palla-
dium, has produced no apparent similar effects. Ac-
cordingly, only the complex salts of platinum appear
to present a health hazard.
Toxicology. Metallic platinum and palladium
are nontoxic and never give rise to occupational
injury. The oxides of platinum cause eczema of the
hands and forearms and some lesions of the nails.
Dust and spray from the complex salts of platinum
have been found to cause asthma after continued
exposure. Initial symptoms begin with repeated
sneezing followed by a profuse running of the nose
with a watery mucous discharge. Later reactions
which may develop include tightening of the chest
shortness of breath, wheezing and blue facial colora-
tion. When a person exposed to platinum salts leaves
the contaminated environment, symptoms clear with
the exception of persistent coughing. Some indivi-
duals exhibit a scaly red skin rash similar to an allergy
reaction. Blood checks, skin tests, or X-rays do not
reveal any abnormalities leading to these symptoms.
Treatment generally consists of removal from expo-
sure. Precautions lie in minimizing exposure and
maintaining allowable concentrations of soluble plati-
num salts in the atmosphere at less than 2 jzg /m3.
Palladium salts commonly used are the chloride
and the aminonitrite. So far as is known, these do not
constitute any human health threats However, labo-
ratory exposure tests on animals show results of
damage to the heart, kidneys, liver, and bone marrow.
Accordingly, close surveillance should be maintained
on the use of palladium salts in industry.
BIBLIOGRAPHY
A Look at Business in 1990, White House Conference
on the Industrial World Ahead, Washington, D.C.,
November 1972.
Automotive News, Marketing Services, Detroit, 1974.
Butterman, W. Dr., U.S. Department of the Interior,
Bureau of Mines, Washington, D.C., Communications
during February and March 1974.
Cajka, C.J., "Platinum Metals," Canadian Mining
Journal, National Business Publications Limited,
Gardenvale, P.Q., Canada, February 1973.
Chemical and Engineering News, Washington, D .C.
Encyclopedia of Chemical Technology, 2nd ed., John
Wiley & Sons, New York, 1966.
Eraser's Canadian Trade Directory, MacLean-Hunter
Publications, Toronto, Ontario, Canada, 1971.
212
-------
Freedman, S.O., Kruper, J., "Respiratory Allergy
Caused by Platinum Salts," J. Allerg. 42:233-7, 1968.
Gerrard, M., "Toxicity and Biological Effects of Plati-
num," Report ORNL-TIP/TIRC-72-75, Oak Ridge
National Laboratory, Tenn., November 1972.
Gertner, H.B., "Toxicity of Palladium, Platinum, and
Their Compounds-An Annotated Bibliography,"
Report ORNL-TIRC-73-19, Oak Ridge National
Laboratory, Tenn., June 1973.
Hunter, D., "Toxicology of Some Metals and Their
Compounds Used in Industry," Brit. Med. Bull.
7:5-15,1950, CA45:8657i.
Hunter, D., Hilton, R., Perry, K.M.A., "Asthma
Caused by the Complex Salts of Platinum," Brit. J.
Indust. Med. 2:92,1945.
International Directory of Mining and Mineral Pro-
cessing Operations, McGraw-Hill Publications, New
York, 1972.
Kusler, D.J., "Demand for Platinum to Reduce Pollu-
tion from Automobile Exhausts," U.S. Department
of the Interior, Bureau of Mines Information Cir-
cular-8565, Washington. D.C., January 1973.
Levene, G.M., "Platinum Sensitivity," Br J. Derma-
tol. 85(6): 590-93,1971.
Marshall, J., "Asthma and Dermatitis Caused by
Chloroplatinic Acid," S.African Med. Journ. 26(1):
8-9, 1952.
Merck Index 7th ed., Merck & Co., Inc., Rahway,
N.J.,1960.
Milne, J.E., "A Case of Platinosis," Med. J. Aust.
2:1194-5,1970.
Parrott, J.L., Saindelle, A., Ruff, F., "Platinum and
Platinosis: Histamine Release by Some Platinum Salts
and Platinum Allergy," Presse Med. (Paris)
75(2817):20-30, 1967.
Parrott, J.L., Saindelle, A., Tazi, T., "Histamine
Liberation by Sodium Chloroplatinate," J. Physiol,
(Paris) 55:314-5,1963 (Fr).
Pickering, C.A., "Inhalation Tests with Chemical
Allergens: Complex Salts of Platinum," Proc. R. Soc.
Med., 65:2724, 1972.
Platinum Metals Review, Quarterly Publication,
Johnson, Matthey & Co., Ltd., London, England.
Rosenberg, B., Vancamp, L., Trosko, J.B., Mansour,
V., "Platinum Compounds: A New Class of Potent
Antitumor Agents," Nature 222(5191):385-6, 1969.
Saindelle, A., Ruff, F., "Histamine Release by
Sodium Chloroplatinate," Brit. J. Pharmacol.
35:313-21, 1969, BA 51:56709.
Sax, N.I., (Ed.), Dangerous Properties of Industrial
Metals, 3rd ed., pp. 1031-2, Van Nostrand Reinhold
Co., New York, N.Y., 1968
Schroeder, H.H., Mitchener, M., "Scandium, Chro-
mium, Gallium, Yttrium, Rhodium, Palladium,
Indium in Mice: Effects on Growth and Life Span,"
J.Nutr., 181:1431-7, October 1971.
Schwartz, L., Tulipan, L., Peck, S.M., (Eds.), Occupa-
tional Diseases of the Skin, 2nd ed., Lea & Febiger,
Philadelphia, Pa., 1947.
Spikes, J.D., Hodgson, C.F., "Enzyme Inhibition by
Palladium Chloride," Biochem. Biophys. Res. Com-
mun. 35:420-2, 1969.
National Materials Advisory Board (NAS-NAE), "Sub-
stitute Catalysts for Platinum in Automobile Emission
Control Devices and Petroleum Refining," Report
NMAB-297, Washington, D.C., March 1973.
Oil and Gas Journal, Petroleum Publishing Co., Tulsa.
Parrott, J.L., Herbert, R., Saindelle, A., Ruff, F.,
"Platinum and Platinosis: Allergy and Histamine Re-
lease Due to Some Platinum Salts," Arch. Environ.
Health (Chicago) 19:685-91,1969, BA 51:45039.
Standard & Poor's Register of Corporations, Directors
and Executives, Standard & Poor's Corporation, New
York, 1974.
Suskind, D.A., "Platinum Group—A Bonanza in the
Automotive Industry?" Engineering and Mining
Journal, McGraw-Hill Publications, New York, March
1973.
The Wall Street Journal Dow Jones & Co., New York,
N.Y.
213
-------
Thomas Register of American Manufacturers Thomas
Publishing Company, New York, 1973.
U.S. Department of Commerce, Statistical Abstract
of the United States, Bureau of the Census, Washing-
ton, D.C., 1973.
U.S. Department of Commerce, U.S. Industrial Out-
look 1974 with Projections to 1980 Bureau of Com-
petitive Assessment and Business Policy, Washington,
D.C., 1974.
U.S. Department of the Interior, Mineral Facts and
Problems, Bureau of Mines Bulletin 650, Washington,
D.C., 1970.
U.S. Department of the Interior, Minerals Yearbook,
Volumes I, II and III, 1970; Vol. I., 1971, Bureau of
Mines, Washington, D.C.
U.S. Department of Transportation, Economic
Impact of Mass Production of Alternative Low Emis-
sions Automotive Power Systems, Office of the Secre-
tary, Washington, D.C., March 1973.
Van Arsdell, P.M., "Toxicity of Chemicals in Electro-
plating," Metal Finishing 45(S):55-60, 67; (9):79-83;
(10):75-81, 1947.
Wood, J.M., "Biological Cycles for Toxic Elements in
the Environment "Science, 183:1049-1052,1974.
214
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APPENDIX A. LITERATURE SEARCH
1. Introduction
The platinum group metals are often referred to as platinoids and are comprised of platinum,
palladium, iridium, osmium, rhodium, and ruthenium. Canada, the Republic of South Africa, and
the U. S. S. R. are the main -world suppliers. Small quantities of platinoids are derived from
Colombia, Ethiopia, Finland, Japan, the Philippines, and the U.S.
Platinoids are found in nature (a) associated with nickel-copper minerals that occur in ultra-
basic rocks, dunite and norite, and (b) in placer deposits. Nearly all of the Canadian production and
most of the U. S. S. R. production are a byproduct of nickel-copper refining. The South Africa produc-
tion comes from mines worked principally for the platinoids with nickel and copper recovered as
coproducts and gold and chromium as byproducts. Ethiopia and Colombia derive their production
from placer deposits, whereas Finland, Japan, and the Philippines produce small amounts of plati-
noids as byproducts of copper refining. Minute amounts are also produced in Papua New Guinea.
The U. S. output comes either from placer mining or is derived in the refining of gold and copper.
Fairly high platinum values were discovered during test drillings in western Australia and in north
Aukland, New Zealand, but further sampling will determine the commercial potential of these finds.
Prospecting in Southern Rhodesia has also uncovered significant occurrences.
In addition to primary platinoid production, the metal group's high costs have stimulated a
substantial effort for secondary recovery from all forms of scrap and used equipment, wherever
economically feasible.
The estimated world production of platinoids is shown in Table A-l.
Table A-l. Estimated World Production of Platinum Group Metals
(million troy oz)
1972
1969 1970 1971 (Prelim. )
Platinum 1.48 1.98 1.82 1.92
Palladium 1.64 1.92 1.92 1.98
Other 0. 29 0. 35 0. 34 0. 35
Total 3.41 4.25 4.08 4.25
Source: E/MJ, March 1973
These data indicate that platinum and palladium are by far the most abundant and the most
important elements of this group. Metals of the platinum group are measured and traded in terms of
troy ounces in the British system of weights. In the metric system, measurements are in kilograms
(1 kg equals 32. 15 troy ounces). Platinum group metals are commercially available in grades ranging
from 99. 8 to 99. 999 percent purity. Platinum and palladium are available in the form of sponge,
single crystals, powder, wire, sheet, foil, and rods. Platinum above 99. 7 percent is normally con-
sidered as commercial grade. According to Federal regulations, an article of trade may be marked
platinum if it contains 98. 5 percent platinum-group metals with a minimum of 93. 5 percent platinum.
Most platinoids are recovered as byproducts of the milling, smelting, and refining of nickel
and copper materials. In the Canadian Sudbury district, sulfide ore is processed by magnetic and
flotation techniques to yield concentrates of copper and nickel sulfates. The nickel flotation concen-
trate is roasted with a flux and melted into a matte which is cast into anodes for electrolytic refining
from which the precious metal concentrate is recovered. The platinum, palladium, and gold in the
concentrate are dissolved with aqua regia, leaving a residue containing the remaining four platinoids.
After the gold has been removed from the solution with ferrous sulfate, platinum is precipitated with
ammonium chloride. Palladium may be precipitated as a chloride by the addition of excess ammonia
and hydrogen chloride. The chloride of platinum and palladium are separately reduced to sponge
metal which can be compacted and melted to massive metal. Byproduct platinoids from gold or
copper ores are sometimes refined by electrolysis and by chemical means.
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Milling and beneficiation of the platinum-bearing nickel ores from South Africa consist of
gravity concentration, flotation, and smelting which produces a high-grade table concentrate called
"metallics" for direct chemical refining and a nickel-copper matte for smelting and refining. The
process of extraction consists essentially of enriching the nickel-copper matte to about 65 percent
platinum metals and then treating the enriched product with acids to separate the individual plati-
noids, followed by final refining.
The mining of crude platinum in placer deposits furnishes a small part of total production.
The mining and processing techniques for recovering crude platinum from placers are similar to
those used for recovering gold.
The industrial applications for platinum and palladium are diverse. Platinum-group metals
find application in the U. S. in the chemical, petroleum, glass, electrical, dental and medical, and
jewelry and decorative industries.
Platinum-group metal producers, in general, experienced overproduction and idle capacity
which lasted from 1970 to 1972. Renewed growth is expected, particularly for platinum and palla-
dium to be used in automobile emission control systems scheduled to be installed from 1975 on.
In addition to obtaining the required performance characteristics of these automotive catalytic con-
verters, lead content in gasoline must be reduced and sulphur and phosphorus content must be limited
to avoid rendering the platinum catalysts ineffective. It has been estimated that each car will require
an average of 0. 1 oz of platinum-group metals, including 30-35 percent palladium, with platinum
comprising the balance. The relatively high costs of platinum and palladium have initiated intensive
research into the use of suitable substitute catalysts. Thus, while the growth of supply is resuming
at a steady pace, the utilization of increased output is precariously dependent on the development
and final timing in the auto emission control area on a worldwide basis.
2. Platinum and Palladium Sources
The platinoid industry in the free world is centered about two major mining companies and
two affiliated refining and fabricating companies. The International Nickel Co. of Canada, Ltd.
(INCO) produces refined platinum-group metals as byproducts of its nickel-copper ore mining and
refining operations in Canada, and accounts for about one-third of the free world output of these
metals.
Rustenburg Platinum Mines, Ltd. , Republic of South Africa, produces platinum-group metals
from ores mined chiefly for platinum and contributes about two-thirds of the free world output of
platinoids.
The refining and fabricating companies are Engelhardt Industries, Inc. , Newark, N. J.
affiliated with INCO and Johnson, Matthey & Co. , Ltd. in Great Britain and their worldwide sub-
sidiaries, affiliated with Rustenburg.
In addition to these major companies in mining, as well as refining and fabricating, a
number of smaller organizations are engaged in these same activities in various countries as will
be shown below; the level of their activities depends to a great extent on the world demand and supply.
A third major source of platinum and palladium in the total world market is the U. S. S. R.
Little information is available on her industry pattern.
Canada. The Sudbury region of Ont. and the Thompson-Wabowden area of Man. are the
major sources of Canadian production, derived in a residue at nickel refineries. A small amount
of platinum metals is recovered from ores at Shebandowan, Ont. by INCO, in Que. by Renzy Mines
Ltd. , and near the Ont. -Man. boundary by Consolidated Canadian Faraday Ltd. and Dumbarton
Mines, Ltd.
Canadian production in 1972 was 399,000 troy ounces compared with 475, 169 ounces in
1971. Cutting back in nickel-copper production by INCO during this time period is the principal
factor for the decline in Canadian platinoid production.
In Ont. , INCO as the largest producer, operated 13 nickel-copper mines, four concentrators,
and two nickel-copper smelters near Sudbury, Ont. in 1972. A new nickel refinery was also being
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tuned up, where platinoid-bearing residues will be recovered. The Coniston Smelter and Totten and
Crean Hill mines were temporarily closed, and production was reduced at several other operations
in early 1972. Development work is continuing at INCO's Levack West mine scheduled for produc-
tion in 1975. In Ont., INCO operated a nickel refinery at Port Colborne and started mining the
Shebandowan deposits.
Falconbridge Nickel Mines, Ltd. operated eight nickel-copper mines, four concentrators,
and one smelter in the Sudbury region in 1972. Their Longvack South mine was temporarily closed.
Consolidated Canadian Faraday, Ltd. closed its Werner Lake mine because ore reserves were
exhausted.
In Que. , Renzy Mines, Ltd. closed its nickel mine and concentrator when the company's
smelter contract expired.
In Man. , INCO operated three mines, one concentrator, and a smelter-refinery complex at
Thompson. Falconbridge had a normal year of operations at its Manibridge mine and concentrator
near Wabowden. Dumbarton Mines, Ltd. which ships nickel-copper concentrate to the Falconbridge
smelter, increased ore production from 700 to 1100 tpd.
INCO's crude platinum-metal-bearing residues are initially concentrated in Canada and then
shipped to INCO's Metals Refinery at Acton, London, England for extraction and refining of the
platinum metals. Much of the refined metals are returned to Canada and exported to the United
States for fabrication and distribution by Engelhard Industries, Inc. Newark, N. J.
Falconbridge ships nickel-copper matte containing precious metals to its nickel refinery in
Kristiansand, Norway from which platinoid-bearing residue also goes to Engelhard for further
refining.
Republic of S^uth Africa is the free world's largest producer of platinoids. Rustenburg
Platinum Mines, Ltd. (RFM) operates three mines, one smelter and a refinery in the Transvaal
district. Rustenburg increased capacity to 1. 1 million ounces of platinoids a year, but reduced
production in 1971 to about 500,000 ounces because of excessive inventory accumulations. As
prospects for a new market are good, the opening of a new mine and an increase of production to
1. 3 million ounces a year are planned.
Impala Platinum Ltd. operates a mine-concentrator-refinery complex near Rustenburg.
Capacity at the operation is 350, 000 ounces of platinum a year, and current production is at an
annual rate of about 300, 000 ounces. Impala has also announced plans to expand its facilities.
Atok Investments (Pty. ) Ltd. , producing at Anglovaal and Middle Witwatersrand made its
first shipment of a platiniferous concentrate and matte from the Middlepunt mine in 1970 and pro-
duced an estimated 10,000 ounces of platinoids.
The Lonrho Ltd. -Falconbridge Nickel Mines Ltd. -South Africa Superior Oil Co. consortium
formed Western Platinum Ltd. , which commenced production at its Middlekraal mine near
Rustenburg in 1971. The operation has an annual capacity of 150,000 ounces of platnoids. Annual
capacity may be increased to 430, 000 ounces of platinoids by 1974-75, and the company is con-
sidering construction of a platinum refinery near the mine.
Platinum group metal production statistics are not reported in South Africa. In 1970, RPM
accounted for an estimated 83 percent of total output, and Impala produced most of the remainder.
An estimate of the platinoid growth potential is shown in Table A-2.
U. S. S. R. - The U. S. S. R. is the second largest producer of platinum-group metals in the
world.
Most of the production of platinum-group metals comes from nickel-copper ores of the
Norilsk region in northwestern Siberia. Palladium accounts for about 60 percent of this production '
and platinum for 30 percent. Nickel-copper ores in the Kola Peninsula also contribute to the output
of these platinoids. Placer platinum deposits in the Ural mountains, which at one time yielded most
of the platinum produced in the U. S. S. R. , now contribute only a small part of the overall output.
Presently, the U. S. S. R. is by far the largest producer of palladium, and ranks second after the
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Table A-2. Growth Potential for South African Platinum and Palladium
(1000 troy oz)
Platinum
Rustenburg
Impala
Western Platinum
Atok
Total Platinum
Total Palladium
Source: E/MJ, March 1973
1972
550
345
93
12
1,000
355
1973
900
400
125
15.
1,440
550
1974
1, 300
500
160
30
1,990
700
1975
1,500
650
200
200
2, 550
890
Republic of South Africa in production of platinum. As official U. S. S. R. output figures are not
available, it is estimated that the U. S. S. R. is currently producing platinum group metals at an
annual rate of well over 2. 2 million oz of which over half is palladium. The U. S. S. R. is supplying
20 to 25 percent of international exports of platinum and 70 to 75 percent exports of palladium.
Colombia is the fourth largest producing country. Crude platinum is recovered largely as a
coproduct of gold; it is marketed in the U.S. through various dealers and refiners. Although placer
deposits contain substantial reserves of platinum, some areas are not easily accessible and the
contained platinum may not be economically recoverable. Colombia's platinum production has
declined for several years and currently is about 25, 000 oz annually.
Ethiopia. Explorations for platinum, copper and petroleum deposits by private industrial
firms and the Ethiopian Geologiral Society are continuing. Placer platinum is retrieved in the
vicinity of Gambela, Ilubabor Province.
Finland. Platinum-group metals are recovered as byproducts from the copper refinery at
Pori, owned by Outokumpu Oy.
Japan. In 1970, Japan has produced 47,000 oz of platinoids, mostly platinum and palladium,
as byproduct of nickel-copper refining, all of which were exported to Mainland China, the United
States and West Germany.
The Philippines. Platinum-group metals, mostly platinum and palladium, come from the
nickel-cobalt concentrates of Acoje Mining Co. at Santa Cruz, Zambales Province, Luzon. The
concentrate, which is 15 percent nickel-cobalt, assays 1.4 ounces of platinum and 2. 8 ounces of
palladium per ton of concentrate.
United States of America. The major part of the U.S. output is recovered as a byproduct of
copper refining in Maryland, New Jersey, Texas, Utah, and Washington. A small part of domestic
output is recovered from a placer platinum deposit at Goodnews Bay, Alaska; this output is pur-
chased by Johnson, Matthey & Co. and refined by its affiliate, Matthey Bishop, Inc. Malvern, Pa.
U.S. refiners also process imported materials such as crude platinum from Colombia and platinum
bearing nickel-copper matte from the Republic of South Africa. In addition, the refiners purcha.se
platinum- and palladium-bearing scrap, residues, cataly&ts, and other platinum-bearing mate rial h.
