EPA 560/6-77-032
MULTIMEDIA LEVELS
CADMIUM
PRO
SEPTEMBER 1977
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
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EPA-560/6-77-032
MULTIMEDIA LEVELS
CADMIUM
September 1977
BATTELLE
Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
Vincent J. DeCarlo
Project Officer
Contract No. 68-01-1983
ENVIRONMENTAL PROTECTION AGENCY
OFFICE OF TOXIC SUBSTANCES
WASHINGTON, D.C. 20460
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NOTICE
This report has been reviewed by the Office of
Toxic Substances, Environmental Protection Agency, and
approved for publication. Approval does not signify
that the contents necessarily reflect the views and
policies of the Environmental Protection Agency.
Mention of tradenames or commercial products is for
purposes of clarity only and does not constitute
endorsement or recommendation for use.
ii
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PREFACE
This review of the environmental levels of cadmium was conducted
for the U.S. Environmental Protection Agency, Office of Toxic Substances,
under Contract Number 68-01-1983. It involved (1) the review and
evaluation of existing monitoring data and (2) development of an inte-
grated data package. Information sources were identified from computerized
and manual searches. Data were obtained from specialized data centers;
university programs; federal programs; state programs; the Smithsonian
Science Information Exchange; EPA's Storet, SAROAD, and NASN data centers;
the USGS, and Fish and Wildlife Service; and from readily available open
literature.
Information gathered included cadmium concentrations in air,
surface and drinking water, groundwater, soil, food, sediment, sludge,
aquatic and terrestrial organisms, human tissues, and body fluids.
Details were obtained on the methods of sample collection, interferences,
meteorological data, and analytical methods employed.
iii and iv
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TABLE OF CONTENTS
1. INTRODUCTION 1-1
Physical and Chemical Properties 1-1
Production and Uses of Cadmium 1-1
Sources of Environmental Contamination with Cadmium .... 1-4
2. CADMIUM LEVELS IN THE ENVIRONMENT 2-1
Air 2-1
Water and Sediment 2-16
Drinking Water 2-26
Sludge 2-28
Rocks and Soils 2-36
Terrestrial Biota 2-42
Aquatic Biota 2-58
3. CADMIUM BEHAVIOR IN THE ENVIRONMENT 3-1
Air Transport 3-3
Soil Transport 3-4
Water Transport 3-8
Sediment Transport 3-12
Food Chain Transport 3-12
4. CADMIUM IN FOODS 4-1
Sources of Food Contamination 4-1
Cigarettes 4-2
Foods 4-2
5. EXPOSURE AND BIOACCUMULATION IN MAN 5-1
Distribution of Cadmium 5-1
Body Burden 5-2
Excretion of Cadmium 5-12
Biological Half-Life 5-19
6. REFERENCES 6-1
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.FIGURES
Number Page
1.1 U.S. cadmium consumption in 1975 1-3
1.2 Projectd cadmium consumption in the United States by end
use, year 2000 1-5
1.3 Geographical distribution of recoverable zinc resources
in the United States 1-6
1.4 Cadmium consumption (percent) by state* * . . i . 1-7
1.5 Geographical distribution of independent job platers by
EPA region (percent) 1-9
2.1 Map showing NASN stations for measuring cadmium 2-2
2.2 Trends in 50th percentile of annual averages for cadmium
associated with metal industry sources at urban sites . . 2-5
2.3 Ambient atmospheric cadmium concentrations, Chicago,
Illinois, November 5, 1972 2-13
2.4 Ambient atmospheric cadmium concentrations, Chicago,
Illinois, November 23, 1972 2-14
2.5 Cadmium concentrations in surface waters at USGS benchmark
stations in 1970 2-18
2.6 Percent of river water samples containing cadmium greater
than 1 ppb in five U.S. regions 2^19
2.7 Frequency distribution of cadmium in Great Lakes sediments. 2-24
2.8 Cadmium in plants grown in 200 mg Cd/1000 g soil ...... 2-46
2.9 Localities of Spanish moss samples, and cadmium concentra-
tions found in these samples ............... 2-49
2.10 The effect of soil pH and cadmium concentration on the
cadmium content of soybean leaves ............ 2*-53
2.11 Locations of study areas for cadmium levels in terrestrial
animals, excluding birds ........... ...... 2-56