Secondary recovery and toll refining are important segments of this industry. In 1970, the refinery
production of new metal in the U. S. was 21, 395 oz, and of secondary metal 349, 126 <>/.; the total
industry consumption was 1, 335,467 oz.
Summary of Sources
Canada, Ont. :
International Nickel Company of Canada, Ltd.
Ontario Division
Copper Cliff, Ont. Canada (705/682-4411)
Location: Sudbury District
President and General Manager: G. McCreedy
Employment: 36, 089 total
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Coniston Smelter
Copper Cliff, Ont. , Canada
Manager of Smelters: J. N. Lilley
Levack West Mine
Copper Cliff, Ont. Canada
Area Superintendent: D. Lennie
Port Colborne Refinery
Copper Cliff, Ont. Canada
Manager: W. V. Barker
Employment: 2, 200
Shebandowan Mine
Copper Cliff, Ont. Canada
Manager: G. W. Johnston
Copper Refinery
Copper Cliff, Ont. , Canada
Manager: G. A. Dick
Falconbridge Nickel Mines, Ltd.
Headquarters: P.O. Box 40, Commerce Court West
Toronto 1, Ont. Canada (416/863-7000)
President and Managing Director: Marsh A. Cooper
Employment: 4049 total
Sudbury Operations Headquarters;
Falconbridge: Ont. Canada (705/693-2761)
Sudbury Operations General Manager: G. A. Allen
Canada, Man.
International Nickel Company of Canada, Ltd.
Manitoba Division
Thompson, Man. Canada (204/677-5211)
President and General Manager: D. E. Munn
Employment: 3, 700
Falconbridge Nickel Mines, Ltd.
Mainibridge, Man. Canada (204/689-2413)
General Manager: W. A. Case
Employment: 190
Dumbarton Mines, Ltd.
Headquarters: 1600, 100 Adelaide St. West
Toronto, Ont. Canada
Mine
Maskwa Lake, Man. Canada
Concentrator Superintendent: K. Dixon
Mine Superintendent: C. P. Moore
Republic of South Africa
Rustenburg Platinum Mines, Ltd.
Rustenburg and Union Sections
Consolidated Bldg. , P.O. Box 590
Johannesburg, Trvl. , S. Africa
General Manager: J. S. Ritchie
Manager, Rustenburg Section: J. C. J. Van Rensburg
Manager, Union Section: F. J. Brown
Employment: 26, 000 total
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Impala Platinum Ltd.
3rd floor, Unicorn House, 70 Marshall St.
P.O. Box 61386, Marshalltown
Johannesburg, Trvl, S. Africa (834-4552)
Managing Director: K. A. B. Jackson
Employment: 10, 000 total
Bafokeng Mine
P.O. Box 363, Rustenburg, Trvl., S. Africa
Telephone: Rustenburg 2616
Mine Manager: R. C. Bovell
Employment: 9, 500
Refineries
P.O. Box 222, Springs, Trvl., S. Africa
Telephone: Springs 56-6777
Chief Engineer: H. W. Read
Manager Platinum Refinery: P. A. Reynolds
Employment: 500
Western Platinum Ltd.
Rustenburg, Trvl. , S. Africa
New Plants
Atok Investments (Pty) Ltd.
c/o Anglovaal House, 56 Main St. , P. O. Box 62379
Marshalltown,
Johannesburg, Trvl. , S. Africa
New Plants
Klockner Werke of West Germany
c/o Rand Mines Limited
The Corner House 63, P.O. Box 62370
Marshalltown
Johannesburg, Trvl. , S. Africa
Exploration
U. S. S. R. All enterprises are owned and run by the communist government.
No detailed data are published outside Russia.
Colombia:
Cia Minera Choco Pacifico, S. A.
Andagoya, Istmina Choco, Colombia
Manager: Jaime Zapata
Employment: 438
Cia Minera de Narino, S. A.
Barbacoas, Narino, Colombia
Manager: Carlos Aspillera
Employment: 192
International Mining Corporation
280 Park Avenue
New York, N.Y. 10017(212/983-7500)
President: Patrick H. O'Neill
(Pato Consolidated Gold Dredging Ltd.
Aparto Aereo 13-06, Medellin, Colombia
General Manager: Edward Moseley-Williams
Employment: 455)
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The Philippines
Acoje Mining Co. Inc.
2283 Pasong Tamo Extension
Makati Rizal, Philippines (89-35-61)
Nickel Project
Santa Cruz, Zambales, Philippines
Mine Superintendent: Elmer B. Gabaldow
Employment: 130
Finland
Oytokumpu
Toolonkatu (Box 10280)
Helsinki (10) Finland
Pori Works
Pori, Finland (Pori 11701)
Works Manager: Aarne Kapanen
Employment: 2000
Australia; Possible future platinum operations.
Matthey Garret Pty. Ltd.
P. O. Box 165, Kogarah
New South Wales 2217
New Zealand; Possible future platinum operations.
Matthey Garret (N2) Ltd.
2Z Drake St., P.O. Box 2073, Auckland
United States of America
Goodnews Bay Mining Co.
(422 White Bldg., Seattle, Wash. 98101)
Platinum, Alaska 99651
Vice President and General Manager: Edward Olson
Employment: 47
American Smelting and Refining Company
Baltimore Plant, Highland and Eastbourne Aves.
Baltimore, Md. 21224 (301/675-0090)
Manager: R. H. Funke, Jr.
Employment: 1, 200
United States Metals Refining Co.
440 Middlesex Ave. , Carteret, N. J. 07008
(201/541-4141)
General Superintendent: Robert N. Brown
Employment: 1,800
Phelps Dodge Refining Corporation
El Paso Refinery, P.O. Box 2001
El Paso, Texas, 79998 (915/772-2701)
Vice President and Works Manager; M. S. Bell
Employment: 880
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3.
American Smelting and Refining Company
Tacoma Plant, P.O. Box 1677
Tacoma, Washington, 98401 (206/759-3551)
Manager: R. E. Shinkoskey
Employment: 1,000
(Company does custom smelting; verification of platinoid smelting necessary)
Kennecott Copper Corp. Metal Mining Division
Utah Copper Div. , P.O. Box 11299
Salt Lake City, Utah 84111 (801/322-1533)
General Manager: J. P. O'Keefe
Employment: 7, 200
(Verification of platinoid smelting necessary)
Platinum and Palladium Processors
It was stated earlier that the platinum-group metals industry in the free world is essentially
centered around two mining companies and two affiliated refining and fabricating companies. The
major refining and fabricating companies processing mainly new platinoid materials (Engelhard and
Johnson Matthey) are not mining companies and are, therefore, not vertically integrated. Imports
of platinum-group metals include refined metals (90%), unrefined metals, crude ores and concen-
trates, grain, nuggets and residue. U. S. exports of platinum group metals, principally as semi-
processed metals and alloys and as manufactured products are small compared with imports.
Secondary recovery and toll refining comprise the bulk of domestic refining operations. In 1968
(latest figure available) 2. 3 million troy ounces were produced by toll refining operations, of which
91 percent represented used material and 9 percent was metal recovered from virgin material. As
it is not possible to separate this intertwined industry clearly by functions like mining, refining,
fabricating, etc. , the following lists show first the key members of this industry (Group I) followed
by those emphasizing refining (Group II) and finally those emphasizing fabricating (Group III). In
reality, some companies may be active in all areas and some only in segments of this industry.
Companies listed are those with over $500,000 total assets. Some may be brokers only. This can-
not be avoided as many of the specialized companies are not listed in Standard & Poor's Register.
U.S.
Group I; Key members
Engelhard Industries Division
(Engelhard Minerals and Chemicals Corp. )
430 Mountain Ave.
Murray Hill, N. J. 07974 (201/464-7000)
Executive Vice President: Robert S. Leventhal
Employment total: 7, 500
Matthey Bishop, Inc.
Malvern, Pa. 19355 (215/644-3100)
Vice President Operations: H. S. Roberts
Also: Johnson Matthey &; Co. , Inc. , 608 Fifth
Avenue, New York, N. Y. 10020 (212/245-6790),
representative of parent company, Johnson
Matthey & Co. , Ltd. , 78 Hatton Garden,
London, E.G. 1, England (01-405-6989)
Group II: Refiners
Handy and Harman
850 Third Avenue
New York, N. Y. 10022
(212/752-3400)
American Chemical and Refining Co.
P. O. Box 4067
Waterbury, Conn.
Canada
Engelhard Industries of Canada, Ltd.
512 King St. E.
Toronto 2, Ont. (416/362-3211)
Johnson Matthey fa Mallory, Ltd.
110 Industry St.
Toronto 15, Ont. (416/763-5111)
Handy and Harman of Canada, Ltd.
141 John
Toronto 20 Ont.
National Refining Co. , Ltd.
136 St. Patrick
Toronto (w)
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U.S.
Canada
National Lead Co.
Goldsmith Division
1300 W. 59th St.
Chicago, 111.
United Refining & Smelting Co.
3700-20 N. Runge Ave.
Franklin Park, 111. 60131(312/455-8800)
Hyperrefiners. Inc.
P.O. Box 80-T
Clifton, N. J.
Engelhard Minerals & Chemicals Corp.
429 Delaney St.
Newark, N. J. 07105
Eastern Smelting and Refining Corp.
35 Bubier Street
Lynn, Mass (617/599-4000)
Selrex Corp
Precision Metals Recovery Division
73 River Road
Nutley, N. J.
Spiral Metal Co.
South Broadway
South Amboy, N. J.
Sabin Metal Corp
310-334 Meserolf St.
Brooklyn, N. Y. 11206 (212/381-5000)
Samuel J. A. & Co. . Inc.
233 Broadway
New York, N. Y. 10007
Midland Processing, Inc.
53 Lafayette Ave.
White Plains, N. Y. 10603 (914/949-9310)
Mercer Refining
2801-T W Lake
Melrose Park, 111.
Group III; Fabricators
Western Gold & Platinum Co.
555 Harbor Blvd.
Belmont, Calif.
Engelhard Industries of Canada, Ltd.
512 King St. E
Toronto 2, Ont. (416/362-3211)
Whittaker Corp.
10880 Wilshire Blvd.
Los Angeles, Calif.
Wildberg Bros. Smelting fa Refining Co.
349 Oyster Point Blvd.
South San Francisco, Calif.
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U.S.
Canada
Ney, J. M. Co.
Drawer 990
Hartford, Conn. 06101
duPont, E.I, de Nemours & Co., Inc.
Wilmington, Del.
National Lead Co.
Goldsmith Div.
1300 W. 59th St.
Chicago, 111. 60636 (312/925-3800)
United Refining & Smelting Co.
3700-20 N. Runge Ave.
Franklin Park, 111. 60131 (312/455-8800)
Mercer Refining
2801-T W, Lake
Melrose Park, 111.
Texas Instruments, Inc.
30 Forest
Attleboro, Mass.
Eastern Smelting & Refining Corp
35 Bubier St.
Lynn, Mass. Oi;01 (617/599-9000)
Engelhard Minerals 81 Chemicals Corp
113 Astor St.
Newark, N.J. 07114 (201/242-2700)
President: Milton F. Rosenthal
Employment: 7, 500 total
Spiral Metal Co.
So. Broadway
So. Amboy, N. J. 08879
Sabin Metal Corp.
310-334 Meserole
Brooklyn, N. Y.
Williams Gold Refining Co. , Inc.
2960 Main
Buffalo, N.Y.
Aderer, J. Inc.
44th Ave. & 22nd
Long Island City, N. Y.
Engelhard Industries of Canada,
512 King St. E.
Toronto 2, Ont. (416/362-3211)
Ltd.
Consolidated Refining,
120 Hoyt Ave.
Mamaronech, N. Y.
Inc.
American Metal Climax, Inc.
1270 Ave. of the Americas
New York, N.Y.
Anaconda Co.
25 Broadway
New York, N.Y.
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U.S.
Canada
Copper Joseph B. & Sons. Inc.
178 Varick
New York, N.Y.
Handy & Harman
850 Third Ave.
New York, N.Y.
Phillip Brothers Div.
299 Park Ave.
New York, N.Y.
Handy and Harman of Canada, Ltd.
141 John
Toronto 20, Ont.
Samuel, J.A. & Co.
233 Broadway
New York, N.Y.
United Mineral & Chemical Corp
Hudson & Bach St.
New York, N.Y.
Midland Processing, Inc.
53 Lafayette Ave.
White Plains, N. Y.
Secon Metals Corp
5-7 Intervale
White Plains, N. Y.
Buckeye Molding Co.
Crysteco Div.
181 E. Main
Wilmington, Ohio
Technic, Inc.
P.O. Box 965
Providence, R. I.
American Chemical fc Refining Co.
P.O. Box 4067
Waterbury, Conn.
Deringer Metallurgical Corp.
1252 E. Town Line Rd.
Mundelen, 111.
Kron J. Williams Co. Inc.
301-303 Veteran Blvd.
Carlstadt, N. J.
Hamos Co.
242 W. 30th
New York, N.Y.
Inc.
4.
Prominent Sources and Processors
In the U. S. , most platinoids are byproducts from copper and gold refining and, therefore,
these types of companies are shown as representative sources. Processors (refiners and fabri-
cators) are those that may include refineries specifically for platinoids and thus direct human
exposure to platinum and palladium is expected to be much stronger during processing than during
copper and gold refining.
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Prominent Sources (for details see pages A-4 through A-7). Most Canadian concentrates, residues
and matte are sent to England and Norway for refining or processing.
U.S.
Canada
American Smelting & Refining Co. International Nickel Comp. of Canada, Ltd.
United States Metals Refining Co. Falconbridge Nickel Mines, Ltd.
Phelps Dodge Refining Corp. Dumbarton Mines, Ltd.
American Smelting and Refining Corp.
Kennecott Copper Corp.
Good News Bay Mining Co.
Prominent Processors :
Engelhard and Matthey Bishop are the most prominent and established platinoid companies, with
Engelhard having several divisions dealing in various platinoid applications. In other companies,
particularly the larger and diversified ones, the number of employees may be misleading, as only
a relatively small number of employees may deal with platinum and palladium.
U.S.
Engelhard Minerals & Chemicals Corp.
Baker Platinum Division
700 Blair Road, Carteret, N. J. 07008
Chemicals & Catalysts; Engelhard Industries
Division of Engelhard Minerals &
Chemicals Corp
429 Delaney, Newark, N. J.
Engelhard Industries
Division of Engelhard Minerals fc
Chemical Corp.
430 Mountain Ave.
Murry Hill, N. J. 07974 (201/464-7000)
Executive Vice President: Robert S.
Leventhal
Employment: 7, 500
Matthey Bishop, Inc.
Malvern, Pa. 19355 (215/644-3100)
Vice President Operations : H. S. Roberts
Handy & Harman
850 Third Ave.
New York, N. Y. 1022(212/752-3400)
Vice President R&D: C. D. Coxe
Employees: 2,200
Eastern Smelting & Refining Corp.
37-39 Bubier
Lynn, Mass. 01903 (617/599-9000)
President: Jordan L. Alperin
Employees: 50
Canada
Engelhard Industries of Canada, Ltd.
512 King St. E.
Toronto 2, Ont. (416/362-3211)
Johnson Matthey fa Mallory, Ltd.
1 10 Industry St.
Toronto, 15, Ont. (416/763-5111)
Handy & Harman of Canada, Ltd.
141 John
Toronto 21, Ont.
226
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U.S. Canada
N. L. Industries, Inc.
Goldsmith Division
1300 Vf. 59th St.
Chicago,'1(1. 60636(312/925-3800)
General Manager: Albert Dipiazza, Jr.
Employees: 160
Consolidated Refining Co. Inc.
120 Hoyt Ave.
Mamaronek, N.Y. 10543 (914/698-2300)
President: Mortimer M. Cass
Employees: 130
Segrex Corp, Subsidiary
Hooker Chemical Corp.
Precious Metals Recovery Division
73 River Road
Nutley, N. J. 07110 (201/667-5200)
Vice President Research: D. Bruce Merrifield
Employees: 10, 000 total
Western Gold & Platinum Co.
(Subs. GTE Sylvania)
555 Harbor Blvd.
Belmont, Calif. 94002 (415/593-3121)
Vice President Manufacturing: Harold O. Richter
Employees: 280
J. M. Ney Co.
Drawer 990
Hartford, Conn. 06101 (203/242-2281)
Production Manager: Ronald G. Robinson
Employees: 300
5. Manufacturers of Automotive Emission Control Systems
U.S.
Engelhard Minerals & Chemicals Corp.
Matthey Bishop, Inc.
Universal Oil Products
W. R. Grace
Airproducts Division of Linde Products Company (Fecor Industries, Ltd. )
Japan
American Cyanamid and Japan Catalytic International
Europe
Deguzza (VW)
French Company (name unknown)
Engelhard Kali-Chemie Autocat G. M. B. H. (West Germany)
6. Production Data
World production of platinum and palladium by country are shown in Tables A-3 and A-4 below.
It should be noted that official data—where available--are usually 2 years behind in publication. All
South African figures are estimates, as no data are published on this industry.
World production expanded greatly in 1970, but demand failed to live up to expectations, partly
because of the influence of business recession in the leading consumer countries. In early 1971,
producers were forced to halt expansion projects and to cut back production. As a result, world
227
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Table A-3. Platinum Production by Country
(troy oz)
Year
Country 1969 1970 1971 1972 (Est.)
Canada 134,715 209,374 203,112 (205,000)
Colombia 27,805 26,358 25,610 (24,000)
Ethiopia 343 273 217 (250)
Finland --- 295 275 (250)
Japan 3,140 3,296 3,451 (3,000)
Philippines --- 352 900 (1,000)
South Africa 676,400 1,068,000 890,000 (1,000,000)
U.S. S. R. 630,000 660,000 690,000 (678,500)
United States 8, 7"2 8. 036 10. 198 (8. OOP)
World Total 1,481,105 1,975,984 1,823,763 (1,920,000)
Source: Minerals Yearbook 1971 and E/MJ, March 1973.
Table A-4. Palladium Production by Country
(troy oz)
Year
Country 1969 1970 1971 1972 (Est. )
Canada 133,163 206,962 200,772 (208,000)
Colombia
Ethiopia
Finland --- 350 325 (375)
Japan 3,877 4,610 5,381 (5,600)
Philippines --- 878 1,800 (2,000)
South Africa 238,450 376,500 313,750 (355,000)
U. S. S. R. 1,260,000 1,320,000 1,380,000 (1,397,000)
United States 8, 387 11, 875 20, 951 (12,025)
World Total 1,643,877 1,921,175 1,922,979 (1,980,000)
Source: Minerals Yearbook 1971 and E/MJ, March 1973.
output slipped in 1971. That trend was again reversed with auto industry developments. Expansion
plans resumed again early in 1972, and it is estimated that the 1972 output reached the previous high
of 1970. The most active growth in the free world occurs in South Africa where platinum output
may be boosted to upwards of 1. 4 million oz in 1973 and further in 1974 and after, if the confidence
in the auto demand outlook is unshaken. Some output recovery may be seen in Canada, although the
long-term trend is relatively static.
7. Consumption Data
It was noted earlier that official data are published usually with a two year delay. Hence, the
U. S. consumption data are now available for the year 1971.
United States. During 1971, the total sales of platinoids to the chemical, petroleum and
electrical industries accounted for 83 percent of all sales compared with 82 percent in 1970. Plati-
num sales decreased slightly despite the 25-percent increase in sales to the petroleum industry and
gains in sales for dental, medical and miscellaneous uses. The increase in sales to the petroleum
industry was for new reforming units to produce non-leaded gasoline. The bulk of platinum sales in
1971 was distributed among petroleum refiners (46.5 percent), manufacturers of organic and
inorganic chemicals (25. 0 percent), and electrical and electronic equipment manufacturers (9. 6 per-
cent). Palladium sales increased 3 percent in 1971 despite sizable declines in sales to the glass
industry. Sales to manufacturers of chemicals increased 18 percent, to manufacturers of electrical
equipment 1 percent and accounted for 29 and 57 percent, respectively, of all palladium sales.
Table A-5 shows the sales of platinum and palladium to consuming industries in totals, and Table A-6
and Table A-7 show sales to industry groups.
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Table A-5. Platinum and Palladium Sold in
the United States (troy oz)
Year Platinum Palladium
1967 633,864 621,141
1968 580,155 721,479
1969 515,578 758,738
1970 566,369 739,343
1971 541,164 760,106
Source: Minerals Yearbooks.
Table A-6. Platinum Sold to Consuming Industries in the United States
(troy oz)
Industry 1967 1968 1969 1970 1971
Chemical 159,384 157,677 175,436 148,289 135,112
Petroleum 245,560 161,050 58,602 202,015 251,876
Glass 45,150 47,935 63,350 46,687 40,703
Electrical 99,686 117,256 112,589 103,318 51,940
Dental and Medical 24,630 24,903 22,266 18,302 23,097
Jewelry and Decorative 33,342 40,184 36,161 29,203 18,577
Miscellaneous 26.112 31.150 47. 174 18.555 19.859
Total U.S. 633,864 580,155 515,578 566,369 541.164
(re-revised) '
Source- Minerals Yearbooks.
Table A-7. Palladium Sold to Consuming Industries in the United States
(troy oz)
Year
Industry 1967 1968 1969 1970 1971
Chemical 192,011 228.318 214,508 184,618 218,651
Petroleum 3,506 22,683 1,337 15,494 2,916
Glass 301 10 3,891 21,147 237
Electrical 324,684 329,012 430,258 429,032 431,505
Dental and Medical 56,085 61,636 52,326 47,583 61,594
Jewelry and Decorative 18,676 17,797 21,837 17,329 18,752
Miscellaneous 25. 878 62, 023 34. 581 24, 140 26,451
Total U.S. 621,141 721,479 758,738 739,343 760,106
Source: Minerals Yearbooks.
Consumption data of countries outside the United States are difficult to assess, as trade data
for each individual country would be needed. These are not readily available. The Rustenburg group
has provided some estimates for the distribution of demand among the total Western world for newly
mined platinum. These estimates are based on data for the period of 1965-69. As secrecy shrouds
platinoid data in some producing countries, the following figures, developed for 1971, can be con-
sidered as only an overview of a complex and highly intermeshed demand-supply relationship for
platinoid using countries. The Rustenburg data estimated that 30 percent is distributed to the
chemical industry, 25 percent to petroleum catalytic uses, 20 percent to electrical and allied
industries, 10 percent to glass manufacture, and the remaining 15 percent are distributed among
various uses including jewelry and medical applications.
The total new world production during 1971 in platinoids was 4, 076, 788 ounces troy of which
1, 823, 763 oz were platinum and 1, 922, 979 oz were palladium. Free world demand distribution for
229
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new platinum and palladium metals is shown in Tables A-8 and A-9. The industry distribution is
based on U. S. 1971 data as shown in Tables A-6 and A-7, with Rustenburg estimates for platinum
given in parentheses. The Rustenburg data differ widely with the U. S. distribution in most industrial
categories. It should be expected that the demand distribution in most industrialized nations of the
Free World follow more closely the U.S. pattern. As Rustenburg assumes an authoritative position
in this metals industry, the actual demand distribution may be between both limits.
Table A-8. Free World Platinum Demand Distribution
(troy oz)
Total 1971 world production 1,823,763
U. S. S. R. estimated total 1971 production 690,000
U. S. S. R. estimated 1971 export 336,375
U.S. new 1971 production 10, 198
Free World available rew production 1,459, 940
Estimated demand distribution
Chemical industry (25 percent) 364,985 (473,852)
Petroleum industry (46. 5 percent) 678,872 (394,876)
Glass industry (7. 5 percent) 109,496 (157,951)
Electrical industry (9. 6 percent) 140, 154 (315, 901)
Dental and medical industry (4. 3 percent) 62, 777
Jewelry and decorative industry (3. 4 percent) 49, 638 (236, 926)
Miscellaneous (3. 7 percent) 54,018
Source: Minerals Yearbook 1971, Universal Facts and Problems 1970
and Southwest Research Institute.
Taole A-9. Free World Palladium Demand Distribution
(troy oz)
Total 1971 world production 1, 922, 979
U. S. S. R. estimated 1971 production 1,380,000
U.S.S.R. estimated 1971 export 1,009,125
U.S. new 1971 production 20,951
Free World available new production 1,531, 153
Estimated demand distribution
Chemical industry (28. 8 percent) 440, 972
Petroleum industry (0.4 percent) 6, 125
Glass industry (0.03 percent) 459
Electrical industry (56. 77 percent) 869, 236
Dental and medical industry (8. 1 percent) 124, 023
Jewelry and decorative industry (2. 5 percent) 38, 279
Miscellaneous (3. 4 percent) 52,059
Source: Minerals Yearbook 1971, Universal Facts and Problems 1970
and Southwest Research Institute.
The determination of consumption figures for individual countries is difficult for several
reasons. The high cost of platinoids has created great demand for secondary sources and recovery.
Recovery takes place by processing scrap materials which include discarded jewelry, used elec-
tronic components and spark plugs, sludges and sweeps. In addition, large quantities of worn out
or contaminated platinum-metal-bearing materials are refined on toll. This metal, compromising
the bulk of domestic refining operations, was received for reworking or re-refining of depleted
catalysts, wornout extension dies, spinners, laboratory ware and other used equipment. Recovery
from scrap is very efficient, and only a small quantity of these metals is wasted or lost. Secondary
recovery of platinum and palladium in the United States is shown in Table A-10.
While quantities of secondary recovery platinoids are well known for the U. S. , the same
information for other countries could not be obtained. Furthermore, the trade patterns worldwide
as well as within the free world vary considerably. Platinoids are shipped in form of ores, con-
centrates, residues, waste, scrap and sweepings, partly worked rolled and partly worked not rolled.
230
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Table A-10. Platinum and Palladium Secondary Recovery
in the United States (troy oz)
Year Platinum Palladium
1967 126.377 215,162
1968 115,587 195,620
1969 126,822 227,763
1970 r!18,298 r208,555
1971 103,429 161,099
(r: revised)
Source: Minerals Yearbook 1971.
For example, during 1971 the U. S. has exported 404, 610 troy oz of platinoids in various
metal stages to 17 countries. These shipments included 154, 775 oz platinum unworked or partly
worked not rolled and 15, 894 oz platinum unworked or partly worked rolled. During the same year,
the U. S. has imported for consumption 1, 302, 740 oz from 24 countries in various unwrought or
semimanufactured conditions. These inputs included 551, 127 oz of platinum and 657, 983 oz of
palladium. These data indicate that no clear picture emerges from these trade patterns to determine
actual consumptions in foreign countries. In addition, and as noted earlier, the U. S. S. R. and the
Republic of South Africa, the major platinoid producers in the world, do not publish data on plati-
noids, and all their figures, found in publications, are estimates by the trade. International trade
data for platinoids are available for the year 1969. Some of these data are given for platinum and
palladium, some are given as a combination of platinoid and silver shipments and some are given
only for non-ferrous metals. In Table A-11, the 1969 percentages of individual countries to the
total 1969 world production of platinum and palladium are applied to the 1971 consumption year.
Table A-il. Platinum and Palladium Consumption by Major Country
(Order of Magnitude in troy oz)
Country 1971
Canada 68,259
France 312,947
Germany, West 451,330
Italy 74,227
Japan 758,309
Netherlands 32, 824
Sweden 17, 158
Switzerland 11,563
U. K. 48, 863
U. S. S. R. 589,340
U.S. 1. 375, 788
Total Approximately 3, 740, 608
Source: Minerals Yearbooks.
The total consumption (3. 74 million troy ounces) compares favorably with the 1971 production
figure of 3. 75 million ounces. The data shown represent an order of magnitude approximation for
major consuming countries. With the exception of Japan and the U. S. , variations are expected.
The causes for these are based on inadequate data on foreign stockpiles, dealer stocks, and foreign
secondary recovery. These data also include small shipments of platinoids from major consumer
countries to a large number of less industrialized and small countries, caused very likely by
Futures trading and speculation.
8. End Use Applications
Platinoids find many applications in industry because of their catalytic activity, resistance to
corrosion, resistance to oxidation at elevated temperatures, high melting point, high strength and
good ductility. Platinum and palladium are the major platinum metals; iridium, osmium, ruthenium
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and rhodium are used mainly as alloying elements to modify properties of platinum and palladium.
Rhodium is also used in plating.
Chemical industry. One of the major uses for platinum, alloyed with 10 percent rhodium, is
as a catalyst in producing nitric acid for use in nitrate fertilizers and explosives. New uses for
platinum and palladium as an oxidation catalyst are evolving in the rapidly expanding pollution con-
trol field. Platinum and palladium are widely used as a catalyst in hydrogenation, dehalogenation
and other reactions used by chemical, dyestuff and pharmaceutical industries.
Platinum and other platinum-group metals are used also as catalysts in a great variety of other
chemical processes as shown in Table A-12.
Table A-12. Chemical Processes Using Platinum-Group Metal Catalysts
Process Catalyst
Hydrogenation Pt, Pd, Ir, Rh, Ru, Os.
Dehydrogenation Pt, Pd, Ir, Ru, Pd-Ag.
Fragmentation Pt, Pd.
Decomposition Ir, Ru.
Hydroc racking Pt, Ir.
Reforming Pt, Ir, Rh, Pt-Ir.
Synthesis Ir, Rh, Ru.
Polymerization Ir-Ni, RhCls.
Isomerization Pd, IrCl3, Ir-Ni, Ir-V, RhCl3, Pt-Ir, Pt-Rh, Pt-Ru,
Pt-Os.
Oxidation Pt, Rh, Ru, Pt-Ir, Pt-Rh.
Regenerable reagents PdCl3-
Homogeneous reactions
Carbonylation Ir, Ru, PdCls, RhCls, Rh(NO3)3-
Oxidation Ir, Ru,
Reductions Ru, Pt-Ir,
Source: Minerals Yearbook 1971
Platinum spinnerets are used in the production of synthetic fibers. New precious-metal catalyst
systems are being developed constantly to reduce utilization of platinum at no loss in catalyst effi-
ciency. A precious-metal-plated titanium anode may replace graphite anodes in the chlorine manu-
facturing industry.
Petroleum industry. Generally, platinum and palladium are used as catalysts in the produc-
tion of high-octane gasolines and for hydrocarbon synthesis to produce numerous petrochemicals.
Reforming units to produce nonleaded gasoline will lead to a substantial increase in platinum con-
sumption. However, application of a new platinum-rhenium catalyst to refining, requiring much
less platinum, may offset the demand for this purpose.
Glass industry. A substantial quantity of platinum-rhodium alloy is used for bushings for
attenuating the glass fibers and for equipment used in manufacturing other glass products. Glass-
making refractory equipment is coated with a thin layer of platinum sheet to prevent contamination
of the molten glass. More uses for platinum-iridium alloys are found in crucibles for growing
crystals for lasers, optical modulators and other scientific applications.
Electrical and electronic industry. Platinum, palladium and various alloys find major
use in such application as light duty contacts, electric furnace windings, thermocouples, cobalt-
platinum permanent magnets for travelling wave tubes, resistance thermometers and precision
thermometers, relays, meters, voltage regulators, and other electrical instruments. Palladium
especially is used in low voltage-low energy electrical contacts in telephone equipment. Platinum
and palladium are also used in powder (paste) form or as electrodeposits in components of electrical
printed circuits. Platinum is also used in fuel cell electrodes, and new developments in this field
could lead to a substantial increase in platinum requirements. Significant quantities of platinum
were also used in impressed current corrosion protection systems. Some pacemakers to stimulate
the heart muscle use platinum or platinum-iridium electrodes.
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Dental and medical industry. Additions of platinum and palladium to gold-based alloys
increase strength, hardness and wear resistance, raise the melting temperature and enhance the
age hardening of the alloys. These alloys are used extensively in fabricating mechanical aids and
devices for application in prosthodontics and orthodontics. Palladium-rich alloys are used as sup-
ports in the porcelain-overlay type of dental restoration because palladium does not stain or discolor
the porcelain after it is fired. Testing of platinum compounds for their therapeutic value in cancer
treatment of humans is well along in many institutes in the U. S. and abroad. The possibility is
indicated that platinum compounds knock out or cause remissions in a very broad range of cancers,
with little or no side effects. It also appears that platinum may have possibilities as an antiviral
agent, and that it may inhibit leukemia.
Jewelry and decorative industry. Platinum, palladium and rhodium are used to fabricate
various jewelry articles such as watch cases, rings, broches and other settings. These metals
provide lightweight, white, tarnish-free alloys. Palladium-ruthenium alloys are used for large
jewelry articles because of their density and thus their light weight. Platinum settings do not
mask the true color of diamonds, whereas gold lends a yellow tint. In addition, and because of
platinum's mechanical properties, platinum settings hold gemstones more securely than gold.
Miscellaneous uses. These uses of platinum-group metals include laboratory ware such as
electrodes and crucibles. Platinum is used to control galvanic corrosion such as the cathodic pro-
tection of ship hulls, and as inert anodes in electrodeposition. New uses for control of corrosion
are found in the metal, chemical, petroleum, sewage disposal and water supply industries. Brazing
alloys which contain palladium have good wetting ability and are relatively free from erosion at high
temperatures. These alloys are frequently used in gas turbines, jet engines, and air frames when
a high level of reliability is required. Platinum and chromium are used to give razor blades a hard,
corrosion-resistant edge. The automotive industry has all but accepted the platinum/palladium/
ruthenium based catalytic mufflers for pollution control beginning with 1975 model automobiles.
In this system, exLaust gases pass over a platinum catalyst in the muffler and the carbon monoxide
(CO) and hydrocarbons (HC) are converted to carbon dioxide and water. Oxides of nitrogen (NOx).
which also have ceilings under Environmental Protection Agency (EPA) guidelines, are not reduced
by the platinum catalyst, but can be reduced by lower engine temperatures, engine modifications,
or other catalysts in the system. The system must use nonleaded gasoline, because lead, even in
small amounts, makes the catalyst inoperable.
Research and Alternates. Extensive research and development programs are pursued with
particular emphasis on applications of platinum-group metals in such industries as petroleum and
petrochemicals, pharmaceuticals, electrical energy and electrical and electronic products, and
powder metallurgy. Considerable effort is being directed toward the development of high-activity
platinum electro-catalysts for the direct conversion of chemical energy into electrical energy in
fuel cells, and there is an increased interest in research to develop a technically and economically
feasible method of recovering palladium and rhodium from atomic wastes.
However, there is also constant economic pressure to substitute less expensive materials
for the platinum-group metals in industrial applications. The platinum metals are only used where
they are justified technically and economically. Platinum and palladium as well as the minor
platinum-group metals are used interchangeably to some extent for certain uses. In some uses,
tungsten and nickel alloys, vanadium, silver and gold can be substituted for platinum-group metals.
Cladding with platinum-group metals enables the surface properties of the noble metals to be com-
bined with the mechanical strength of cheaper metals. Cladding is common in glass melting pots
and in chemical ware. Rhenium-platinum reforming catalysts may replace platinum to some extent
in petroleum refining. Cobalt-copper-rare-earth alloys may be substituted for platinum-cobalt
as a high-energy magnetic alloy in certain electronic applications.
In the automotive industry, there are three approaches competing with the platinum/palladium
catalytic muffler. (1) The nonplatinum catalyst system uses a cheaper catalyst that is resistant to
lead poisoning and hence can use currently available gasoline. Some catalysts for this type of sys-
tem are oxides of vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum,
tungsten and rare-earth elements. Although few details have been released on the performance of
these systems, they apparently have not been tested as extensively as the platinum system, and
their long-term reliability is uncertain. (2) The thermal reactor represents an afterburner to con-
vert CO and HC to carbon dioxide and water, in coordination with engine modifications and exhaust
gas recirculation to reduce NOX- While these systems approach the emission standards for the life
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of the car (versus platinum systems 25, 000 to 50, 000 mile reliability), they reportedly reduce gas
mileage and "driveability" considerably. Nevertheless, this system is a strong contender.
(3) Experimental automobiles with radical engine designs are being tested. Their engines are
inherently pollution-free. Some of these are steam-driven cars, battery-run electric cars, turbine-
engine cars, or they may use the Warren engine and other stratified-charge engines. Although the
design changes and lack of proved reliability and other characteristics make these cars unlikely
candidates for 1975 production by major manufacturers, some of these engines may be adopted as
long-range solutions to the pollution problems in the 1980's.
9. Attrition and Transfer to the Environment
In providing attrition and transfer rates, it is necessary to review the following breakdowns
according to published statistics.
Chemical Industry. In 1971, this industry purchased 135, 112 oz of platinum and 218,651 oz of
palladium. It is estimated that these purchases were divided as follows:
1971 1972
Platinum Palladium
(troy oz) (troy oz)
Chemical (inorganic) 83,229 (61.6%) 47,227 (21.6%)
Chemical (organic) 51.883 (38.4%) 171.424 (78.4%)
Total Chemical Industry 135,112(100.0%) 218,651(100.0%)
The rough data estimates for consumption rates in the chemical industry provided by the
Bureau of Mines are for nitric acid production only. These consumption data are related to the
latest industry purchased data of platinum and palladium, published for 1971 (Tables A-6 and A-7).
In inorganics, the two largest production items using catalysts with platinum-group metals are
shown below in billions of pounds (bp):
Sulfuric acid, 100% 58. 84 bp
Nitric acid, 100% 13. 48 bp.
In organics, the three major production groups, utilizing such catalysts are:
Ethylene 18. 30 bp
Cyclohexane 1. 75 bp
Benzene 1.08 bp.
The total chemical industry produced in 1971 about 203. 00 bp inorganics and about 77. 00 bp organics,
or a total of 280. 00 bp.
Petroleum Refining. The major data in this industry are published for crude-oil throughput
capacity, catalytic cracking, catalytic reforming and hydroprocessing. The rough data estimates of
consumption rates, available at this time, are for catalytic reforming. The development of total
U.S. refinery, cracking and reforming capacities are shown below in 1,000 barrel per calendar day:
Crude Oil Cracking Reforming
Capacity Capacity Capacity
Year (1000 b/cd) (1000 b/cd) (1000 b/cd)
December 31, 1971 13,284.9 4,512.5 2,885.2
December 31, 1972 13,087.0 4,852.0 3,169.1
December 31, 1973 13,383.0 4,512.5 3,278.1
The following Tables A-13 and A-14 provide rough consumption estimates, available at this time,
for use, replacement, scrap, attrition and transfer rates for platinum/palladium catalysts in major
industrial use categories. Based on the data shown above, order of magnitude comparisons are
possible for amounts of platinum and palladium used in those consuming industries for which detail
data are not available at this time.
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Table A-13. Estimated Platinum Consumption Rates in the United States
(troy oz/Year)
Industry
Chemical1)
(inorganic)
Chemical
(organic)
Chemical Total
Petroleum
(reforming)
Petroleum total
Glass4)
Electrical
Dental & medical
Jewelry &
decoration
Miscellaneous
Total known
at this time
Replacement
Rate
397,000
270,000
---
667,000
Use
Rate
~ - —
92,000
30, 000
20,000
50.0006)
192,000
Scrap
Rate
_--
18,000
900
4,600
23, 500
Attrition
Rate
53, OOO2)
---
over 8, 5003)
74,000
29, 100
15,400
180, 000
Transfer
Rate to
Envi ronment
49, 000 est.
---
over 8, 500 est.
74,000 est.5)
29, 100 est.
15,400 est.
176,000 est.
1971
Purchase for
Consumption
83, 229
51,883
135, 112
---
251,876
40, 703
51, 940
23,097
18,577
19,859
541, 164
est.
est.
1) nitric acid production only
2) includes 4000 oz. refining, rest transferred to environment or into products
3) includes losses
in reprocessing, does not
include
entrainment in products
4) no data available
5) includes transicr to environment direct and through manufactured
6) scrap, attrition
Source: Bureau of
and ti ansfer
goods
rates unknown at this time
Mines and Southwest Research Institute
Table A- 14. Estimated Palladium Consumption Rates
in the United States
(troy oz/Year)
Industry
Chemical )
(inorganic)
Chemical1)
(organic)
Chemical Total1)
Petroleum1)
(reforming)
Petroleum Total1)
Glass2)
Electrical3)
Dental & medical
Jewelry &
decorative
Miscellaneous4)
Total known
at this time
Replacement
Rate
Use
Rate
425,000
94,000
19,000
28,000
566, 000
Scrap
Rate
3, 000
4, 500
7, 500
Attrition
Rate
91,000
14,500
_.-
105,500
Transfer
Rate to
Environment
91,000 est.
14, 500 est.
_--
105, 500 est.
1971
Purchase for
Consumption
47, 227
171,424
218, 651
2,916
237
431, 505
61, 594
18, 752
26,451
760, 106
est.
est.
1) no data available at this time.
2) no data available yet, as glass industry is difficult to assess
3) telephone industry is dominant user; scrap, attrition and transfer rates unknown.