2.12 Locations for cadmium sampling in birds .......... 2-74
2.13 Mean cadmium concentrations in Atlantic- and Gulf of Mexico
(Crassostrea virginica) and Pacific Ocean oysters
(C_. gigas) ....................... , 2-80
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FIGURES (Continued)
Number Page
2.14 Cadmium in marine fish—muscle tissue, ppm 2-84
3.1 Environmental flow of cadmium emitted by man's activities . 3-2
3.2 Flow of cadmium in a land area segment 3-6
4.1 Average values (in ppm) of cadmium content in institutional
total diets, 1967 4-5
5.1 Zinc, cadmium, and mercury distributions in the kidney of
a 42-year-old female 5-9
5.2 Molar relationship of cadmium and zinc in the renal cortex. 5-13
TABLES
1.1 Cadmium Discharge Rates to the Environment from Steelmaking
and Coke Production 1-10
1.2 Cadmium Concentrations from Five Power Plants 1-13
1.3 Revised Cadmium Emission Estimates 1-15
2.1 Annual Average Urban Atmospheric Cadmium Concentrations
Reported by the National Air Surveillance Networks,
1970-1974 2-3
2.2 Atmospheric Cadmium Concentrations for Urban Sampling
Stations in Eight States, 1971-1976 2-7
2.3 Atmospheric Cadmium Concentrations for Nonurban Sampling
Stations in Eight States, 1971-1976 2-12
2.4 Cadmium Levels in Surface Waters of the United States . . . 2-20
2.5 Cadmium Levels in Ground Waters of the United States. . . . 2-21
2.6 Summary of Cadmium Concentrations in U.S. waters 2-22
2.7 Cadmium Concentrations in the Ohio River and Some of Its
Tributaries 2-25
2.8 Sewage Sludge Data on U.S. Cities 2-29
2.9 Variability of Cadmium Contents in Sewage Sludges 2-35
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TABLES (Continued)
Number Page
2.10 Cadmium Content of Rock Types 2-37
2.11 Cadmium Concentrations in Missouri Soils 2-37
2.12 Concentrations of Cadmium in Urban and Suburban Soils—
1972 2-38
2.13 Cadmium Concentrations in Soil Near East Helena, Montana. . 2-40
2.14 Cadmium Soil Concentrations in Northwestern Indiana .... 2-41
2.15 Cadmium Concentrations in Plants of an Industrial Region. . 2-44
2.16 Cadmium Concentrations in Plants Remote from Industriali-
zation 2-45
2.17 Cadmium Levels in Spanish Moss, Tillandsia usneoides. . . . 2-48
2.18 Concentration of Cadmium in Wheat and Grass Growing Under
Normal Conditions in 19 States East of the Rocky
Mountains 2-50
2.19 Cadmium Content of Crops Grown in the Greenhouse on
Calcareous Domino Silt Loam With and Without Treatment
With Sewage Sludge 2-52
2.20 Levels of Cadmium in Terrestrial Invertebrates 2-54
2.21 Cadmium Levels in Cattle 2-57
2.22 Cadmium Levels in Starlings Measured in 1971 and 1973 . . . 2-60
2.23 Freshwater Fish—Cadmium Levels in Tissues 2-64
3.1 Cadmium Content and Zn/Cd Ratios in Uncultivated Soil
Surrounding East Helena Stack 3-4
3.2 Distribution of 284 pCi of 115mCd in Microcosm Experiments
at 27 Days after Tagging with 115mCdCl2 3~7
3.3 Cadmium Content of Water, Suspended Sediment, and Bottom
Sediment in Two Tennessee Streams 3-9
3.4 Concentration Ratios of 109Cd in a Stream Ecosystem .... 3-1°
3.5 Cadmium Cycling Budgets in Several Watersheds and Salt
Marshes 3-11
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TABLES (Continued)
Number Page
3.6 Trends of Arithmetic Average Concentrations (ppm) of
Cadmium in Dietary Food Groups in Two Major Food
Pathways to Man 3-13
4.1 Media Contributions to Normal Retention of Cadmium 4-3
4.2 Estimated Daily Cadmium Intake from Foods in Various
Locations in the United States 4-4
4.3 Cadmium Content in Different Food Categories in the U.S.A.. 4-6
4.4 Food Groups by Mean Cadmium Content and their Contribution
to Daily Cadmium Intake 4-8
4.5 Cadmium Content of Selected Adult Foods 4-9
4.6 Cadmium Content of Selected Baby Foods 4-10
4.7 Cadmium Content of Foods by Year and Daily Intake 4-11
4.8 Potential Exposures of Human Beings to Cadmium from Food
Sources • 4-11
5.1 Summary Data on Cadmium Levels in Various Tissues of
Exposed and Nonexposed Persons 5-3
5.2 Cadmium Concentration in Wet Tissue, Smokers and
Nonsmokers 5-4
5.3 Cadmium Body Burden Media Retention 5-5
5.4 Mean Cadmium Levels in Human Placentas, Maternal Blood, and
Fetal Blood 5-6
5.5 Whole Blood Assays 5-7