4) scrap, attrition and transfer rates unknown at this time
Source: Bureau of Mines and Southwest Research Institute
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10. Supply and Demand Trends
Apparent Supply. U.S. reserves are almost entirely in copper ores with a very small quantity
in placers at Goodnews Bay, Alaska. The copper ores are estimated to average about 1 oz of platinum-
group metals per 6000 tons of ore. Production from placer deposits at Goodnews Bay, with signifi-
cant amounts of iridium, rhodium and ruthenium,has been slowly declining in recent years, and the
remaining reserve is believed to be relatively small. The aggregate reserve of byproduct platinum-
group metals in gold ores also is relatively small.
The recoverable reserve in the Republic of South Africa is estimated at 200 million ounces,
averaging on the basis of past production about 70 percent platinum, 25 percent palladium and 5 per-
cent minor platinoids. Actually, the occurrence of platinum-group metals in significant quantities
in the Merensky Reef Horizon of the Bushveld igneous complex indicates that the quantity of platinum-
bearing ore may be considerably larger. The reserve of byproduct osmium and iridium in the gold
ore of the Republic of South Africa is significant. In Southern Rhodesia, prospecting and exploration
of the Great Dyke ultrabasic formation has disclosed the existence of platinum-group metals which
may potentially reach 100 million ounces.
Ethiopia has provided small quantities of metals from platinum placer deposits for years.
Exploration for additional sources is underway.
In Canada, the platinum-group metal content of the proven nickel-copper ore reserve of the
Sudbury Basin and Thompson, Manitoba areas is estimated at 16 million ounces, comprising 7.4 mil-
lion ounces of platinum, 7. 0 million ounces of palladium, and 1. 6 million ounces of minor platinoids,
chiefly rhodium.
Colombian placer deposits contain substantial reserves of platinum.
U. S. S. R. production of platinum-group metals has been rapidly expanding in recent years,
and it is estimated that reserves of platinum-group metals in the U. S. S. R. are at least 200 million
ounces.
Finland is providing small amounts of platinum-group metals from copper refining.
Japan provides small amounts of platinoids, mostly platinum and palladium as byproducts of
nickel-copper refining.
The Philippines are furnishing mostly platinum and palladium from nickel-cobalt concentrates.
In Western Australia, high platinum values were found on the Northwest Oil and Mineral Co.
property.
In New Zealand, high platinum values were found on the Georgia-Kaolin Co. property near
Kerikeri, North Auckland.
In Papua New Guinea, an independent nation since December 1973, and formerly under
Australian administration, increasing platinoid production is expected at or near the island of Bougain-
ville as substantial copper ore deposits are opened up.
Estimated proved reserves of platinum and palladium metals from known conventional sources
are shown in Table A-15.
The estimated proportions of six coproduct metals in the platinum group are shown on
Table A-16.
Demand. Of immediate effect on the demand for platinum, palladium and possibly ruthenium
metals is the development in the automobile emission control and petroleum refining areas. But, the
market outlook and hence the market price for these metals is still clouded. In the U. S., the major
automobile manufacturers have negotiated substantial supply contracts to permit all-out production
of 1975 cars equipped with platinum/palladium based converters. Volvo (Sweden) has contracted for
100,000 antipollution units to equip cars for U.S. delivery. Nissan Motors (Japan) have signed a
letter of intent to purchase 400, 000 converter devices to equip that firm's cars for U. S. delivery.
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Table A-15. Estimated World Reserves of Platinum and Palladium
(million troy oz)
Country Platinum Palladium
United States 0.95 1.96
Canada 6.94 6.86
Colombia 5.00
South Africa, Republic of 142.40 50.20
U. S. S. R. 60.00 120.00
Total 215.29 179.02
Source: Mineral Facts and Problems, 1970
Table A-16. Estimated Composition of Platinoids by Source
(percent)
Source Country
Metal Canada U. S. S. R. South Africa
Platinum 43.4 30.0 71.20
Palladium 42.9 60.0 25.10
Iridium 2.2 2.0 .78
Rhodium 3.0 2.0 2.41
Ruthenium 8.5 6.0 .50
Osmium .01
Source: Mineral Facts and Problems, 1970
Toyota Motor Co. (Japan) has also contracted for catalysts, Leyland Motor Corp. (Great Britain) is
reportedly negotiating with prospective suppliers of platinum-based converters. Engelhard Kali-
Chemie Autocat G. M. B. H. (West Germany) will provide catalysts for D.riouer-Benz, Peugeot and
Renault cars. Although the Environmental Protection Agency (EPA) has resisted requests for an
extension of the 1975 deadline, Detroit is still pressing for delay. This delay is also supported by
the Administration for reasons of the current energy and gasoline crises. Despite the fact that the
major U.S. manufacturers have negotiated substantial supply contracts, the industry's actual com-
mitment is small, because of the escape clauses in these arrangements.
Perhaps a still more serious problem concerns the availability of unleaded gasoline. Since
platinum/palladium catalysts are rendered ineffective by the presence of lead, unleaded fuel must be
made available in time to supply 1975 cars, and autofirms have indicated that the maximum residual
lead content permissible in such fuels is 0. 03 g per gal. However, sources in the petroleum industry
have continued to express doubt as to the possibility of producing sufficient quantities of unleaded
gasoline in time to meet 1975 auto requirements. It seems almost certain that great quantities of
platinum and palladium (and possibly some ruthenium) will be required in manufacturing converters
for 1975 automobiles and that the petroleum companies will utilize additional quantities of platinum
catalysts in petroleum refining, to boost the octane rating of gasoline without lead additives. It has
been estimated by Engelhard that each car will require an average of 0. 1 oz of metals including 30-
35% palladium and 65-70% platinum. If upwards of 10 million 1975 model U.S. cars were equipped
with these converters, then first year requirements beginning in 1974 could amount to 700,000 to
800, 000 oz of platinum and 300, 000 to 400, 000 oz of palladium with still larger quantities demanded
in ensuing years.
Based on these factors and allowing for expanded use by auto manufacturers outside the U. S. ,
it has been estimated that world consumption of platinum could increase from an estimated 1.92 million
oz in 1972 (Table A-l) to about 3.0 million oz in 1974 and considerably more thereafter. Over the
same period, global use of palladium might expand from around 1.98 million oz in 1972 (Table A-l)
to perhaps 2.4 million oz in 1974 and 2.6 million oz in subsequent years. These data suggest a pos-
sible increment in annual world use during 1972-74 of over 1 million oz of platinum and 500, 000 oz of
palladium. Present trends of platinum and palladium production were shown in Tables A-l, A-3, and
A-4 and estimated reserves in Table A-15.
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Among the established producing areas, South Africa may experience the most active growth.
As shown in Table A-Z, platinum output in 1972 was estimated to be 1 million oz, and palladium out-
put 355, 000 oz. The output could be boosted to about 2. 5 million oz of platinum and 890, 000 oz of
palladium in 1975. The U. S. S. R. was expected to produce close to 700,000 oz of platinum and about
1.4 million oz of palladium in 1972. Although she is exporting a substantial amount of both metals,
her output in these metals appears to increase. It is estimated that Canada produced about 399, 000 oz
of platinum group metals in 1972, and that she could increase production to over 500,000 oz.
In emergencies, and if Congress approves the release of stockpile material, platinum and
palladium reserves could be provided for eventual sale. The U.S. national stockpile on Dec. 31,
1971 consisted of 402,646 oz of platinum and 507,314 oz of palladium. The supplemental stockpile
included 49, 999 oz of platinum and 747,680 oz of palladium.
Recent Developments. Supply and demand trends will be influenced, above all, by possible
changes in the Clean Air Act with regard to auto emission standards and timing for conformance.
Earlier, in April 1973, the EPA had established modified interim standards for auto emissions
and granted automobile manufacturers-a one-year extension in implementing the federal 1975 exhaust
emission standards on all cars manufactured with the exception of those sold in California. Later,
at the end of 1973, the Administration requested Congress to amend the Clean Air Act and proposed
that 1975 interim levels should be frozen for 2 years to "permit auto manufacturers to concentrate
greater attention on improving fuel economy while retaining a fixed target for lower emissions. "
On March 22, 1974, the Administration has made several proposals to Congress to sacrifice
some air quality for making the nation self-sufficient in energy by 1980. Again included are proposals
to freeze the auto-emission standards through 1977.
According to current trade sources. General Motors has indicated it may install platinum/
palladium catalytic converters on many of its 1975 U. S. models to ensure compliance with interim
standards, and Ford considers that about 25 percent of its 1975 production will be fitted with platinum
converters. Other manufacturers expect to use catalytic converters on cars manufactured for the
California market. Hence, the EPA extension will have a moderate effect on delaying the projected
platinum and palladium consumption in catalytic converters and while the near term requirements
have become less stringent, the medium term outlook for these metals appears encouraging.
It also is of interest to note that in July 1973, the Canadian Government announced new exhaust
emission control standards for 1975 model cars in Canada that are much less stringent than those
adopted by the United States.
11. Medical and Toxicological Information
The information in this section is in part based on two literature searches, conducted by the
MED LINE Data System of the University of Texas Health Science Center at San Antonio and by the
National Technical Information Service, U. S. Department of Commerce, Springfield, Va.
Human Exposure Cases
Synopsis: Contact with the platinum oxide has been reported to cause eczematous lesions, and the
development of sensitivity to platinum chloride was observed in a chemist, who suffered
a generalized eruption from contact with a small amount of the substance. The trioxide
has also given rise to dermatitis in the Jewelry and Allied Industries. Photographers
have been reported to contract dermatoses from platinum solutions used in their work.
Asthmatic symptoms are not uncommon among workers exposed to the salts of platinum.
Palladium compounds show little or no irritation, when applied locally to the skin.
Platinum (Pt) is a silver-white metal, tenacious, very malleable, ductile and softer than silver.
Exposure to platinum in industry occurs in the metallurgical and chemical processes used in the pre-
paration of the metal and its salts.
Platinum was considered relatively harmless until 1945 when Hunter, Milton & Perry published
the results of their investigation of four platinum refineries. They found that, of 9 1 workers exposed
to the dust or spray of complex salts of platinum, 52 suffered from running of the nose, sneezing,
tightness of the chest, shortness of breath, cyanosis, wheezing, and cough. Thirteen of the men
complained of dermatitis. None of these symptoms were apparent in the workers exposed to metallic
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platinum dust only, or to the complex salts of the other precious metals, including palladium. Tin-
platinum content of the air samples taken at various stations throughout the works was determined
spectrographically and found to vary from S^g to 70 ^ g per cubic meter (Fothergill, Withers & Cle-
ments, 1945). One may safely conclude, therefore, that the soluble platinum salts, whether carried
as dust or mist, present an industrial hazard, and that they should be carefully controlled and not
exceed a maximum allowable concentration of 2 [i g per cubic meter.
The following case histories are given as examples of the syndrome.
Milne (1970) reports the following clinical record from Australia: The patient, a tall, brown-
haired, blue-eyed male, aged 37 years, was first examined in early May 1969, when he stated that
he had been born in Germany and had migrated to Australia at the age of 20 years. He had worked
as a laborer, a hospital orderly and a laboratory assistant. In 1967, he came to his present position
as a chemical assistant in a firm which intermittently processes platinum. He said that he had had
no skin affliction of any sort until two years before coming for examination, when his hands broke
out in a "weeping rash". He was not directly involved in the handling of platinum alloys or salts at
that time but in the course of his daily tasks would often enter the refinery. He went to many
practitioners, registered and otherwise, in an effort to obtain a cure. The condition which was
mostly diagnosed as "nerves" or "eczema" had slowly regressed until it had become a dry, itchy
rash on each hand and wrist. He had, for years, also suffered from occasional acute attacks of
asthma, and had consulted many doctors for this.
About a year before being interviewed, he had first worked on platinum refining, without
incident. About nine months later he noticed one day that his face was red and itchy. Next day it
began to "weep" and took several days to heal. A few weeks later, the same sequence of events
occurred, and a fellow workman suggested to him that exposure to platinum salts might be a causa-
tive factor.
Although he handled platinum alloys constantly in the interim, the patient then avoided platinum
refining for six weeks until the day of interview, when, after only 10 minutes' exposure in the refinery,
he noticed facial itch and swelling around the eyes. He stopped work after about half an hour, but
"little blisters" formed on his forehead, and they began to "weep". He put hot towels and "Vaseline"
on his face in an effort to gain relief, and after an hour he left work feeling "shaky". Soon after his
arrival home he vomited, then went to bed, and having drunk a glass of beer, he slept fitfully.
Six hours later, when I saw him, the swelling had largely subsided, but he had noticeable
infraorbital oedema and some blotchiness of the face. The itch had almost disappeared. He had no
further shakiness, and his hands were unaffected.
In late October 1969, he was interviewed again, and said that he had worked in a different
department in the meantime, almost completely detached from precious metals. His general health
had improved. The hands and -wrists had completely cleared, his face showed no swelling, and the
asthma had been "mild"--that is, one attack in four months. There were no patches of eczema any-
where on his body.
For two months after that hr was free of skin troubles and in good health, and then, about the
beginning of December 1969, he went as usual into the refinery, which he was in the habit of entering
once a week to make a complex gold salt--potassium-gold-cyanide. Unknown to him on this occasion,
the refining and filtration of platinum salts were in progress. Soon after this, his face broke out
again, with "little pimples" over the forehead and cheeks. The skin was itchy, red and swollen.
The "pimples" dried up over the next three or four days. His neck was also affected, and the same
thing occurred at his wrists. At the time of the interview, a few small, dry patches remained on
his wrists.
Since that time he has continued to work away from the precious metal refinery, and has been
untroubled by skin complaints except on one occasion, when, according to the firm's chief chemist,
he was again exposed, unknown to himself, and a similar series of events occurred.
Parrot (1969) reports the following cases from France:
Case 1. --A 50-yr old man was assigned directly to the platinum refining workshop in January
1960. No personal nor hereditary history of allergy was present. After two months, an erythemato-
vesicular, pruriginous dermatitis of the eczema type appeared on the anterior face or wrists and
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forearms, in the interdigital spaces, and on the elbow folds. An eczematous area was noted on the
right thigh behind the pocket where the handkerchief was kept. For three months, this dermatitis
was the sole symptom. Then suddenly, at the end of June I960, an asthmatic condition developed
requiring emergency hospitalization. The status asthmaticus persisted for 36 hours, then receded
under the action of intravenously administered adrenocorticotropic hormone.
Back to work, he had asthmatic attacks treated with aminophylline (theophylline ethylenedia-
mine). He required another month of hospitalization for asthma. The dermatosis finally vanished.
This worker was then transferred to another department. But if he only entered the platinum-
refining workshop or was in presence of platinum workers, that was enough to trigger an attack of
dyspnea. Subsequently, from June 1961 to May 196Z hyposensitization to house dusts was carried
out because tests for house dusts had been positive; no test with chloroplatinic acid or chloroplatinate
had been done. In July 1964, an attack of asthma required emergency transfer to a hospital. Later,
although this man had been discharged from the platinum workshop, he continued to have asthmatic
attacks when he met people from that workshop.
Case 2. --A 45-year old man was taken on in July 1964 for the manufacture of chloroplatinates.
He had no personal nor family history of allergy. After eight months' latency, bouts of nocturnal
asthma occurred. These were treated with triamcinolonediacetate and aminophylline. Over one
month, the asthma gradually worsened. Attacks occurred during work, more specially during the
hydrolysis operations. Then the subject exhibited dyspnea night and day. Despite symptomatic
treatment, the dyspnea increased with more or less violent paroxysms. A one-month work stoppage
brought complete recovery. Forty-eight hours after return to work this man had a very severe
attack of asthma, was transferred to another workshop, and has remained asymptomatic since then.
Cutaneous tests were negative but no test with chloroplatinate or chloroplatinic acid was carried out.
Case 3. --A 52-year-old man was employed in 1958 to manufacture chloroplatinic acid. For
one year there was no trouble. Then cutaneous pruriginous eczematoid lesions appeared on the fore-
arms, elbow folds, face, and neck. Hydrocortisone acetate ointment produced regression of the
dermatitis over the weeker.J; ^-elapse occurred on Monday when work was resumed. Platinum salts
tests were highly positive. Hypos ens itization to chloroplatinates and chloroplatinic acid was per-
formed without appreciable result: epidermal reaction with 1/1,000 platinum chloride solution still
yielded eczema. This man could carry on with the same work until 1962 when he was transferred to
another workshop where palladium was extracted from solutions containing various precious metals
among them platinum. Under those conditions slight eczema persisted. In 1964, the factory was
moved to a new very modern building. The worker was assigned to chloroplatinate calcination. A
generalized eczema immediately occurred, with nightly attacks of asthma. The asthma persisted and
attacks occurred several times a day; a violent attack required hospitalization.
This worker resumed his work in May in another workshop where he no longer had contact
with platinum salts. Eczema remained cured, but slight asthma persisted, triggered by irritating
vapors or by the presence of workers from the platinum refining shop.
Case 4. --A 22-year-old man was assigned to the platinum workshop. Two months later,
pruriginous erythema appeared on the forearms, elbow folds, armpits, and interdigital spaces.
Dermatitis improved on Saturdays and Sundays but recurred Mondays. For the two subsequent
months, lesions reached the neck, groin, and chest. The alternate application of hydrocortisone
ointment and acid paste, as well as intramuscularly injected cortisone acetate, brought a complete
cure although the patient did not interrupt his work. After eight days, dermatitis recurred. Then,
subsequent to slight choking following the accidental inhaling of a few puffs of chlorine, dry cough
and then attacks of asthma started. At the hospital, cutaneous tests with chloroplatinic acid and
ammonium and sodium chloroplatinate were highly positive: chloroplatinic acid tests in 1/1,000
dilution were followed by an epidermal reaction, then a tremendous cutaneous reaction; so we had to
remove the patch right away. Solutions of more dilute chloroplatinic acid and chloroplatinates were
also positive. Hyposensitization was not done. Permanent dyspnea developed, exaggerated by
activity. This required many days away from work. Transfer to another job brought a complete
cure.
Case 5. --A 19-year-old man was employed on March 16, 1964, at platinum refining. After
six months on this job, some attacks of asthma occurred at night. They did not occur at work, but
dyspnea was permanent and breathing remained wheezy. Weekly work stops for two days would
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cause complete recession of respiratory signs. Sometimes before the onset of asthma this worker
exhibited eczematoid dermatitis on wrists, forearms, face, and neck. He was treated with topical
applications of corticoids and aminophylline suppositories. Despite epidermal reaction tests showing
allergy to chloroplatinates, chloroplatinic acid, and rubber, no hyposensitization was started. During
military service this man was hospitalized, then discharged for asthma and allergic eczema. When
back at work, he was assigned to another workshop; asthma did not recur, but eczema persisted.
Finally, this man had to leave the factory.
Case 6. --A Z3-year-old man was employed at the test laboratory where chloroplatinates were
calcined. After seven years, he found that skin contact with such products triggered a nettle-rash
reaction after one minute latency which lasted about two hours. These phenomena became more
severe: as soon as he walked into the laboratory, conjuiitivitis, allergic rhinitis, asthma, and edema
of the eyelids appeared for half an hour. Transfer to another department produced complete cure.
Case 7. --A 27-year-old man was employed at the chloroplatinic acid workshop. Three months
after starting this work, he exhibited eczema of wrists and forearms, then of the neck. Fifteen days
later, while dermatitis remained, bronchial asthma occurred nightly and did not stop for four or five
days. Bouts of asthma also occurred during work. Transfer brought cure after one month. Now
this man can even walk into the platinum workshop without trouble.
Case 8. --A 30-year-old employee in the chloroplatinate workshop for five months developed
eczema on his upper limbs extending to the shoulders; he did not stop working. Since he did not
touch chloroplatinates any longer, he remained cured.
Freedman et. al. (1968) report the following case from Canada: Dr. T. T. , a 34-year-old
inorganic chemist on the teaching staff of a large university in the Montreal area, consulted one of us
(S. O. F. ) in April 1967, because of possible allergy to platinum salts. His history was that he had
worked with platinum compounds for about 10 years. During the previous 3 years, he noted that
whenever he came in close contact with platinum salts he would develop acute rhinitis and asthma.
His symptoms became progressively worse, finally reaching a point where he could no longer enter
his own laboratory without experiencing severe cough, wheezing, and shortness of breath. On one
occasion, a solution of ammonium chloroplatinate was accidentally splashed in his face by a co-worker
in the laboratory. Almost immediately, he developed massive angioedema of the face and acute genera-
lized urticaria which required epinephrine and steroids for control.
The patient was admitted to the Montreal General Hospital during an asymptomatic period for
detailed investigation. In the allergy history, it was determined that the patient had suffered from
mild ragweed hay fever for many years and that his daughter had infantile eczema. Otherwise, he
was completely free of atopic symptoms, except when exposed to platinum salts.
Complete physical examination was within normal limits. The resting blood pressure was
recorded as 140/80 mm Hg. A chest x-ray was reported as showing no evidence of pulmonary, cardiac,
or pleural disease. Respiratory function studies showed normal values for the vital capacity, timed
vital capacity, maximum breathing capacity, and maximum midexpiratory-flow rate. The electro-
cardiogram was within normal limits. Thus, there was no evidence for underlying pulmonary or
cardiac disease which may have been aggravated in a nonspecific fashion by inert dust particles.
Routine intradermal allergy tests showed moderate positive reactions to house dust and rag-
weed. There was no peripheral blood eosinophilia.
Marshall (1952) reports from South Africa: Mr. D. B. S. , a European male aged 25, was
first seen in July 1951 when he complained of a rash affecting his left thigh, hands and face. He gave
no history of any previous skin or allergic disease and there was no family history of allergy.
He had worked as a laboratory assistant for over a year and had been employed intermittently
during the previous eight months in the prepar.itiori of a platinum catalyst. Part of thi s process con-
sisted ot the deposition of platinum metal on .1 b.iso; and this was accomplished by evaporating chloro-
platinic acid over hot plates in an exIiauHl-vcnti lated fume cupboard. The fluid had, however, to lie
stirred by hand and the operator was bound to inhale a certain small amount of fumes and to have his
hands contaminated by the acid.
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In March 1951, about four months after he had first begun work on this process, the patient
began to experience attacks of 'tightness of the chest1 while at work. He felt 'as if no oxygen were
reaching the lungs'. At the same time his eyes and nose watered and he soaked his handkerchief
many times in a day. The attacks worked up to an evening climax, but had passed off by the next
morning. On one occasion he was off work for a week with 'bronchitis' which he considers to have
been a major attack.
One day in June 1951 he wiped his work bench clean of chloroplatinic acid (concentration unknown)
with his handkerchief. The next morning there was a patch of erythema on his left thigh, corresponding
to his trouser pocket where he kept his handkerchief. Two weeks later a rash appeared on the dorsa
of both hands; and about ten days later still the face became affected.
When first examined he presented a patch of erythematous, oedematous, scaling and excoriated
acute dermatitis, about 10 cm. in diameter, on the upper and anterior aspect of the left thigh. The
dorsa of both hands and wrists were similarly affected; and there were similar lesions of both cheeks,
and oedema of the eyelids.
Patch tests of the substances used in his work were applied to the anterior surfaces of the
forearms and the following results were obtained:
1% Hydrochloric acid: Negative after 48 hours.
1% Nitric acid: Negative after 48 hours.
1% Chloroplatinic acid: Positive 4-plus (bullous reaction) in less than 24 hours.
Removed from work and treated only with bland applications, the patient rapidly recovered
from his dermatitis and had no further asthmatic attacks.
Hunter, et. al. (1945) report the results of an investigation of workers in four platinum
refineries in Great Britain:
Case 1.--R.C., aet. 58, research chemist, worked a refinery A from 1907 to 1924 (18 years).
From the first year at this work he noticed a tightness of the chest witha wheeze when certain pro-
cesses in the refinery which caused a spray were in operation. He noticed a tightening also in the
muscles of the back and marked sneezing. There was a watering of the eyes and a dislike of light.
He would go home and go straight to bed, and would wake up in the morning quite fit, only to repeat
the same symptoms the next day. He was forced to leave the refinery in 1924 because the symptoms
became so bad he could no longer carry on. Since then he has been perfectly well. On one occasion
he returned to the refinery on business and immediately noticed a tightness of his chest, even though
the process to which he was sensitive was not going on in the room. However, it was discovered
that sodium chloroplatinate had been weighed out in the room about half an hour previously. There
was no family history of asthma. He now showed no abnormal physical signs. His blood count was
4, 160, 000 red cells per c. c. , haemoglobin 111 percent, (photoelectric estimation of alkaline
haematin 100 percent. , equivalent to 13.8 gm. haemoglobin percent. ), white cells 12, 200, poly-
morphs 61 percent., small lymphocytes 6 percent, large lymphocytes 27 percent, large hyalines
6 percent. Dr. D. Jennings reported on an X-ray of his chest--old bilateral apical infection with
fibrosis and drawing upward of both hila; emphysema of both bases.
Case 2. --A. W. , male, aet. 38, started work at the age of 15 in a chocolate manufacturing
factory. He worked here for 6 months and then transferred to platinum refinery A. After six years
on this work he noticed that when certain processes were in operation his nose started to run and he
would start sneezing. This lasted for half an hour. The symptoms gradually got worse and after
ten years he began to get tightness of his chest, shortness of breath, wheeze and cough, but he
produced no sputum. He never had an attack at home. The attacks gradually got more frequent
and more severe, and two months before he was interviewed he was moved to the "other precious
metals" department. Since this move he has not had further attacks. He had had no previous
illness, and there was no family history of asthma. On examination no abnormal physical signs
were found, except that when he painted a 3 percent solution of sodium chloroplatinate on his fore-
arm a large wheal appeared. His blood count showed 5, 120,000 red cells, 100 percent, haemoglobin
(photo-electric estimation), 11,200 white cells, 50 percent polymorphs, 41 percent, lymphocytes,
3-5 percent eosinophils, 5.5 percent monocytes. X-rays of his chest showed emphysema.
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Case 3. --E. V. N. , chest, assistant manager of wet process at refinery B, aet. 28, had
worked for five years in the laboratory and for 2-1/Z years as assistant manager of the wet process.
Immediately he started on the process he became aware that if he entered the room where ammonium
chloroplatinate was dried his nose started to run, producing perfectly clear fluid. He would soak
three handkerchiefs in an hour. He would develop severe sneezing attacks and some irritation of his
eyes. After he had been there three months these symptoms were followed by tightness of the chest
which would last for half an hour, and wheezing which lasted 5 hours. He would be awakened in the
early hours of the morning with a cough which might last an hour, but the following day he would be
quite fit. He had had no previous illness, and there was no family history of asthma. He entered
the drying-room on the day he was interviewed and was observed in an attack. He was cyanosed,
dyspnoeic and had an audible wheeze. His respiration rate was 34. He had no clubbing of his fingers.
His chest moved evenly, was hyper-re sonant with normal air entry but many sibilant rhonchi through-
out. There were no other abnormal physical signs. His blood count showed 6,350, 000 red cells,
130 percent, haemoglobin (photo-electric estimation), 8200 white cells, 60 per cent, polymorphs,
30 per cent, lymphocytes, 5 per cent, eosinophils, 1 per cent, basophils and 4 per cent, monocytes.
X-ray of his chest revealed no abnormality. During the attack he was given 10 minims of 1/1000
adrenalin intramuscularly, but it did not produce any relief of the symptoms, though it raised the
pulse rate from 80 to 120.
Case 4. --L. J. , aet. 36, process hand, worked 7 years at a chemical plant and then for
14 years at platinum refinery B on the wet process and in the "other precious metals' department.
During the past 3 years he had had attacks of running nose, sneezing, shortness of breath, tightness
of the chest, wheeze and cough. He was frequently awakened by attacks of coughing at 2 a. m. , and
had had such an attack every night for the three months previous to his sick-leave which had lasted
3 weeks at the time of interview. He had never had any attacks while away from the works. He was
moved to the time office, but still got some attacks, and was therefore transferred to another depart-
ment where he would not be exposed to the salts of platinum. He had had pleurisy at the age of 8,
and had his tonsils removed 1 year previously because of his asthma. There was no family history
of asthma. When examined he had not been at the refinery for three weeks, so he appeared a healthy
man, and showed no abnormal physical signs. His blood count showed 4, 760, 000 red cells, 104 per
cent, haemoglobin (photo-electric estimation), 7450 white cells, 57 per cent, polymorphs, 1.5 per
cent., eosinophils 39.5 percent lymphocytes and 2 percent, monocytes. Dr. M. H. Jupe reported on
an X-ray of his chest as follows: "There are a few scattered calcified nodules over the lung fields.
The hilar shadows are well seen, but not excessive. "
Case 5. --M. D. , female, aet. 20, had worked as a press operator before entering platinum
refinery C; 3 months before her interview? she was observed sieving spongy platinum without exhaust
ventilation or mask, and was seen to be without any symptoms. She said that when she handled the
dry complex salt her eyes and nose would run, and she sneezed continuously. She experienced some
tightness of the chest the same evening, but this never woke her at night. She had never been ill, and
had no family history of asthma. On examination she had no abnormal physical signs. Her blood
count showed 4,500,000 red cells, 98 per cent, haemoglobin (photo-electric estimation), 12,000 white
cells, 58 per cent, polymorphs, 2 per cent, eosinophils, 3. 1 per cent, lymphocytes, 6 per cent.
monocytes. X-ray of her chest revealed no abnormality.
Case 6. --A. A. , chemist, aet. 33, for past 4 years had been in charge of platinum refinery
D. For 12 years before that he had been an analytical chemist. He had no symptoms except when he
treated the filtrates with granulated zinc; this caused effervescence and droplets containing complex
salts to be thrown into the atmosphere. Then his nose ran and he sneezed. This might last for half
an hour. He had no tightness of his chest, shortness of breath, cough or -wheeze. He had had scarlet
fever as a child, but there was no family history of asthma. On examination, apart from a very mild
degree of funnel chest, he had no abnormal physical signs. His blood count showed 5, 950, 000 red cells,
118 per cent, haemoglobin (photo-electric estimation), 7000 white cells, 60 per cent, polymorphs,
36 per cent, lymphocytes. 1 per cent, eosinophils, and 3 per cent, monocytes.
Toxicological Information
Synopsis:
Platinum:
Exposure to complex platinum salts has been shown to cause allergic symptoms of
asthma and dermatitis such as wheezing, coughing, running of the nose, tightness in
243
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the chest, shortness of breath, cyanosis, and itching of the skin, whereas exposure to
dust of pure metallic platinum causes no symptoms. People working with complex
platinum salts are often troubled with dermatitis. This does not appear to include
the complex salts of other precious metals.
Palladium:
Toxicity is low. This metal, in the form of palladium chloride, has been administered
orally in dosage of about 1 grain daily in the treatment of tuberculosis. These amounts
resulted in no toxic effects. Applied locally to the skin, palladium chloride shows little
or no irritation. In experimental animals, palladium chloride has been given by
intravenous injection, producing damage to bone marrow, liver and kidneys when the
dosage was of the order of 0. 5 to 1. 0 mg per kg of body weight.
Levene(1971) provides the following comments on platinum sensitivity: Disease caused by
platinum worked into annular or trinket form is not an everyday problem. Dermatitis from metallic
platinum has apparently only been recorded in one patient (Sheard, 1955). However, those concerned
in the refining or analysis of platinum are required to work with the complex salts of the metal and
it is these which give rise to a characteristic syndrome. The complex salts are sodium, potassium
or ammonium tetrachloroplatinate or hexachloroplatinate. Apart from being essential intermediate
compounds in the refining and assaying of the metal, they are used in the manufacture of platinum
sponge, a finely divided form of the metal which is a most valuable industrial catalyst. Individuals
may work in an atmosphere containing these salts for periods of months or years without trouble,
but sooner or later the majority of workers will develop symptoms referable to the respiratory sys-
tem and/or the skin.
The respiratory symptoms were clearly described in a classic paper by Hunter, et. al. (1945)
and consist of rhinorrhoe-i, sneezing, cough, tightness in the chest, wheezing, shortness of breath
and cyanosis. In short, they resemble a mixture of hay fever and asthma. Symptoms can arise
within minutes of exposure. lr the patients reported by Hunter, et. al. , 52 of 91 employees who
worked in platinum refineries in the London area had the asthma/hay fever syndrome to a significant
degree. Thirteen of the 91 had a skin eruption of scaly erythematous type but a few had urticarial
lesions. Jordi (1951) in Zurich described 3 cases in which asthma followed inhalation of platinum
salts and immediate urticaria followed splashing of solutions on the neck and forearms. One case
produced a cutaneous weal within 2 min. of painting with a 3% solution of sodium chloroplatinate but
the responses were not clear-cut. Roberts (1951) in Malvern, Pennsylvania investigated reactions
seen in employees in a platinum laboratory and refinery over a period of 5 years. He coined the
term "platinosis" for the syndromes he encountered.
He noted that once disabling symptoms arose in any one case that person never again became
asymptomatic in a platinum-containing atmosphere. His observations concurred exactly with the
other reports, and it was advised that sufferers from the effects of platinum salts should be trans-
ferred to other work. Five cases with both asthma and eczematous dermatitis have been described
from Paris by Parrot, et. al. (1969); in a study of 51 subjects 35 had symptoms of platinosis.
Freedrnan and Krupey (1968) report a man with the respiratory syndrome who developed massive
angio-oedema and acute generalized urticaria following accidental splashing of ammonium chloro-
platinate solution on the face.
Roberts carried out scratch tests with aqueous solutions of sodium chloroplatinate on 60 plati-
num workers. He found that all subjects developed a one plus ( + ) reaction with a 1:10 dilution of the
salt. Following the onset of symptoms, either of the cutaneous or respiratory type, a reaction was
always obtained with a 1:1000 dilution. He decided that initial scratch-testing was an unreliable
index of liability to develop future symptoms and he claimed that a person with a strong personal or
family history of atopy or of contact dermatitis was more likely to succumb to platinosis than others.
However, he believed that individuals with moles, acne or sebaceous cysts were also particularly
prone to the condition.
The elicitation of an immediate skin weal and symptoms resembling asthma and hay fever
after exposure to complex platinum salts suggest that either a pharmocological or an allergic hista-
mine liberating process is operating. Parrot, et. al. (1963) injected sodium chloroplatinate solution
intravenously into normal guinea pigs and found that when a sufficient dose was given, the animal
2HH
-------
developed intense asthma and died within a few minutes. Smaller doses provoked non-fatal asthma,
and if the dose was repeated several times the effect became successively less intense. Complete
protection against such asthmatic episodes was afforded by prior injection with the antihistamine
drug mepyramine. From these observations and further experiments using isolated guinea pig ileum
in vitro, the authors concluded that platinum salts act as powerful histamine liberators in the guinea
pig. However, despite these findings it seems clear that the clinical syndrome of platinosis in man
is largely the result of hyper sensitivity to platinum salts. Evidence in favour of this contention is as
follows: (1) workers do not have symptoms initially, the syndrome comes only after months or even
years of exposure to the salts, (2) symptoms increase in severity with repeated exposure, (3) cutan-
eous scratch tests to platinum salts at a dilution of 1:1000 become positive with the onset of symptoms
when they had been previously negative (Roberts, 195J), (4) passive transfer tests (Prausnitz-
Kustner reaction) using patient's serum have been positive using both the platinum salt alone and in
conjunction with human serum albumin (Freedman and Krupey, 1968).
It is worth pointing cut that scratch or intradermal testing can be hazardous to the point of
being life-threatening in these patients. A single intradermal test using potassium hexachloroplati-
nate at a concentration of 1 ng/rnl produced an anaphylactic reaction in the patient of Freedman
and Krupey (1968). It is wise for these patients to be protected by systemic antihistamine prior to
skin testing.
It has hitherto been recommended that patients with platinosis should change their occupation.
There is no doubt that this management is effective since symptoms resolve rapidly when the patient
is removed from exposure to platinum salts. However, since the main components of the syndromes
of sensitivity to platinum salts are those of an hypersensitivity response.it would seem reasonable
to attempt hyposensitization by progressively increasing intradermally injected doses of platinum
salt in a way analogous to that employed using pollen in hay fever (Frankland, 1965), and strepto-
mycin in cases of immediate hypersensitivity to this drug (Cohen, 1954; Levene and Withers, 1969).
Successiui hyposensitization was recently achieved in an analytical chemist who exhibited
typical severe symptoms of hay fever, asthma and contact urticaria when exposed to platinum com-
plex salts in the course r>f his work (Levene and Calnan, 1971). Starting with a dose of 1 0 ng he was
given increasing doses of ammonium hexachloroplatinate intradermally several times daily for a
month. Immediate symptoms were weal and flare at the site of injection, and wheezing and flushing,
which usually passed off within 30 minutes. On the twelfth day of the course of injections he began to
develop crops of widespread symmetrical erythematous papules and joint pains coming on 2 hours
after injection, i.e. he developed a strum sickness-like reaction. Histology of the papulec showed
an intense perivascular infiltrate of polymorphonuclear leukocytes--mainly eosinophils. The injection
sites at first produced very prominent weals and flares but these tended to diminish with increasing
doses. At first the weals faded rapidly with no sequelae but later in the course, with higher doses,
the injection sites developed pinkish-brown tender papules after the initial weal had subsided. With
the highest injected dose (100 p.g), the injection site became very tender and necrotic after 2 days.
The appearance resembled the Arthus phenomenon as seen in experimental animals. An injection
of this dose into a normal subject produced only a slight transient reaction at 24 hrs. By this time
it was found that the patient could carry out his usual work and handle ammonium hexachloroplatinate
without the hay fever and asthma symptoms and urticaria which had previously partially disabled
him. He remained well while working with hexachloroplatinate although a chance exposure to tetra-
chloroplatinate produced symptoms, suggesting that his reduced sensitivity was specific for the hexa-
chloroplatinate. A further chapter in his pathology occurred after he stopped working with platinum
salts for about 3 months. When he was again exposed he found that he had partially relapsed, and he
required readmission to hospital for a further course of injections. Since-then, he has had continuous
exposure and has remained well.
It is of interest to consider the mechanism of his hypersensitivity and its amelioration by the
technique of hyposensitization. It is postulated that the original symptoms were mediated by
reaginic (IgE) antibody and that injections of the platinum salt stimulated production of IgG (blocking)
antibody which combined preferentially with the antigen to prevent anaphylactic symptoms. The
development of a serum sickness-like and Arthus-like reaction during hyposensitization give support
to this hypothesis since there is evidence that such reactions are caused by immune complex forma-
tion involving precipitating antibody (Cream and Turk, 1971). Although specific IgG antibody was not
directly demonstrable in this case by double diffusion in agar or by haemagglutination using either
the platinum salt alone or in conjugation with human serum albumin, it was found that intradermal
245
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injection of the platinum salt incubated with post-hyposensitization serum gave a much smaller weal
and flare than salt incubated with pre-hyposensitization serum. This indicated that post-hyposensiti-
zation serum had acquired the ability to block the immediate weal and flare response and it seems
very likely that newly formed IgG antibody was responsible for this blocking activity. The platinum
salt presumably acts as a hapten which combines with an endogenous protein to form an allergenic
hapten-protein complex. A likely candidate for the protein concerned is serum albumin as suggested
by Freedman and Krupey (1968). Although it has been assumed that the anaphylactic symptoms in
these cases are the result of IgE antibody, it has recently been shown (Parish, 1970) that IgG antibody
can have limited anaphylactic activity. However, Parish considers it unlikely that anaphylactic IgG
could participate in the classical reagin-mediated reactions--asthma, hay fever, or urticaria--that
occur within minutes of exposure to antigen.
The situation with regard to the eczematous dermatitis in response to complex platinum salts
as described by several authors is less clear. It is quite likely that allergic contact sensitivity can
occur but this has not yet been convincingly proven by patch tests in appropriate cases. Allergic
contact sensitivity is a delayed hypersensitivity reaction, and the situation is complicated by the well-
documented ability of these salts to produce urticaria on contact. It is not even clear what is an
appropriate concentration to be used for patch testing. For a patch test to be valid it must, of course,
be shown that the chosen concentration does not produce an irritant reaction in control subjects (Bett
and Calnan, 1957). Complex salts of platinum are not readily soluble in distilled water, but solubility
is improved if physiological saline is used. They dissolve in dilute hydrochloric acid but such solu-
tions are probably not suitable for patch testing. These problems remain to be resolved.
Although platinosis is a rare disease outside platinum refineries, recent reports indicate that
platinum salts may be of value in cancer chemotherapy (Rosenberg, et al. , 1969; Harder and Rosen-
berg, 1970). Platinum compounds have not been widely used as therapeutic agents despite an early
report that they were "very effective" in syphilis and rheumatism (Hoefer, 1841). If these com-
pounds do come into generaluse, one can anticipate that allergic reactions to them may be seen.
Schroeder, et. al., (*?71) report on studies of the innate effects of low doses of abnormal
trace elements in drinking water on mice and rats exposed for life, conducted in an environment
built so as to exclude metallic contaminants:
In order to evaluate possible innate toxic effects of small doses of rhodium and palladium in
terms of growth and survival, mice divided as to sex were raised in an environment limited in
metallic contamination and given 5 ppm metal in drinking water from weaning until natural death.