5.6 Cadmium Concentrations in the Human Renal Cortex, by Age. . ^ in
5.7 Renal Cadmium and Zinc Levels in 40 to 79-Year-Old Males,
by Smoking Category 5-11
5.8 Cadmium in Renal Cortex, by Sex and Age 5-11
5.9 Summary of Tests Between Patients With and Without Cancer,
by Tissue and Metal 5-14
5.10 Cadmium Concentration in Human Liver, by Age 5-14
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TABLES (Continued)
Number Page
5.11 Concentrations of Cadmium in Kidney Cortex in Workers
Exposed to Cadmium Oxide Dust in Relation to
Morphological Kidney Changes Seen at Autopsy or Biopsy. . 5-15
5.12 Urinary Excretion of Cadmium in "Normal" Subjects 5-16
5.13 Cadmium Levels in Acculturated and Unacculturated
Populations 5-17
5.14 Cadmium in Hair from Boys Living in Urban Areas 5-18
5.15 "Normal" Concentrations of Cadmium in Hair 5-20
5.16 Cadmium in Blood, Urine, Hair, and Feces 5-21
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EXECUTIVE SUMMARY
This report is a review of environmental levels of cadmium based
on published reports and other information sources.
Cadmium is a relatively rare element in the earth's crust always
found in association with zinc and ranking in abundance between mercury
and silver, that is, about 0.1 to 0.5 ppm. The annual release of cadmium
to the environment is approximately 2,000 metric tons (1974 estimate).
About 20 percent of this comes from zinc mining and smelting (primary
cadmium production is a by-product of zinc production). Another 30
percent comes from the manufacture, use, and disposal of cadmium products.
These include electroplating (the major use for cadmium), paint pigments,
alloys, plastics, and nickel-cadmium batteries. The remaining 50 percent
comes from inadvertent releases resulting from cadmium being a contaminant
in other substances. The principal inadvertent sources are phosphatic
fertilizers, sewage sludge, and combustion of fossil fuels. The major
portion (82 percent) of these releases is land-destined waste, followed
by air emission (16 percent). Waterborne effluents constitute a little
over 1 percent.
Cadmium concentrations in the atmosphere of the U.S. are a few
hundredths or thousandths of micrograms per cubic meter of air, with
certain exceptions. The principal exceptions are areas where zinc or
lead mining and smelting is or has been conducted. In Shoshone County,
Idaho, for example, levels exceeding 0.1 yg/m have been reported.
Surface water concentrations of cadmium are less than 10 ppb near
headwaters of tributary streams, increase somewhat in areas of high popula-
tion density, and reach ppm levels near mining and smelting operations. In
12 percent or less of samples obtained from surface waters in the 50 states
the U.S. Public Health Service limit for potable waters (10 ppb) was
exceeded. The highest level found (1,400 ppb) was near mining and smelting
operations in Idaho. On the average, groundwater quality with respect to
cadmium exceeds that of surface waters. In U.S. drinking water, cadmium
levels are normally less than 1 ppb. The present concentration of cadmium
in the oceans is about 0.11 ppb.
Cadmium is found to concentrate in sediments, and whereas water
concentrations are in the ppb range, cadmium concentrations in sediments are
in the ppm range, particularly in localized areas exposed to industrial or
mining wastes. Levels as high as 60,700 ppm have been reported in Hudson
River sediment below the outfall of a nickel-cadmium battery plant. Sedi-
ments not exposed to wastes may contain only fractions of a ppm.
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Concentrations of cadmium in marine sediments are the highest in harbors,
with mean concentrations on the order of 10 ppm being reported.
Cadmium concentrations in sludge resulting from treatment of
wastewater are extremely variable among U.S. cities, with levels ranging
from a few ppm to several thousand ppm. The highest values occur in
sludges from cities that are highly industrialized. Municipal sewage
sludge disposition in 1975 in the U.S. has been reported to be 15 percent
in the ocean, 25 percent in landfills, 35 percent by incineration, and
25 percent by application to land.
Cadmium concentrations in U.S. soils not excessively disturbed
by man approximate those found in rocks, i.e., 0.2 to 0.5 ppm. Fertilizer
applications do not appear to have raised this level above 1 ppm. Highest
soil concentrations are found in the vicinity of smelters. In the vicinity
of major urban industrial areas, several ppm of cadmium may be found in
surface soils.
In terrestrial plants and animals, cadmium concentrations are
generally a few ppm or less, with higher levels appearing near smelters
(up to 50 ppm). Similar levels have been found in aquatic plants, with
levels of the order of hundreds of ppm being found in contaminated areas
near smelters and nickel-cadmium battery plants. Plants differ greatly
in their ability to take up cadmium, and this is an important consideration
in selecting crops to be grown on sludge-treated land. To minimize cadmium
concentrations in food crops grown on sludge-treated land it is also
necessary to control soil pH, to limit annual applications of sludge, and
to use sludge that is low in cadmium.
Vascular plants, algae, and plankton have been shown to contain
levels of cadmium in their tissues several orders of magnitude greater than
that found in their immediate environment. Invertebrates accumulate cadmium
from both soils and foods, and levels in marine mammals are generally much
higher than those found in prey fish species. Immature mammals were also
found to contain lower cadmium concentrations in their tissues than adults.
The highest concentration of cadmium found in fish was 1.7 ppm, in the
Columbia River. The levels are lower in marine fish than in freshwater fish
and they are somewhat higher in aquatic invertebrates (up to 5 ppm in
Atlantic oysters).
The available data on biota do not permit definition of trends over
time. The studies are rarely concerned with analysis of comparable species
or tissues analyzed, the same location, similar sampling or analytical
methods or monitoring conducted over more than 1 year. Data from the
National Pesticide Monitoring Program for starlings provide the most
uniform base from which trends may be indicated. These data show an overall
slight increase in the cadmium concentration found in starlings between 1971
and 1973.
Unlike plants, the species' dependency of the cadmium levels in
animals were not very clearly demonstrated. Most of the animals from the
same geographical areas seemed to have approximately the same levels of
xii
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cadmium in their bodies. Exceptions were domestic rabbits and mountain
cottontails found in the polluted Helena Valley, Montana. Their levels
were 7 to 16 times higher than those of cows, ground squirrels, and mice.
No clear indication of any difference in the cadmium content of herbivorous
and carnivorous animals were observed from the available data.
Knowledge gaps still exist on the behavior and fate of cadmium
in atmospheric, terrestrial, and aquatic environments, but some statements
can be made. Airborne cadmium particles are presumed to eventually return
to the land and water environments, the major fallout appearing to be
within a few kilometers from the source, e.g., a smelter stack. Soil
receives cadmium directly from emission sources as land-destined wastes
and fallout deposition from the atmosphere, the estimated amount being
nearly 96 percent of the total environmental cadmium emissions. About 95
percent of this is retained in the soil, the remainder being leached or
washed into streams. There is a lack of information on sedimentation
losses of cadmium in the freshwater environment; thus the flux of cadmium
from freshwater streams into the oceans can only be estimated.
Although cadmium is present in measurable quantities in virtually
all areas, for the general population oral ingestion in foods can represent
the most important source of cadmium intake. Airborne sources appear to
constitute a significant portion of cadmium intake for those occupationally
exposed or those residing in areas heavily polluted by cadmium-emitting
industries. Data from the FDA's Total Diet Studies indicate no trend of
increasing or decreasing cadmium exposure from foods during the period 1968
through 1974.
The estimated biological half-life of cadmium in man is from 13 to
47 years. The average body burden of cadmium in adults in the United States
is reported to be 15 to 20 mg. This is reflected by increased concentrations
in the kidney, liver, pancreas, and blood vessels. The adult American male
nonsmokers with mean age of 60 have, on the average, a total body burden of
13 mg of cadmium. In contrast, the adult cigarette smokers have a total
body burden of 30 to 40 mg. Studies of cadmium levels in whole blood in
normal, nonexposed human populations generally reveal whole blood cadmium
levels of less than 1 ng/100 ml but in exposed workers the range may be
1 to 10 ng/100 ml.
Based on the information in this document, current cadmium releases
to the environment appear to be declining. However, the cadmium content in
fossil fuels and fertilizers is only partially controllable, and these two
sources may set the lower bounds of attainable minimums in cadmium
emissions to the environment. Most of the dissipated cadmium eventually
becomes bound to soil, sediment, and ocean sinks. Biological accumulations
of cadmium are found in most living organisms.