Body weight was measured at monthly intervals up to 6 months, at 1 year and at 18 months of age.
The feeding of palladium was associated with growth suppression at 7 and of rhodium at 6 of 16 inter-
vals compared to mean weights of controls. Survival of palladium-fed males was greater than that
of controls. Tumors were found at necropsy in 16. 3% of one group of controls, 28. 8% of the rhodium
and 29.2% of the palladium groups. Malignant tumors were increased in rhodium and palladium
groups, at a minimally significant level of confidence (P < 0. 05), all but one tumor being malignant.
In a second series, tumors were present in 26.8% of controls. All tumors in these latter groups
were malignant. Rhodium and palladium appear to exhibit slight carcinogenic activity in mice.
Spikes, et. al. , (1969) report on experiments of enzyme inhibition by palladium chloride:
In the course of examining palladium porphyrins as possible sensitizers for the photodynamic
inactivation of enzymes, it was observed that palladium (+2) inactivated trypsin directly by a non-
photochemical process. Although palladium (+2) has been shown to bind to proteins such as carboxy-
peptidase, casein, papain and silk fibroin, and to interfere with plant growth, reports were not
found in the literature on its action as an enzyme inhibitor. For this reason a preliminary examina-
tion of the effects of palladium ( + 2) on several enzymes was carried out.
Of the enzymes listed above, only chymotrypsin and trypsin were inactivated by palladium (+2).
The inactivation was time- and pH-dependent. Trypsin was very rapidly inactiviated at pH 4. 2, but
was not inactivated at pH 8. 9. Alphachymotrypsin was also inactivated very rapidly at pH 4. 2, but,
in contrast to trypsin, was inactivated fairly rapidly at pH 8.9.
The mechanism of the inactivation of chymotrypsin and trypsin by palladium (+2) is not known.
Other metals (copper, zinc, mercury) in the divalent form also inhibit these enzymes; mercury
246
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presumably inhibits trypsin by reacting with sulfhydryl groups. It has been suggested that mercury
may inactivate chymotrypsin (which has no free sulfhydryl groups) by forming a stable chelate with
the active-site histidine. Palladium (+2) binds to papain with the same stoichiometry as does mercury
(+2), which suggests that, for this enzyme, its binding is due to interaction with sulfhydryl groups.
Palladium (+2) forms complexes with L-cysteine, L-cystine and L-methionine in solution, but not
with L-histidine. Thus, one could envision that palladium (+2) inactivates trypsin by combining
with free sulfhydryl groups and/or with cystine groupings, while the inactivation of chymotrypsin
might result from reactions with cystine groupings.
Wood (1974) reported recently:
Platinum and palladium will be methylated in the environment by microorganisms. These
metabolic products could be more toxic than other forms of the metals. Platinum and palladium were
listed as very toxic and relatively accessible.
Summary of Medical and Toxicological Information
Metallic platinum is-non-toxic and never gives rise to occupational injury. The oxide causes
eczema of the hands and forearms and some lesions of the nails. Dust and spray from the complex
salts of platinum have been found to cause asthma after continued exposure. The initial symptoms
of the reaction begin with repeated sneezing followed by a profuse running of the nose with a watery
mucous discharge. Later reactions which may develop are tightness of the chest, shortness of the
breath, with wheezing and blue coloration of the face. When the operator leaves the work, the
symptoms clear with the exception of the persistent bouts of coughing in the night which may endure
for about one-half hour. When the work is resumed, the symptoms recur. Certain typical skin
reactions may also develop in some individuals; this is characterized by a scaly red rash. Blood
checks, skin tests, and X-rays do not reveal any abnormalities leading to the lesions noted. Pre-
cautions lie in minimizing the exposure by adequate means not to exceed a maximum allowable con-
centration of 2 ng per cubic meter for the soluble platinum salts. Treatment consists in removal
from exposure ar.H consultation with a physician with a full-history of the exposure.
Palladium salts commonly used are the chloride and the amino-nitrite. So far as is known,
the palladium salts do not constitute any threat of injury in industry, but laboratory tests show that
when these substances are introduced inanimals, damage occurs to the heart, kidneys, liver and
bone marrow. From these indications, it would seem that palladium salts should be carefully watched
for chronic and cumulative toxic effects.
The Environmental Protection Agency has efforts underway at EPA-Cincinnati on the toxicity
of platinum and palladium. The results of these studies should provide substantial additions to the
toxicity data presently available.
247
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APPENDIX B. ANALYSIS AND PROJECTIONS
1. End Use and Production Projections
The projected forecast base for total demand of platinum and palladium was established for
each of the end use categories. The forecast bases were derived by relating domestic end uses of
each metal in 1971 to the anticipated growth of such indicators as the gross national product (GNP)
or total population, adapted from the White House Conference on the Industrial World Ahead: A Look
at Business in 1990. Relevant contingency factors, which would have a positive or negative influence
on the projected demand in each end use category, were then considered to obtain a high and low range
of demand. The aggregation of these internal ranges for each end use category constitutes the
median, low and high forecast ranges in the years 1980 and 1990 for platinum and palladium.
In the rest of the world, the demand for platinum catalysts in the petroleum industry is
increasing more rapidly than in the United States as the use of platinum in reforming processes to
produce higher octane motor fuels is being adopted. Rest-of-the-world growth in chemical uses will
probably increase fairly rapidly as the demand for fertilizer materials increases. Within the electric
industry, where palladium is used, the move to electronic and other means of switching may result
in a relatively slow rate of future growth in the rest of the world. Demand in dental, medical, glass
and jewelry applications in other countries will probably grow at rates approximating those in the
United States. Based upon these considerations, the rest-of-the-world demand for platinum is
expected to range between 1.565 and 2. 087 million ounces in 1980 (with a median of 1.826 million
ounces), and between 2.317 and 3.089 million ounces in 1990 (median, 2.703 million ounces). The
growth rate corresponds to 4.0 percent. The rest-of-the-world palladium demand is expected to
range between 1. 182 and 2. 128 million ounces in 1980 (median, 1.655 million ounces). In 1990, the
range is projected from about 1. 750 to 3. 150 million ounces at a median of 2. 450 million ounces.
The median growth rate corresponds also to 4.0 percent. The following Tables B-l and B-2 show
the domestic and rest-of-the-world forecast ranges of demand for platinum and palladium. Tables
B-3 and B-4 present forecast bases for each category of end use.
Table B-l. Forecast Range of World Demand for Platinum
(thousand troy oz)
1971 1980 1990
United States
Rest-of-the-world
Total world demand
estimate
high
median
low
high
median
low
high
median
low
541
1283
1824
1900
1508
1141
2087
1826
1565
3987
3334
2706
2442
1910
1453
3089
2703
2317
5531
4613
3770
Source: Mineral Facts and Problems 1970 and Southwest Research
Institute
The projections for platinum and palladium in catalytic mufflers are based on an immediate
demand of 700, 000 oz platinum and 300, 000 oz palladium, required at the original 1975 timetable.
The rest-of-the-world demands in 1971 are taken from Tables A-3, A-4, A-8, and A-9, where it was
shown that about 1.82 million oz of platinum and about 1. 92 million oz of palladium were produced in
1971. The projection of production figures to 1980 and 1990 are given in terms of requirements from
major producers on Table B-5.
A comparison of the 1975 production objectives for major producing countries with the pro-
jected world demand shows that a constant 1975 production rate for platinum would meed the 1980
median demand, whereas the constant 1975 production rate for palladium would not meet the 1980
median demand. Based on the 1975 objective, it would appear that the world platinum production
needs to be increased by 2. 064 million oz to meet the 1990 high demand projection, and by 1. 146 mil-
lion oz to meet the 1990 median projections. World palladium production would need to be increased
248
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Table B-Z.
Forecast Range of World Demand for Palladium
(thousand troy oz)
1971
1980
1990
United States
Rest-of-the-world
Total world demand
estimate
high
median
low
high
median
low
high
median
low
...
760
1163
19Z3
1589
1Z30
78Z
Z1Z8
1655
118Z
3717
Z885
1964
1919
1466
96Z
3150
Z450
1750
5069
3916
Z71Z
Source: Mineral Facts and Problems 1970 and Southwest Research
Institute
Table B-3. Contingency Forecasts of U. S. Demand for Platinum
by End Use, 1980 and 1990
(thousand troy oz)
U.S.
End Use Demand
by Industry 1971
Chemical ,
(inorganic)
Chemical,
(organic)
Petroleum
Glass
Electrical and
Electronic
Dental and
Medical
Jewelry and
Decorative
Miscellaneous
Automotive
Catalysts
Total (Rounded)
81
54
25Z
41
5Z
Z3
18
ZO
541
U.S.
Forecast
Base 1980
117
60
365
59
58
Z5
Zl
Z9
774
1508
U.S.
Low
1980
105
43
Z61
54
30
Z5
19
Z4
580
] 141
U.S.
High
1980
195
69
489
88
74
50
47
36
85Z
1900
U.S.
Forecast
Base 1990
177
67
551
90
64
28
23
44
866
1910
U.S.
Low
1990
159
48
394
83
33
28
Zl
37
650
1453
U.S.
High
1990
Z95
77
738
135
8Z
56
51
55
953
2442
Source: Mineral Facts and Problems 1970 and Southwest Research Institute
ay 2.496rnillion oz to meet the 1990 high demand projection, and by 1 .343 million oz to meet the 1990
median projection. Table A-15 showed that platinum reserves of major producing nations are estimated
as 215.29 million oz and palladium reserves as 179. 02 million oz. It would appear that the projected
iemands for platinum and palladium can be met amply during the forecast period from known reserves.
\. Contingency Assumptions
Contingency assumptions made to establish the U. S. forecast range of demand for each end use
n 1980 and 1990 are presented below.
Industrial Inorganic Chemicals. The forecast base in the years 1 980 and 1990 for this end use was
obtained by relating the growth in demand for platinum and palladium to the growth in GNP which is
anticipated as 4.2% annually according to the White House Conference Board. The forecast bases of
lemand for platinum are 117, 000 (1980), 177,600 (1990) oz and for palladium 191, 000 (1980) and
i89,000 (1990) oz. The chemical industry is a large consumer, especially for the production of nitric
icid which is used in tonnage quantities in the production of fertilizers and explosives. With the steady
ncrease in population as well as demand for food products world wide, there is a continuing demand
249
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Table B-4. Contingency Forecasts of U. S. Demand for Palladium
by Efid Use, 1980 and 1990
(thousand troy oz)
End use
by Industry
Chemical
(inorganic)
Chemical
(organic)
Petroleum
Glass
Electrical and
Electronic
Dental and
Medical
Jewelry and
Decorative
Mi s c ellane ous
Automotive
Catalysts
U.S.
Demand
1971
132
87
3
0.20
432
61
19
26
U.S.
Forecast
Base 1980
191
96
4.3
0.29
478
69
21
28
332
U.S.
Low
1980
179
96
3.2
0.27
212
69
21
36
166
U.S.
High
1980
298
128
6.5
0.43
584
104
49
54
365
U.S.
Forecast
Base 1990
289
108
7
0.44
534
77
23
57
371
U.S.
Low
1990
271
108
5.3
0.40
237
77
23
54
186
U.S.
High
1900
452
144
10.5
0.66
653
116
54
81
408
Total (Rounded)
7bO
1230
782
1589
962
J919
Source: Mineral Facts and Problems 1970 and Southwest Research Institute
Table B-5. World Production Requirement for Platinum and Palladium
World Demand
(thousand troy oz)
1971 1980 1990
Canada
Production Objective 1975
(thousand troy oz)
U.S. S. R. U.S.A. Total
Platinum:
high
medium
low
Palladium:
high
medium
low
1824
1923
3987 5531
3334 4613
2706 3770
3717 5069
2885 3916
1964 2712
217
283
700
1400
2550
890
3467
2573
Source: Southwest Research Institute
for fertilizers. The demand for explosives may increase due to increased activity in mining and
quarrying operations and in the construction of roads, dams and reservoirs. The present rate of
growth for the chemical industry is about 10 percent per year. At this growth rate, the high demand
for platinum would be 195, 000 (1980), 295,000 (1990) oz and for palladium 298,000 (1980) and 452, 000
(1990) oz. More efficient use of these metals or the use of alternate metals in catalysts for producing
nitric acid may contribute to a low demand for platinum and palladium. It is also possible that nitro-
gen replenishment of the soil by direct application of ammonia will increase substantially. Addition-
ally, the use of mechanized boring machines for mining and quarrying operations may reduce the
demand for explosives. These contingencies may result in a low demand for platinum of 105,000
(1980), 159, 000 (1990) oz and for palladium of 179, 000 (1980) and 271, 000 (1990) oz.
Industrial Organic Chemicals. The forecast bases in the years 1980 and 1990 were obtained by
relating the growth in demand for platinum and palladium to the anticipated growth rate of total popula-
tion at 1. 125 percent per annum, resulting in platinum demand of 60,000 (1980), 67,000 (1990) oz and
in palladium demand of 96, 000 (1980) and 108, 000 (1990) oz. The use of medicinals proportional to
total population will probably rise due to increase in longevity and an expansion in Medicare and other
health programs. It is also anticipated that synthetic fibers will be used increasingly in lieu of
natural fibers. Thus, the demand could reach highs for platinum of 69, 000 (1980), 77, 000 (1990) oz
250
48
-------
and for palladium 128, 000 (1980) and 144, 000 (1990) oz. A low demand in this category may result
from the development of alternative processes for producing medicinals. Moreover, education may
result in higher health standards achieved through preventive medicine. New techniques in fabrica-
ting and producing synthetic fibers may reduce the demand for spinnerets made from platinum-group
metals. Due to these contingencies, the low demand could be for platinum 43,000 (1980), 48,000
(1990) oz and for palladium 96,000 (1980) and 108,000 (1990) oz.
Petroleum Refining. The forecast bases in this end use are for platinum 365, 000 (1980).
551, 000 (1990) oz and for palladium 4, 300 (1980) and 7, 000 (1990) oz, obtained by relating the growth
in this sectorto the projected growth of the GNP at 4. 2 percent per annum. Increased affluence could
result in greater production of automobiles and other motorized recreation vehicles, and thus in
increased demand for gasoline. As lead is outlawed as a means of controlling antiknock characteris-
tics of gasoline and for rendering catalytic mufflers effective, platinum requirements may be sub-
stantially increased in the production of gasoline of higher octane ratings. Based on the increased
mobility, limitations on environmental pollution, and other considerations, the demand for platinum
could reach a high of 489, 000 (1980), 738, 000 (1990) oz and for palladium 6, 500 (1980) and 10, 500
(1990) oz. However, innovations in transportation such as the development of electric automobiles
or the introduction of mass transit systems would severely limit the demand for gasoline. In addition,
new techniques in petroleum refining or use of alternate materials for catalysts could reduce the
demand for platinum and palladium. These contingencies could result in a low demand for platinum
of 261,000 (1980), 394,000 (1990) oz and for palladium of 3,200 (1980) and 5,300 (1990) oz.
Glass Industry. The end use in this category was obtained by relating the growth to the GNP
at 4. 2 percent per annum, resulting in forecast bases for platinum of 59, 000 (1980), 90, 000 (1990) oz
and for palladium of 290 (1980) and 440 (1990) oz. Concern over fire hazards could lead to increased
use of fire-resistant glass fibers for carpeting and drapes by the domestic and industrial sectors.
Also, tire manufacturers may adopt increasingly the use of fiberglass for belting in tires. More-
over, if there is a drastic change in transportation, fiberglass belting may be used for conveyer-type
sidewalks. Fiberglass w. Ill probably be utilized increasingly in the production of boats, snowmobiles
and car bodies. Based on these assumptions, a high demand could result for platinum of 88,000
(1980), 135, 000 (1990) oz and for palladium of 430 (1980) and 660 (1990) oz. However, mass trans-
portation systems may greatly reduce the demand for automobiles. Manufacturers may continue to
use aluminum in boats. Moreover, natural fibers, chemically treated for fireproofing, maybe
aesthetically preferred to glass fibers. These considerations could result in a low for platinum of
54, 000 (1980), 83, 000 (1990) oz and for palladium of 270 (1980) and 400 (1990) oz.
Electrical and Electronic Industry. The forecast bases for platinum of 58, 000 (1980), 64, 000
(1990) oz and for palladium of 478, 000 (1980) and 534, 000 (1990) oz were obtained by relating the
growth in this end use to the projected growth rate of total population at 1. 125 percent annually. Due
to affluence and the growth in population, communications equipment, including telephone and tele-
vision, is expected to be in large demand. It is also likely that fuel cells which will utilize platinum
or palladium will be developed. Moreover, the reliability of platinum-group metals as electrical
components will sustain their use in aerospace applications. These contingencies could result in a
high demand for platinum of 74, 000 (1980), 82, 000 (1990) oz and for palladium of 584, 000 (1980) and
653,000 (1990) oz. Conversely, current applications, utilizing these metals may decline. For
instance, the major use of thermocouples, containing platinum, is currently in the steel industry.
The production of steel by the basic oxygen furnace requires fewer thermocouples than production by
the open hearth and the electric furnace. Demand for spark plugs with platinum contents in aircraft
engines is expected to decline due to increased use of jet propulsion. Use of other metals in alloys
for magnet materials and increased use of solid state devices for electronic switching will contribute
to a decline in demand for platinum-group metals. These contingencies could result in a low demand
for platinum of 30,000 (1980), 33,000 (1990) oz and for palladium of 212,000 (1980) and 237,000
(1990) oz.
Dental and Medical Industry. The forecast bases for platinum of 25,000 (1980), 28,000 (1990)
oz and for palladium of 69, 000 (1980) and 77, 000 (1990) oz were obtained by relating the growth in
this end use to the anticipated growth rate for total population of 1. 125 percent per annum. Affluence,
increased awareness of dental hygene and vanity considerations will probably result in increased
attention to orthodontic treatment and prosthetic dentistry. Hence, the use of the platinum-group
metals in corrective devices for straightening teeth, dental plates, and supports may result in a high
demand for platinum of 50, 000 (1980), 56, 000 (1990) oz and for palladium of 104, 000 (1980) and
116, 000 (1990) oz. Conversely, prophylaxis either through teaching or through such means as chemical
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treatment of drinking water with fluoride may decrease the need for dental plates or other prosthetic
devices. These considerations could result in a low demand for platinum of 25, 000 (1980), 28, 000
(1990) oz and for palladium of 69, 000 (1980) and 77, 000 (1990) oz.
Jewelry and Decorative Industry. The forecast bases for platinum of 21, 000 (1980), 23, 000
(1990) oz and for palladium of 21, 000 (1980) and 23, 000 (1990) oz were obtained by relating the growth
in this category to projected growth of total population at 1. 125 percent annually. On the assumption
of increased affluence and the desire for quality jewelry, the demand can be expected to reach a high for
platinum of 47, 000 (1980), 51, 000 (1990) oz and for palladium of 49, 000 (1980) and 54, 000 (1990) oz.
However, changes in style and taste may result in a low demand for platinum of 19, 000 (1980), 21, 000
(1990) oz and for palladium of 21, 000 (1980) and 23, 000 (1990) oz.
Miscellaneous Uses. These uses include such applications as laboratory ware and brazing
alloys containing the platinum-group metals. The forecast bases for platinum of 29,000 (1980),
44, 000 (1990) oz and for palladium of 38, 000 (1980) and 51, 000 (1990) oz were obtained by relating
the growth in this end use to the growth in the GNP of 4. 2 percent per annum. The forecast bases
for automobile catalysts for platinum of 774, 000 (1980), 866, 000 (1990) oz and for palladium of
332, 000 (1980) and 371, 000 (1990) oz were obtained by relating the growth in this end use to the pro-
jected growth rate of total population of 1. 125 percent per annum. The high demand may be realized
by the development of industrial anti-pollution devices and by fuels cells which may use platinum-
group metals: platinum 36, 000 (1980), 55, 000 (1990) oz and palladium 54, 000 (1980), and 81, 000
(1990) oz. The low demand in miscellaneous uses could be as the result of the substitution of alter-
nate metals. The low demand would be for platinum 24, 000 (1980), 37, 000 (1990) oz and for palladium
36, 000 (1980) and 54, 000 (1990) oz.
The low demand for catalytic mufflers in automobiles may be due to alternate catalytic
materials or due to different technical solutions to the emission problems. The low demand for
platinum would be 580, 000 (1980), 650, 000 (1990) oz and for palladium 166, 000 (1980) and 186, 000
(1990) oz respectively. The high demand could be realized, if the alternate materials and technical
solution would not be feasible. These considerations could result in a high demand for platinum of
852, 000 (1980), 953, 000 (1990) oz and for palladium of 365, 000 (1980) and 408, 000 (1990) oz.
3_. U. S. Supply and Demand Statistics
Table B-6 shows salient U. S. platinum and palladium statistics for the latest published year.
Table B-6. Salient Platinum and Palladium Statistics for 1971
Platinum Palladium
United States (18,029)
Mine production
Refinery production
New Metal 10, 198 20,951
Secondary Metal 103,420 161,099
Exports (except manufacturers) 319,642 76,471
Imports for consumption 551, 127 657,983
Stocks Dec. 31: refiner, importer, dealer 445,821 316,126
Consumption 541,164 760,106
World Production 1,823,763 1,922,979
Source: Minerals Yearbook 1971 and Southwest Research Institute
Data on mine production include production from crude platinum placers and byproduct
platinum-group metals recovered largely from domestic gold and copper ores. The product from
placer dredging operations at Goodnews Bay, Alaska assays about 64 to 76 percent platinum and
0.23 to 0.39 percent palladium. Byproduct production from copper and gold refining is mostly palladium.
U. S. exports of platinum-group metals include 79 percent platinum of a total of 404, 610 oz
for all metals. It was assumed that 18.9 percent represented palladium and 2. 1 percent minor
platinum-group metals.
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Appendix B9.7
WOR K PLAN
for
'Determine Requirements for Obtaining Baseline
Levels of Platinum and Palladium
in Human Tissue"
SwRI Project 01-3881-003
EPA Contract No. 68-02-1274
Environmental Protection Agency
Dr. Douglas L. Worf , Project Officer
Research Triangle Park, North Carolina
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Selection of Sites
Four areas are to be surveyed during this contract:
Platinum - Palladium refineries in New Jersey
. Mining area in Canada
Metropolitan Los Angeles
Rural area in Southern California
Preliminary contacts have been made with two refining companies
in the New Jersey area, and efforts are continuing to secure their
cooperation. Contacts have not been made as yet with mining companies;
however, the two primary companies in the refining industry are also
parent companies operating in the mining of platinum and palladium. The
probable site for the study will be in the Sudbury area of Ontario, Canada.
It is likely that ore concentration facilities producing platinum and palladium
concentrates in these mining areas will be the best choice for human
subjects.
Baseline studies will be conducted in metropolitan Los Angeles and
in a rural area in southern California. The exact site in the Los Angeles
basin will be selected so that a large apartment complex is available near
a heavily trafficked freeway. The Department of Health of the State of
California will be contacted for their advice regarding areas and apartment
complexes appropriate for this study.
Their assistance will also be obtained regarding the location of a
non-urban community near Los Angeles. This area should be representative
of a relatively pollution-free environment. The community should have a
hospital of some size, as the recruitment of volunteers will center on the
hospital staff members and their families. Other residents of the
community will be included if necessary for the makeup of the volunteer
group.
Selection of Subjects
All aspects regarding the use of human subjects for this study will
conform to the regulations established by the National Institutes of Health.
This protocol has been evaluated by our review committee involving human
subjects, and it has been approved for use on this study. This committee
will maintain supervision of all aspects involving human subjects.
The questionnaire has been prepared, and revisions have been made
at the request of the Sponsor. The form with supporting information has
been submitted to OMB for approval and assignment of a number. This
questionnaire will be used to select subjects and to collect information such
as age, sex, ethnic background, smoking habits, etc. on the subjects.
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Each subject that completes the sampling protocol will be paid
$25 for his or her services. The subjects will not be paid partial sums
for partial completion of the sampling program. Subjects will be free
to withdraw from the study at any time they wish, however .
The selection of subjects for the refineries and the mining
operation will be made by first securing the cooperation of the company
and then the heads of the unions operating in the plants. Through their
assistance, notices will be posted and announcements made at appropriate
meetings about the time and place of a meeting concerning this study.
Potential volunteers will be male or female, no age restrictions, must work
primarily in the plant environment and must have worked for the company
at least six months .
The procedure for selection of subjects living near a freeway in
Los Angeles will be as follows:
1. Apartment complex owners for a number of appropriate
complexes will be contacted to secure permission for soliciting paid
volunteer participants.
Z. An initial meeting with potential volunteers will be scheduled
for each complex, and the time, place and purpose of the meeting will be
advertised through notices posted and delivered individually as is
necessary.
3. At the initial meetings, the purpose of the study and
requirements for participants will be thoroughly explained, and
completed questionnaire forms will be obtained from those wishing to
volunteer.
4. Data obtained from the questionnaire forms will be used to
select an appropriate group of volunteer participants.
5. The selected volunteers will be notified by mail of the time
and place for the first sample collection.
6. Upon receipt of all required samples from a given volunteer,
payment for services, as agreed to at the outset, will be made with a
letter of thanks.
Human Subjects Living in a Non-Urban Community near Los
Angeles .
1. The administration of a hospital will be contacted to secure
permission of soliciting paid volunteer participants. More than one
hospital complex will be contacted if this seems appropriate and necessary.
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2. - 6. Same as for Los Angeles above.
7. Limiting the volunteer group to the staff and families of
the Hospital Complex may provide an insufficient number of volunteers
or an inappropriate composition of the participant group. In such a ease,
volunteers will be solicited from other sectors of the community as
appropriate, and with the help of the hospital administration, staff, and
families. Church groups and civic organizations would be considered
first. The subjects living in the non-urban area must not work in the
metropolitan area of Los Angeles.
There will be a total of 40 subjects from the two refineries in
New Jersey and 40 subjects from the mining area. As stated earlier,
these may be male or female subjects; however, it is probable that most
will be male. There will be a spread of age groups, but no selection will
be made with regard to age.
There will be 1ZO subjects in each of the two baseline studies for
a total of 240 subjects. There will be approximately 50% male and 50%
female subjects in these studies. Three age groups will be selected -
2-18, 19-50, 51 and over. There will be 40 subjects in each age group.
In the selection processes, no pretesting is planned nor will any
attempts be made for handling non-responses other than to assume that
the total response is adequate in numbers to satisfy the survey objectives.
Collection of Samples
The following samples will be collected for this study:
1. Biological samples
a. Up to ten autopsy cases from each of the five sites.
b. Human subjects - a total of 320. From each subject
two samples each of the following will be collected;
Hair
Urine
Blood
Feces
2. Air Samples
Approximately fifteen air samples from each site.
Sampling will include both ambient and "inside-paint" air.
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3. Soil Samples
Ten soil samples will be collected from each site.
4. Water Samples
Ten water samples (if available) will be collected at
each site from ponds, lakes, reservoirs, etc.
Collection of Biological Samples
A short meeting will be held with the subjects before the sampling
period commences. Specific instructions will be given to each participant
as to the procedures to be used in the collection of blood, urine, feces
and hair. Each volunteer subject will be informed of all the details of
sample collection and the overall objectives of the project. Ample
opportunity will be given for each subject to ask questions about the project.
Once the subject has been fully informed, he will be asked to sign an
informed consent form. A copy of a form which has been used previously
is attached. The form will also be signed by two witnesses, and then the
original will be filed at SwEI in the office of the Principal Investigator.
Access to the names of these volunteers will be limited to the Principal
Investigator and his project staff.
Sample collection containers for urine and feces will be handed out
at this time. The urine samples will be overnight specimens. Collection
of urine is to begin after supper (generally between 6 and 10 PM) and is to
continue until 8 AM the next morning. The sample containers will be
labeled, wide-mouth, polyethylene, one-half gallon bottles that have been
pre-rinsed with deionized water. Sample containers for fecal specimens
will be labeled, wide-mouth, polymethylpentene, 250-ml jars that have
also been pre-rinsed. Total feces collection will also cover the same time
period as does the urine, i.e., an overnight specimens from after supper
to the following morning. The subjects will be cautioned against putting
anything into these separate containers other than urine and feces,
respectively. It will be emphasized to the subjects that the total urine and
fecal, output for this time period is needed for the proper conduct of this
project.
The following morning, the subjects will bring their specimens to
the survey team for processing. Upon arrival at the survey point, the feces
containers will be placed in dry ice and the urine containers placed in wet
ice. Approximately 20 ml of blood will then be collected from each
individual except children under the age of four from which only 10 ml will
be withdrawn. Blood will generally be collected between 5 and 7 PM. A
B-D vacutainer, low-lead content (0.5 micrograms or less) containing
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sodium heparin as an anticoagulant will be used. The collection of
blood samples will be conducted by a clinical laboratory technician under
the supervision of a physician. The blood samples will be placed on wet
ice. Blood from refinery and mining workers will be collected at the
end of their work shift.
Hair samples of uniform length and at least Z or 3 grams per
sample will be taken from the nape of the neck by a barber at the survey
collection area. If the individual plans to have a regular haircut during
the sampling period, he will be instructed to have his barber collect only
his hair in the bags provided. All hair samples will be placed in labeled
"zip-lok" polyethylene bags. The intent of this project is to collect all
samples, i.e. blood, urine, hair and feces, from the subjects for the
same time period.
After all the samples are collected for a particular day,
processing and preparation for shipment will take place. Approximately
a 150-ml aliquot of thoroughly mixed urine will be placed into a poly-
ethylene container and made to 1% acetic acid and then frozen. The weight
of the feces specimen will be recorded and the sample returned to the dry
ice. Whole blood will be transferred from the vacutainer used in collection
to a pre-rinsed 1-ounce polyethylene bottle and then frozen. A selected number
of random bloods from the refinery and mining subjects will be divided so
that approximately 10-ml is frozen as whole blood and the remaining
portion centrifuged and separated into plasma and red blood cells with each
portion frozen separately. All samples will then be shipped to the SwRI
laboratories and kept frozen, with the exception of hair specimens, until
analysis can be performed.
After the subjects bring their urine and fecal specimens to the
survey collection point and blood is drawn, it is estimated that the samples
will be kept on wet ice for no more than three hours before they are
processed and frozen for shipment to the San Antonio laboratories.
All samples will be analyzed within 60 days after collection or they
will be processed to a digest and stored in this state until analyzed.
Collection of Air Samples
Sampling of air in the refineries will be accomplished using a
precalibrated Bendix Hurricane air sampler. This air sampler is capable
of maintaining an air flow of 120 cfm with an 8" x 10" glass fiber filter
attached to collect the metals. This high volume sampler will be used to
monitor the air in the refineries covering the workday of the subjects
(8-hour samples). At the end of the 8-hour collection period, the glass
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fiber filter will be removed with a pre-rinsed pair of Teflon-coated
tweezers to preclude extraneous contamination and the filter placed in a
labeled pre-rinsed "zip-lok" polyethylene bag. The air sampling period
will continue for a total of 5 days for each refinery.
Because of the proprietary nature of the work areas in the
refineries, it is probable that SwRI personnel will be prevented from
personally placing the high volume air samplers in the work areas. In
the event that such a situation occurs, specific instructions on the operation
and placement of the air samplers will be given to the shop foreman or
another suitably responsible person so that these individuals can place the
air samplers in the work areas. In addition to the high volume air samplers
placed in the refineries, Bendix Micronair personal air samples will be
given to individuals working in the plant. With a lapel-attached holder and
glass fiber filter, the individual will be instructed to collect continuous air
samples in his work area, but turn off the pump and cover the filter when
he leaves the work area. At the end of the working day, the filter will be
carefully removed from the holder and placed in a pre-rinsed "zip-lok"
polyethylene bag.
The sampling of ambient air around mining operations will be based
on the wind rose pattern with the majority of samples taken downwind.
The sampling period will be for 24 hours and the samplers placed at ground
level. Air samples will also be taken around the source of high
concentration of metals such as the work area where the ore is concentrated.
High volume (120 cfm) samplers will be used to accomplish this task.
Assuming that proprietary information is also involved in the concentration
work area, the problem of SwRI personnel placing the equipment in this
area will again be solved by soliciting the help of the shop foreman or
another responsible person in placement of the air samplers.
The baseline study of the free living population will entail the use
of outdoor high volume samplers to collect ambient air samples. The
placement of the samplers will be near apartment complexes where the
subjects live. Sampling of ambient air will be at ground level with 24 hours
being the period for each sampling. As stated previously, all filters will
be handled in the most efficient manner to preclude possible contamination
of the sample .
Collection of Soil Samples
Approximately 100 g of soil will be taken for each sample around the
refineries, mine and apartment complexes. Sampling points will be
determined by the windrose pattern around each site. Samples will be
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placed in pre-rinsed polyethylene containers and shipped to the San
Antonio laboratories. Some upwind samples will be taken. It is likely
that the samples from the refineries and the mining operations will be
collected within 200 meters of the work areas.
Collection of Water Samples
If suitable ponds, rivers, etc. are within a one-km radius of the
site to be studied, then water samples will be collected from them. Grab
samples of water will be collected from ponds or lakes at different depths
and locations around the body of water. Water samples from a flowing
stream will be collected using a composite sampler which will provide a
flow averaged sample over a period of time.
The water samples will be placed into clean polyethylene containers
and frozen until analyzed.
Analysis of Samples
The following analytical methodologies are proposed based on
limited laboratory investigations. It may be necessary to modify these
procedures once an evaluation of each method has been completed.
All analytical work will be performed on a Perkin-Elmer Model 306
Atomic Absorption Spectrophotometer using a Perkin-Elmer HGA-2000
Graphite Furnace.
Biological Samples
Preparation of these samples (blood, urine, tissues, etc.) will
follow one of two schemes depending upon which metals are to be
determined: Scheme number one will include the analysis of platinum,
palladium and lead. Scheme number two includes the analysis of only
platinum and palladium.
It is necessary to have alternate methods of preparing the biological
samples, depending upon the analyte metals to be determined. There is
a wide variance in the volatility of lead and platinum, and this directly
affects the speed and accuracy with which these samples may be prepared
for analysis.
Also included in the sample preparation methodologies will be
methods used on a limited number of samples to better define the chemical
form and/or location of the analyte species (e.g. the analysis of RBC's
or the leaching of soil).
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Blood
\ . Whole Blood
a. Platinum, Palladium and Lead
A 10-ml aliquot of whole blood is freeze-dried and then
ashed in a low temperature asher. The ash is then solubilized with
HC1 (0.5M) using a hot-plate on low heat (70°C). Once the ash has been
completely solubilized, it is allowed to cool and is then filtered through
a glass-fiber filter (acid-washed with 0.1 M HCl). The filter is rinsed
three times with HCl (0.5M), and the filtrate is collected in a 10-ml
volumetric flask. Deionized water is used to make up the volume to 10ml.
Five milliliters of the sample solution is transferred to
an extraction vessel, and the molar concentration of HCl is adjusted to
approximately 1.5M. Then 0.25 ml of stannous (II) chloride solution
(35% in 3M HCl) is added and vigorously shaken for 30 seconds. Immediately,
0.5 ml of 0.2M tri-n-octylamine (in benzene) is added and shaken for one
minute. The aqueous and organic phases are allowed to separate, and
the organic phase is removed and stored in a screw-cap vial at 4°C until
ready to analyze for platinum and palladium.
The remaining 5ml of sample solution is used for lead
analysis. The pH is adjusted to 7 with IN NaOH and 1 ml of tris(hydroxymethyl)
aminomethane buffer added. The solution is shaken vigorously to ensure
complete mixing. AU of the samples are pipetted into an extraction vessel and
0.25 ml of sodium diethyldithiocarbamate solution (1%) added. The solution
is shaken for 30 seconds. The lead complex is extracted by adding 2.5ml
of methyl isobutyl ketone (MIBK), shaking vigorously and centrifuging
10 minutes at 3300 RPM. The organic layer is removed from the aqueous
layer and stored in a screw-cap vial (at 4°C) until ready for lead analysis.
b. Platinum and Palladium
A 10-ml aliquot of whole blood is wet ashed in a Vycor
beaker with 15 ml of HNC>3: HC1O4 (70:30) mixture on a hot plate at 100°C.
A stream of nitrogen is used to help evaporate the digested blood to near
dryness. The sample is reconstituted with 5ml of HCl (0.5M) and again
evaporated to near dryness. This evaporation and reconstitution process
is repeated three times, and on the final reconstitution, the sample is
removed from the hot plate and allowed to cool. The digested sample is
then filtered through a glass-fiber filter and the filtrate collected in a
10-ml volumetric flask. Deionized water and concentrated HCl are used
to adjust the molar concentration of HCl in the sample to 1.5M and to
adjust the volume to 10ml. The sample is then transferred to an extraction
vessel and 0.5 ml of stannous (II) chloride solution (35% in 3M HCl) added.
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The trichloro complexes of platinum and palladium are immediately
extracted with 1ml of 0.2M tri-n-octylamine (benzene solution).
The extract is analyzed by the graphite furnace technique.
2. Solid Fraction (RBC's)
a. Platinum, Palladium and Lead
A 10-ml aliquot of whole blood is centrifuged at 2500 RPM
for 20 minutes to separate the plasma from the red blood cells (RBC).
The plasma is decanted from the tube, and the RBC's are rinsed twice
with deionized water. The RGB's are then placed in the low temperature
asher. The resulting ash is treated and analyzed by the same procedure
outlined for whole blood -- platinum, palladium and lead analysis.
b. Platinum and palladium
A 10-ml aliquot of whole blood is centrifuged for 20
minutes at 2500 RPM. The plasma is decanted off and RBC's washed
twice with deionized water. The RBC's are then digested, extracted and
analyzed by the same procedure used for whole blood -- platinum and
palladium analysis.
Urine
1. Platinum, Palladium and Lead
A 10-ml aliquot of acidified urine is freeze-dried then
ashed in a low temperature asher. The ash is dissolved in HC1 (0.5M)
using a hot-plate on low heat (70°C). The dissolved ash is then transferred
to a 10-ml volumetric flask. The flask is made to volume with deionized
water and mixed well. A 5-ml aliquot is taken for platinum and palladium
analysis.
The 5-ml aliquot is placed in an extraction vessel, and the
molar concentration of HC1 is adjusted to approximately 1, 5M with
concentrated HC1. Then 0.25 ml of stannous (II) chloride solution (35% in
3M HC1) is added, and the sample is shaken vigorously for 30 seconds.
One-half milliliter of 0.2M tri-n-octylamine (in benzene) is added and
shaken for 1 minute. The aqueous and organic layers are allowed to
separate, and the organic layer is removed and stored in a screw-cap vial
at 4°C until ready for platinum and palladium analysis.
The other 5-ml aliquot of solubilized sample is used for lead
analysis. The 5 ml solution is transferred to an extraction evssel and the
pH adjusted to 7 with IN NaOH solution. One ml of tris(hydroxymethyl)
aminomethane buffer is added and mixed well. All of the samples are
transferred to an extraction vessel, and 0.25ml of sodium diethyldithio-
carbamate solution (1%) is added and the sample is vigorously shaken for
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30 seconds. 2.5ml of MIBK is added, and the sample is again vigorously
shaken for 1 minute and then centrifuged for 10 minutes at 3300 RPM.
The organic layer is removed and stored in a glass vial with a screw-cap
until ready for lead analysis by the graphite furnace.
2. Platinum and Palladium
A 10-ml aliquot of urine is wet-ashed with 15 ml of
HNO3:HC1O4 (70:30) in a Vycor beaker on a hot plate at 100° C. The digested
urine is evaporated to near dryness with the aid of a nitrogen stream.
The sample is reconstituted with 5 ml of HC1 (0.5 M), and the evaporation-
re constitution process is repeated twice more. Following the last
reconstitution, the sample is allowed to cool to room temperature and is
then filtered through a glass-fiber filter. The filtrate is collected in a
10-ml volumetric flask. Concentrated HC1 and deionized water are used
to adjust the volume to 10 ml and the concentration to 1.5 M HC1. The
sample is then placed in an extraction vessel, 0.5 ml of stannous (II)
chloride solution (35% in 3 M HC1) added and mixed well. One ml of a
0. 2M tri-n-octylamine (benzene) solution is added immediately to the
sample to extract the trichloro complexes of platinum and palladium.
The extract is placed in a screw-cap vial at 4°C until ready for analysis.
Feces
1. Homogenization
The total fecal sample is homogenized in a tissue grinder
with a Teflon-coated pestle. A small amount of deionized water may be
used to aid in the homogenization if the sample is relatively dry.
2. Platinum, Palladium and Lead
A 5-gram aliquot of the homogenized sample is weighed into
a Pyrex dish, freeze-dried, and then placed in a low temperature asher.
The ashed sample is solubilized with HC1 (0.5M) and transferred to a 10-ml
volumetric flask. Deionized water is used to adjust the volume to 10 ml.