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1. INTRODUCTION
PHYSICAL AND CHEMICAL PROPERTIES
Cadmium is a relatively rare element in the earth's crust, ranking in
abundance between mercury and silver, 0.1 to 0.5 ppm, and does not occur in
sufficient abundance to be mined as an ore. Cadmium is a soft metal with
low melting and boiling points, 312 C and 765 C, respectively. These
physical properties account for its volatility and high vapor pressures
encountered at only moderate temperatures and contribute to its release to
the atmosphere through the pyrometallurgical operations in its recovery from
ores and in welding and torch cutting, and from incineration of wastes and
the combustion of coal. However, ambient concentrations of cadmium in the
air are, in general, of the order of a few hundredths or thousandths of a
microgram per cubic meter, suggesting the existence of an effective removal
mechanism (fallout and rainout). More detailed information is available in
Hammons and Huff (1975).
Cadmium sulfide (CdS) , carbonate (CdC03>, and oxide (CdO) are
insoluble compounds. The hydroxide, Cd(OH)2, is also insoluble and can be
precipitated from solution by the addition of hydroxide ion (OH~). Unlike
zinc hydroxide, cadmium hydroxide does not redissolve in excess hydroxide
(Fulkerson and Goeller, 1973). Because of the low solubility of the carbo-
nate and the sulfide, the amount of cadmium which can remain dissolved in
natural waters is quite low. Additionally, in waters free of sulfide or
any complex-forming ligands, dissolved cadmium concentrations can be very
low as a result of the equally low solubilities of the carbonate. In
nonacid waters, at a pH less than 9.5 and with <10~5 M total carbonate, the
concentration of dissolved cadmium can be as low as a few parts per billion
(Fulkerson and Goeller, 1973). Nearly all of the U.S. Geological Survey
benchmark surface water stations which are discussed later exhibit dissolved
cadmium concentrations of this order of magnitude, where cadmium was detect-
able at all. Most cadmium found in aquatic systems tends to be associated
with particulates.
PRODUCTION AND USES OF CADMIUM
Production
Cadmium is one of the lesser nonferrous metals, produced almost
totally as a by-product of zinc mining and smelting. Annual consumption in
the U.S. has during the last several years averaged around 5,000 metric tons
(De Filippo, 1975). Although the U.S. has been the leading producer for
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over half a century, that portion of domestic consumption which is produced
by the U.S. has steadily declined. Nearly 40 percent of U.S. demands are
now imported. In 1974, domestic demand, 5,600 metric tons (6,200 short
tons), was 33 percent of world production.
Uses
Total U.S. cadmium consumption in recent years has been in the range
of 4,000 to 6,000 metric tons/year and is expected to reach about 10,000
metric tons annually. The uses of cadmium are almost totally dissipative;
there is no significant recycling. Although data on the ultimate end use of
cadmium are sparse, the largest single use which consumed about 46 percent
of the total (2,700 metric tons) in 1974 is for electroplating and coating,
including that for transportation uses. Cadmium is widely used for plating
motor vehicle parts, aircraft parts, marine equipment, hardware, household
appliances, and miscellaneous industrial machinery parts (nuts, bolts,
springs, washers, rivets, and other fasteners) to prevent corrosion
(De Filippo, 1975).
Cadmium has many superior properties compared to competitive materials
for corrosion protection and its use is likely to continue, at least in the
near term. The properties of cadmium which have led to its widespread use
in electroplating include the following: (1) good protection from only a
thin coating, (2) low electrical resistance of plated contacts, (3) retention
of luster for long periods, (4) ease of soldering plated parts, (5) good
corrosion resistance to salt water and alkalies, (6) uniform deposition on
intricately shaped objects, and (7) little effect on strength of steel parts
stressed in high-temperature service (Heindl, 1971).
The second largest use (M.,000 metric tons in 1974) is for paint
pigments; cadmium sulfide, yellow to orange, and cadmium sulfoselenide,
orange to deep maroon, are the most widely used pigments.
Cadmium salts of long-chain organic acids are used as plasticizers and
heat stabilizers for plastics, ^900 metric tons in 1974. However, because of
its toxicity, cadmium cannot be used in plastics for food containers.
The only other identified use of significance, 550 metric tons in 1974,
is in nickel-cadmium batteries. There are a number of other uses. Cadmium
has a very high neutron-absorbing cross section and is accordingly used in
nuclear reactor controls. It finds some use in fluorescent phosphors, in
low-melting alloys, in bearing alloys, and in brazing alloys and solders.