Five milliliters of the ashed sample is placed in an extraction
vessel and extracted with i ml of 0.2M tri-n-octylamine (in benzene)
solution by the same procedure used for blood and urine.
The remaining 5 ml of ashed sample is extracted with sodium
diethyldithiocarbamate and MIBK using the same procedure that was used
for lead analysis of blood and urine.
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3 . Platinum and Palladium
A 5-gram aliquot of homogenized feces is weighed into a
Vycor beaker and 15 ml of HNO3: HC1O4 (70:30) added. The beaker is
covered with a watch glass and allowed to stand at room temperature for
15 to 20 minutes. It is then placed on a hot plate (100°C) and a stream of
nitrogen added. The feces is digested/evaporated until only 1 or 2 ml of
solution remains. The sample is reconstituted with 5ml of HC1 (0.5M), and
the evaporation-reconstitution process is repeated twice more. Following
the last reconstitution, the sample is allowed to cool to room temperature
and is then filtered through a glass-fiber filter (prewashed with 0.1M HC1).
The filtrate is collected in a 10 mi-volumetric flask. Concentrated HC1
and deionized water are used to adjust the volume to 10 ml and the
concentration ot 1.5M HC1. The sample is then extracted with 0.2M-tri-
n-octylamine (in benzene) after the formation of the tinchloro complexes
of platinum and palladium. The same procedure used for blood and urine
is followed.
Hair
1. Washing Procedure
The complete hair sample is placed in a 250-ml Erlenmeyer
flask and 200 ml of a sodium lauryl sulfate solution (0.12 g/1) is added.
The sample is then placed on a mechanical shaker for 1 hour. The solution
is then decanted off, and the hair is rinsed twice with deionized water.
Following the last rinsing, the hair is transferred to a fritted glass filter.
Another deionized water rinsing, followed by a 100 ml of 95% ethanol wash,
is carried out. The sample is vacuum filtered and then placed in an oven
(65°C) to dry. The dry hair is then ready for the following procedures.
2. Platinum, Palladium and Lead
A 1- to 3-gram sample of the washed and dried hair is weighed
into a Pyrex dish and placed in a low temperature asher. Theashed hair
is taken up with HC1 (0.5M) and transferred to a 10-ml volumetric flask .
A 5-ml aliquot of the ashed hair sample is transferred to an
extraction vessel, and the molar concentration of HC1 is adjusted to 1.5M.
The sample is then extracted by the same procedure used for blood and
urine, platinum and palladium analysis.
The remaining solution is used for lead analysis, following
the extraction procedure given for blood and urine using the chelating/
extraction system of sodium diethyldithiocarbamate/MIBK .
264
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3. Platinum and Palladium
A 1- to 3-gram sample of the washed and dried hair is
weighed into a Vycor beaker and 10 ml of HNC>3: HC1C>4 (50:50) added.
The sample is placed on a hot plate (100° C) and a stream of nitrogen
added to aid in the evaporation. The sample is digested and evaporated
to near dryness and then reconstituted with 5 ml of HC1 (0.5M). This
evaporation procedure is repeated twice more, and finally the sample is
removed from the hot plate after the last 5-ml reconstitution with HC1.
Concentrated HC1 and deionized water are used to adjust the volume to
10 ml and the concentration to 1.5 M HC1.
An aliquot of this solution is complexed with stannous (II)
chloride and extracted with 0.2M tri-n-octylamine using the same
procedure given for blood and urine. The extract is analyzed by the
graphite furnace for platinum and palladium.
Tissues
1. Platinum, Palladium and Lead
A 1- to 5-gram portion of the tissue sample is weighed into
a Pyrex dish and placed in a low temperature asher. Once the sample is
completely ashed, it is dissolved in HC1 (0.5M) and filtered through a
glass-fiber filter (prewashed with 0.1M HC1). The filtrate is collected
in a 10-ml volumetric flask, and the filter is rinsed twice with 0.5M HC1.
Deionized water is used to fill . the volumetric flask to the mark.
A 5-ml aliquot of the ashed sample is transferred to an
extraction vessel, and the tinchloro complexes of platinum and palladium
are extracted with 0.2M tri-n-octylamine (benzene) solution after the molar
concentration of HC1 is adjusted to 1.5M. The procedure is the same used
for blood and urine.
An aliquot of the remaining solution is used for lead analysis
following the sodium diethyldithiocarbamate/MIBK extraction used for blood
and urine lead.
2. Platinum and Palladium
A 1- to 5-gram weight of the tissue sample is placed in a
Vycor beaker and 10 ml of HNO.,: HC1O, (50:50) added. The sample is
allowed to digest at room temperature for 15 to 20 minutes . It is then
placed on a hot plate (100° C) and a stream of nitrogen added. The sample
is evaporated to near dryness and reconstituted with 5 ml of HC1 (0.5M).
265
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This evaporation process is repeated twice before the sample is
removed from the hot plate and the last 5 ml reconstitute HC1 is allowed
to cool. The sample is then filtered through a glass fiber filter
(prewashed with 0.1 M HC1) and the filtrate is collected in a 10 ml
volumetric flask. The molar concentration of HC1 is adjusted to 1.5M
with cone. HC1 and the flask is filled to the mark with deionized water.
The sample is then extracted with 0. ZMtri-n-octylamine
(benzene) solution using the same procedure used for blood and urine
extraction. The extract is then analyzed by the graphite furnace.
Air Samples
The primary method for the air filter samples will be a
leaching procedure. A limited number of samples will be digested
completely with only platinum and palladium being determined.
1. Leaching - Platinum, Palladium and Lead
The glass-fiber air filter is cut into 1-cm strips using
stainless steel scissors and placed in a 250-ml Erlenmeyer flask. 50 ml
of leaching acid (1M HC1) is added, and the flask is placed in a shaking-
water bath (70°C) for 4 hours. The leach solution is then decanted from
the flask into a small beaker. The filter is rinsed several times with
1M HC1, and the rinsings are added to the beaker. The beaker is placed
on a hot plate ('90-100°C) and a stream of nitrogen added to aid in the
evaporation. The solution is evaporated to several milliliters and
transferred to a 10-ml volumetric flask which is q.s. to the mark with
deionized water.
A 5-ml aliquot of the sample is placed in an extraction vessel,
and the molar concentration of HC1 is adjusted to 1.5M. Then 0.5 ml of
stannous (II) chloride solution (35% in 3M HC1) is added, immediately
followed by 0.5 ml of 0.2M tri-n-octylamine (in benzene) solution. The
solution is centrifuged for 10 minutes at 2500 RPM to separate the aqueous
and organic phases. The organic layer is removed and placed in a.
screw-cap vial and stored at 4°C until ready for platinum and palladium
analyses by the graphite furnace.
An aliquot of the remaining sample is placed in an extraction
vessel, and its pH is adjusted to 7 with sodium hydroxide. Then 0.5 ml of
tris(hydroxymethyl) aminomethane buffer solution is added. Next, 0.25ml
of sodium diethyldithiocarbamate solution (1%) is pipetted into the vessel,
and the sample is shaken for 1 minute. One ml of MIBK is added and the
sample is shaken vigorously for 1 minute. The solution is centrifuged for
15 minutes at 3300 RPM to separate the aqueous and organic phases. The
MIBK is removed and stored in a screw-cap vial at 4°C until ready for
lead analysis .
266
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2. Total Digest - Platinum and Palladium
The glass-fiber filter is cut into 1-cm strips as before
and placed in a Teflon beaker. Fifty milliliters of aqua regia is added,
and the beaker is placed on a hot plate (100°C). After approximately
30 minutes, 5 ml of hydrofluoric acid (48%) is added and heating on the
hot plate is continued until the sample has been digested. A stream of
nitrogen is added to aid the evaporation of the solution. Once the sample
has been evaporated to 1-2 ml, it is reconstituted with 5 ml of concentrated
HC1. The evaporation process is repeated twice more, and after the last
evaporation the sample is removed from the hot plate and allowed to cool.
The remaining 1 or 2 ml is transferred to a 10-ml volumetric flask and
q.s. to the mark with deionized water. The sample is then transferred
to an extraction vessel and 0.5 ml of stannous (II) chloride solution
(35% in 3M HC1) is added. Immediately, 1 ml of 0.2M tri-n-octylamine
(in benzene) solution is added and the sample shaken for 1 minute. The
sample is centrifuged at 2500 RPM for 10 minutes, and the organic layer
is removed for platinum and palladium analyses.
Water Samples
Water samples will be processed by the same procedure outlined
for urine except there will be no digestion step. The samples will be made
1.5M in HC1 for the tri-n-octylamine extraction of platinum and palladium.
Another sample aliquot will be adjusted to pH 7, buffered, and extracted
with sodium diethyldithiocarbamate/MIBK for the analysis of lead.
Soil Samples
1. Leaching - Platinum, Palladium and Lead
A 2-gram sample of soil is placed in a 250-ml Erlenmeyer
flask, and 20 ml of leaching solution (a 3:7 mixture of 25% hydroxylamine
hydrochloride and 35% acetic acid) is added. The flask is stoppered with
a polyethylene stopper and placed on a mechanical shaker overnight
(18 hours). The solution is filtered through a glass-fiber filter (prewashed
with 0.1M HC1) and the flask is rinsed three times with 10ml of leaching
solution. The filtrate is collected in a small beaker and evaporated on a hot
plate (90-95°C) to near dryness. The sample is reconstituted with 5ml of
0. 5M HC1, and the evaporation process is repeated twice more. After the
last 5 ml of HC1 is added, the beaker is removed from the hot plate and
allowed to cool to room temperature. The solution is transferred to a 10-ml
volumetric flask with rinsings of 0.5M HC1 and filled to the mark with
deionized water.
267
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A 5-ml aliquot of the sample is taken and the molar
concentration of HC1 adjusted to 1.5M with concentrated HC1. One-half
ml of stannous (II) chloride solution (35% in 3M HC1) is added,
immediately followed by 0.5ml of 0.2M tri-n-octylamine solution
(in benzene). The sample is vigorously shaken for 1 minute and the
benzene layer removed. The extract is placed in a screw-cap vial and
stored at 4°C until ready to analyze for platinum and palladium.
Using another 1 ml aliquot of the sample, the pH is adjusted
to 7 with IN NaOH solution and 1 ml of tris(hydroxymethyl) aminomethane
buffer (pH 7) solution added. One-quarter ml of sodium diethyldithiocarbamate
solution (1%) is pipetted into the solution, and the sample is shaken well. Then
pipet 1ml of MIBK into the solution and again shake vigorously for 1 minute.
The sample is centrifuged for 10 minutes at 3300 RPM to separate the layers.
The organic layer is removed and stored in a screw-cap vial at 4°C until
ready for lead analysis.
2. Total Digestion - Platinum and Palladium
A 2-gram soil sample is placed in a 250-ml Teflon beaker
and 25 ml of HNO~ : HC1 (10:30) added. The beaker is placed on a hot plate
at 150-175 °C. After digesting for 10 to 15 minutes, 10 ml of hydrofluoric
acid (48%) is adde^1, very carefully, and heating is continued. A stream of
nitrogen is added to aid in the evaporation of the solution to near dryness.
Once the solution has been evaporated to 1 or 2 ml, 5ml of HC1 (0.5M) is
added, and the evaporation process is repeated twice more. After the last
reconstitution with HC1, the sample is removed from the hot plate and
allowed to cool. The sample is filtered through a glass-fiber filter
(prewashed with 0.1M HC1) and the filtrate collected in a 10-ml volumetric
flask. Concentrated HC1 and deionized water are used to adjust the volume
to 10-ml and the concentration to 1.5M HC1.
The solution is transferred to an extraction vessel and 0.5ml
of stannous (II) chloride solution (35% in 3M HC1) added. Immediately,
1 ml of 0. 2M tri-n-octylamine (in benzene) solution is added. The sample is shaken
vigorously for 1 minute, then centrifuged for 10 minutes at 2500 RPM.
The organic layer is removed and stored in a screw-cap vial at 4°C until
ready for platinum and palladium analysis.
Evaluation of Data
It is planned that questionnaire and human subject sample data will
be collected at two platinum and palladium refineries and at one mine for
the study of current platinum and palladium exposure and at two sites, one
urban and one rural, for the baseline studies. Air sampler data will also
be gathered from two or three locations scattered about each site.
268
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Formats for the human subject and air sample data will be developed
to coincide with the questionnaire format. The following data will be
coded and keypunched:
Study of Current Exposure
Platinum, Palladium and Lead Questionnaire . Select
at least 20 workers at each of two refineries and 40
miners at one mine as volunteers.
Human Subject Samples. Collect two sets of samples
during the same week from each volunteer worker.
For each sample set, code the questionnaire ID number
of the worker, the date of sample, site, comparable
air sampler, and the platinum and palladium
concentrations in the blood, urine, feces, and hair.
Air Samples. Collect 8-hour air samples daily for
five days from at least one location within each plant
situated near the human subject volunteers' work areas.
If the plant has dissimilar working environments, locate
one rampler in each such area. Code the air sampler
number, site, date, and platinum and palladium air
concentrations.
Baseline Study
Platinum, Palladium and Lead Questionnaire. From
the interviews, select 120 residents of an apartment
complex near a Los Angeles freeway and 120 residents of
a clean non-urban area in California. Each sample of
120 residents would be composed of three age groups of
40 individuals each, with equal male and female
representation.
Human Subject Samples. Collect two sets of samples
from each resident volunteer during the same week. For
each sample set, code the questionnaire ID number of the
resident, the date of sample, site comparable air sampler,
and the platinum, palladium, and lead concentration
in the blood, urine, feces, and hair.
Air Samples. Collect 24-hour air samples daily for
fourteen days near the human subject volunteers residences.
Code the air sampler number, date, and platinum, palladium,
and lead air concentrations .
269
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The current exposure study is exploratory in nature. Its
purposes are to identify which tissues are the best indicators of various
facets of the body burden of platinum and palladium, to examine the
distribution of body burden variables in an exposed population, to
establish the relationship between air concentration and body burden for
platinum and palladium, to determine the relative absorption of the
soluble versus the insoluble forms of platinum and palladium, and to
identify which human variable factors appear to have an effect on the body
burden. Insights from related EPA toxicological projects in progress
will be utilized as appropriate. There are no systematic data on the
distribution of platinum and palladium levels within an exposed population.
Hence, it is often premature to specify which statistical procedures will
be used to draw inferences, because many procedures are not very robust
to departures from underlying distributional assumptions. When
statistical techniques are specified below, it is anticipated that they will
be suitable. However, the actual techniques used will be dictated by
the nature of the data obtained.
Analysis of the refinery data will meet most of the current
exposure study objectives. A tissue comparison analysis will be conducted
on the urine, blood, feces, and hair tissue data for platinum and palladium.
The tissue comparison will attempt to identify the tissues that are the best
indicators of various body burden aspects, such as chronic inhalation,
recent acute inhalation, and recent ingestion. For example, the best
chronic inhalation indicator will be the tissue meeting the dual criteria of
a high mean concentration level over all refinery workers and minimal
variance on the two samples collected from each worker. The tissue(s)
found to be the best indicator of each platinum and palladium body burden
aspect will be treated as the primary dependent variable in the subsequent
analyses of that aspect. Based on a volunterr's job and his work area, his
human subject samples will be identified with the air sampler at the refinery
in the most comparable situation. Then the relationship of air concentration
on body burden will be examined via histograms for the workers identified
with each air sampler and by a plot of the body burden mean for each air
sampler as a function of the mean air sampler concentration. The effect of
human variables, such as age, length of refinery employment, cigarette
smoking, sex, ethnic origin, and hair color, on the appropriate body burden
variable will be assessed using pertinent techniques, such as t-tests, one
factor analysis of variance, or correlation. Through this process, the
major covariates will be identified. If asthma and allergies, the health
effects linked to high platinum body burdens, are prevalent amont the
refinery worker volunteers, an effort will be made to correlate these and
other health variables with the body burdens of platinum and palladium.
Some soil samples from locations within and around each refinery
will also be analyzed for their platinum and palladium concentrations.
These soil sample concentration means may be useful in quantifying the
long term refinery site effect. These means might thus be used to
characterize each refinery and to explain site and employment effects, should
they prove to be significant.
270
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Two air samplers will be set up around the refinery on each
of the five days of the study at different distances from the refinery
in order to sample throughout the plant's working hours.
Analysis of the mine data will be directed toward the solubility
question. Nearly all the airborne platinum and palladium produced by a
refinery is expected to be in the soluble form which apparently can be
absorbed by the human body by inhalation, contact, and ingestion. Much
of the airborne platinum and palladium in a metal mine is expected to be
in the insoluble form. Thus, a comparison of the body burden of refinery
workers at a given airborne concentration against that of mine workers
exposed to the same concentration, but primarily in the insoluble form,
should confirm or reject the solubility hypothesis. Histograms and plots
would again be used to examine the dependence of body burden on air
sampler concentration. Comparison of the body burdens for refinery and
mine workers exposed to the same platinum/palladium concentration
would be made from their respective plots to detect any substantial
difference. If a difference is detectable, suitable tests would be devised
to determine whether it is a significant difference.
The main purpose of the baseline study is to provide baseline
body burden data for later platinum and palladium studies. After widespread
usage of platinum and palladium converters on automotive exhaust systems
begins, the exposure of the general population to airborne platinum and
palladium may increase dramatically. Hence, a summarization of the
baseline body burden data, giving the mean and standard deviation of each
tissue variable overall, by site, by age group within site and by sex within
site and age group, will be very useful. This summarization should suffice
to characterize the current body burdens of platinum, palladium, and lead
for the upper and lower extremities of exposure in the U.S. population.
Air (plant and ambient) platinum, palladium, and lead concentrations will
also be summarized overall and by site. The effect of human and
residential factors, such as age, sex, ethnic origin, smoking history, site,
air sampler concentration, air conditioning, and length of residence on the
body burdens of lead will also be assessed. If sizable platinum and
palladium body burdens are detected, these analyses will also be performed
for platinum and palladium. The effect of the more important factors,
anticipated to be site, age group, and air conditioning, will be studied,
independently and with nesting, by analysis of variance. The effect of the
other factors will be determined by simpler techniques, such as t-tests.
The computing required to perform the statistical tasks discussed
above will be performed on a CDC CYBER 74 computer system accessible
via teleprocessing from the Southwest Research Institute's Computer
Laboratory. Whenever possible, the BMD statistical package will be utilized.
However, computer programs will be written as necessary to perform
specialized tasks not available in the BMD package.
271
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I HI.PIIR i
EPA-600/3-75-010J
1. RECIPII-.MTT. ACCESSION NO.
.1. TITIE ANDSUOTITLE
ANNUAL CATALYST RESEARCH PROGRAM REPORT
Appendices, Volume IX
5. RCPOHT DATE
September 1975
G. PERFORMING ORGANIZATION CODE
7. AUTHORIS)
Criteria and Special Studies Office
0. PE/lfORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Health Effects Research Laboratory
Office of Research & Development
U.S. Environmental Protection Agency
Research Triangle Park, N.C. 27711
I?. SPONSORING AGENCY NAME AND ADDRESS
Same as above
1O. PROGRAM ELEMENT NO.
1AA002
11. CONTRACT/GRANT NO.
13. TYPE Of REPORT AND PERIOD COVERED
Annual Program Status 1/74-9/7
14. SPONSORING AGENCY CODE
EPA-ORD
1!>. SUPPLEMENTARY NOTES
This is the Summary Report of a set (9 volumes plus Summary).
See EPA-600/3-75-010a through 01 Oi. Report to Congress.
16. AOSTRACT
This report constitutes the first Annual Report of the ORU Catalyst Research
Program required by the Administrator as noted in his testimony before the
Senate Public Works Committee on November 6, 1973. It includes all research
aspects of this broad multi-disciplinary program including: emissions charac-
terization, measurement method development, monitoring, fuels analysis,
toxicology, biology, epidemiology, human studies, and unregulated emissions
control options. Principal focus is upon catalyst-generated sulfuric acid
and noble metal particulate emissions.
7. KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
t
Catalytic converters
Sulfuric' acid
Uesulfurization
Catalysts
Sul fates
Sulfur
Health
. UIT, r miiurioN STATEMENT
Available to public
(•.IDENTIFIERS/OPEN LNDED TERMS
Automotive emissions
Unregulated automotive
emissions
Health effects (public)
t
10. SECURITY CLASS f 1 '•« Hrportl
Unclassified
20. grcuwtV CLASS (n,,, /»,«•/
Unclassified
C. COSATI 1 lclll/('KMl|>
21. NO. OF PAGES
22. PRICE
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