Total consumption for other uses in 1974 was approximately 450 metric tons.
Figure 1.1 represents U.S. cadmium consumption in 1975. In contrast
to 1974, plastics stabilization utilized more cadmium than the processes
involved in developing pigments.
The forecasts by the U.S. Bureau of Mines for the year 2000 estimate
cadmium consumption to lie between 8,400 and 15,600 metric tons (9,300 to
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PLASTICS
STABILIZATION
20%
(16%)
ELECTROPLATING
55%
(35%)
PIGMENTS
12%
(23%)
MISCELLANEOUS
8%
(13%)
BATTERIES
5%
(13%)
Figure 1.1. U.S. cadmium consumption in 1975
(American Metal Market, 1975).
Figures in parentheses represent consumption
in 1975 for U.S., West Germany, Britain, and
Japan (Anonymous, 1977).
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17,200 short tons) with the most probable value being 11,500 metric tons
(12,700 short tons) (De Filippo, 1975). The projected breakdown of this
total by end uses is shown graphically in Figure 1.2.
Zinc and zinc-tin alloys are expected to be satisfactory substitutes
for cadmium in some electroplating uses. Organotins are being considered
as a cadmium replacement in the plastics stabilizer market. Ion Vapor
Deposition (IVD) of aluminum is currently under consideration as a
substitute for cadmium in electroplating. McDonnell Aircraft Company and
the Department of Defense have developed the IVD aluminum process and have
adapted it to numerous military aircraft coating applications. Some of
the advantages of IVD aluminum plating are higher temperature usability,
lower cost, reduced hydrogen embrittlement, and reduced plating thickness
which is translated to both reduced weight and cost.
SOURCES OF ENVIRONMENTAL CONTAMINATION WITH CADMIUM
Cadmium is introduced into the environment either as a result of the
manufacture, use, or disposal of some cadmium product, or as a contaminant
in some other substance. Sargent and Metz (1975) pointed out that while
20 percent of the release arises from the primary nonferrous metals industry,
and 30 percent from the conversion, use, and disposition of cadmium in our
economy, an approximately equal amount is estimated to arise from inadver-
tent sources.
Release from Production and Use of Cadmium Products
Introduction of cadmium into the environment from primary production
operations is a fairly localized problem and the number of primary sites is
small (Figure 1.3). While, as shown later in the sections on environmental
levels in air, water, and soil, the environs around many of these plants
received significant cadmium burdens in past years, the trend now is toward
effective control of emissions. Incremental burdens in future years are,
therefore, being reduced.
The cadmium-consuming industry is geographically somewhat concentrated.
Fulkerson and Goeller (1973), reporting to a 1960 U.S. Bureau of Mines
survey, noted that approximately 58 percent of the cadmium-consuming industry
of the United States was in states bordering the Great Lakes. The remaining
28 percent of the consuming industry was distributed among the other states.
Thus, releases of cadmium to the environment from manufacture, use, and
disposal would be expected to follow a similar geographic distribution
(Figure 1.4).
An assessment of industrial hazardous waste practices in the electro-
plating and metal-finishing industries (U.S. Environmental Protection Agency,
1975b) developed a model of the geographic distribution of independent job
shop platers based upon survey response (Figure 1.5).
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Transportation
Coating and Plating
Batteries
Paints
Plastics & Synthetics
Others
2 3
Thousands of Metric Tons
Figure 1.2. Projected cadmium consumption in the United States
by end use, year 2000.
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I
ON
Figure 1.3. Geographical distribution of recoverable zinc resources
in the United States (Wedow, 1973).
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Figure 1.4. Cadmium consumption (percent) by state. Remaining
37 states—28% (Fulkerson and Goeller, 1973) .
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Cadmium is associated with all zinc ores and is a by-product of the
zinc industry. Its removal from zinc is necessary and would be performed
even in the absence of a market for cadmium. Cadmium follows the zinc
through the beneficiation step and, as in the past, effluents from zinc mill
tailings ponds introduced very significant quantities of both into the
environment.
The major use for cadmium, electroplating, has also been a major
contributor to the escape of cadmium to the environment. It has been
estimated (Ottinger et al., 1973a and b) that approximately 18 percent of
the cadmium used in electroplating is lost as a liquid, solid, or semisolid
sludge during the plating operation, usually to the sewers. The sources of
the liquid, solid, and semisolid wastes generated in the electroplating
industry include the following:
• Rinse waters from plating, cleaning, and other
surface finishing operations
• Concentrated plating and finishing baths that
are intentionally or accidentally discharged
• Wastes from plant or equipment cleanup
• Sludges, filter cakes, etc., produced by
naturally occurring deposition in operating
baths or by intentional precipitation in the
purification of operating baths, chemical
rinsing circuits, etc.
• Regenerants from ion exchange units
• Vent scrubber waters.
The most important of these wastes, especially from the standpoint of
the smaller plater, is the rinse water. This is the constantly flowing,
production-oriented stream which is generally so large in volume that some
form of concentration is warranted before it can be economically trans-
ported to a central disposal facility for treatment (Ottinger et al.,
1973a and b). Ottinger's estimate of loss suggests a loss of approximately
490 metric tons from the approximately 2,700 tons of cadmium consumed
annually in electroplating. After application of pollution abatement
practices in compliance with effluent guidelines, Sargent and Metz (1975)
estimate 10.5 MT/yr waterborne waste and 73.5 MT/yr wastes to land disposal
for the electroplating industry.
Yost's (1976) projections of cadmium discharged (in metric tons) from
electroplating facilities to natural waters are:
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38.6
13.4
Figure 1.5. Geographical distribution of independent job platers
by EPA region (percent). (Source: U.S. Environmental
Protection Agency, 1975b.)
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Year Direct
1976
1980
1985
13.6
1.0
0.22
Through
Publicly Owned
Treatment Works
35.8
3.3
0.74
To Publicly Owned
Treatment Works
Sludge
107.3
10.0
2.23
Concentrated
Waste and Sludge
to Landfill
18.3
160.7
135.3
He forecasts a downward trend in cadmium discharge, though landfill cadmium
will first increase until after 1980 when it will turn downward.
Cadmium discharge rates to the environment from steelmaking and coke
production are summarized in Table 1.1. The steel industry is considered
to be among the leading contributors of cadmium to the environment.
Cadmium emissions are associated primarily with the refining processes
(open-hearth, basic-oxygen, and electric arc furnaces) in which No. 2 scrap
steel (contains galvanized and plated metal) is used and coke production.,
TABLE 1.1. CADMIUM DISCHARGE RATES TO THE ENVIRONMENT
FROM STEELMAKING AND COKE PRODUCTION3
Year
1975
1980
1985
Total
Production,
tons x 106
116.8 (steel)
82.2 (coke)
152 (steel)
107 (coke)
158 (steel)
111 (coke)
Cadmium Discharge, metric tons per year
Atmosphere
13
7
13
10
10
10
Landfill
105
290
322
Aqueous Discharge
6
5
3
Source: Yost, 1976.
Powers (1976), in discussing disposal of toxic substances in industrial
wastes, claims that the only adequate method for the disposal of concentrated
cadmium wastes is coagulation with lime, then sedimentation, followed by sand
filtration. The cadmium hydroxide sludge produced can be dried and placed in
an approved landfill. Powers further points out that cadmium hydroxide is
not very soluble, 2.6 mg/£, so that contamination of water supplies from a
landfill operation should not be a problem, at least in an approved chemical
1-10
-------
landfill area of the California Class I type ("those at which complete
protection is provided for all time for the quality of ground and surface
waters from all wastes deposited therein and against hazard to public
health and wildlife resources") (Fields and Lindsey, 1975).
Most processes associated with cadmium in pigments involve a high-
temperature calcination treatment so air emissions are encountered,
estimated at 9.5 MT by Fulkerson and Goeller (1973). While it does appear
that little cadmium is lost to the environment in manufacturing of paints,
the cadmium is ultimately dispersed in use by weathering and discarding of
painted items. Although their use and disposal results in almost total
dispersal to the environment, other major uses of cadmium (alloys, plastics
manufacture, and nickel-cadmium batteries) contribute only minor quantities
of cadmium to the environment in their manufacture.
Inadvertent Sources of Cadmium Release
Principal inadvertent sources of cadmium released to the environment
are phosphate fertilizers, sewage sludge, and the combustion of fossil
fuels. Minor sources are rubber tire wear, from the cadmium associated
with zinc oxide vulcanization accelerator, as well as use and recycling of
galvanized steel which already have been discussed.
Fulkerson and Goeller (1973) estimate a range of 110 to 900 metric
tons of cadmium inadvertently emitted per year, corresponding to a
consumption of 450 million metric tons of coal and assuming cadmium
contents in the rather wide range of 0.25 to 2 ppm. Estimation of the
total quantities of cadmium released is subject to considerable uncertainty
as a result of the large variability in intrinsic cadmium contents of
natural raw materials. Fulkerson (1975) later revised this estimate to
150 MT/yr of atmospheric emissions, based on 600 million MT/yr of coal at
an average of 2.5 ppm cadmium and 90 percent precipitator efficiency. These
appear to be high values for average cadmium concentrations on the basis of
available coal analyses. Ruch et al. (1974) reported the results of
the analyses of 101 coal samples, 82 of which were from the Illinois basin.
Only about 50 percent of the samples exceeded 0.6 ppm and only 34 percent
exceeded 1.2 ppm. Thus, a more realistic estimate appears to be the one
developed by Sargent and Metz (1975) who estimated 80 MT/yr atmospheric
emissions and 470 MT/yr in the residues and captured fly ash, on the basis
of 450 million MT/yr of coal and an average 1 ppm cadmium content.
Klein et al. (1975) studied the pathways of 37 trace elements through
a coal-fired plant, measuring the concentrations and mass flows in the
coal, slag, fly ash, and exit gas stream. Cadmium was analyzed by isotope
dilution spark source mass spectroscopy. The following ppm concentrations
of cadmium were observed:
Coal - 0.47
Slag -1.1
Precipitator inlet fly ash - 8.0
Precipitator outlet fly ash - 51.0
1-11
-------
The increased concentration in the particles leaving the electrostatic
precipitator suggests that cadmium losses will be associated with ultrafine
particulate matter. Size ranges of outlet fly ash particles were not
reported, although other test data indicated that they would be 0.1 to
0.5 micrometer in diameter or less. The cadmium mass balance indicated
less than 2.5 percent was contained in the exit gas stream, considerably
lower than the 17.5 percent assumed by Sargent and Metz (1975) in their
estimation of atmospheric emissions.
A more detailed study of flow pathways of cadmium through power plants,
including the flue gas desulfurization step, has recently been reported by
Holland et al. (1975). Cadmium concentrations determined in the coal feed
and in various streams in 5 coal-fired power plants are summarized in Table
1.2. These results provide evidence that collected cadmium is satisfactorily
immobilized in flue gas scrubber sludges as indicated by the 0.5 to 2 ppb in
leachate from the sludge.
Oils exhibit the same type of variability in cadmium content as does
coal, so that selecting an average value for purposes of estimating emissions
presents problems. Lagerwerff and Specht (1971) found 0.07 to 0.11 ppm in
diesel oils and 0.42 to 0.53 ppm in heating oils. Fulkerson and Goeller
(1973) assumed an average of 0.3 ppm and a 50 billion-gallon annual consump-
tion in deriving an estimate of about 55 MT/yr emitted. The practical
technology to eliminate cadmium from oils does not appear to be available,
and this source of cadmium will probably continue at about its present levels.
Cadmium is found associated with the phosphate in phosphate rock, and
tends to follow the phosphorus in processing, and thus is a contaminant in
phosphate fertilizers. Fulkerson and Goeller (1973) assumed a range of 2 to
20 ppm and estimated an input of 23 to 230 MT/yr from commercial fertilizers.
Sargent and Metz (1975), assumed a lower value of 7.8 ppm on the basis of
other analyzes, and estimated cadmium input to the soil from this source of
100 metric tons in 1975.
Sewage sludge is a third significant source of inadvertent cadmium
release. Fulkerson and Goeller's (1973) estimate of inadvertent releases
assumed a cadmium content in sludge of 15.6 ppm, based on some Swedish data.
On the basis of recent U.S. data, this appears to be low for the more
industrialized wastes of this country. Salotto et al. (1974) analyzed about
100 digested sludge samples from 33 wastewater treatment plants in 13 states;
they found the cadmium contents to be log-normally distributed, with a
geometric mean of 43 ppm, an arithmetic mean of 75 ppm, and a median value
of 31 ppm. Sargent and Metz (1975) , using an assumed average cadmium content
of 75 ppm, derived an estimate of 300 MT/yr from sludge. They further
assumed that 60 percent is applied to land, 10 percent is dumped at sea, and
30 percent is incinerated, producing 20 metric tons of air emissions at an
incinerator scrubber efficiency of 80 percent.
1-12
-------
TABLE 1.2. CADMIUM CONCENTRATIONS FROM FIVE POWER PLANTS'
(in ppm)
Electric Power Generating Station
Source
Coal
Bottom ash
Particulate collector ash
Lime or limestone scrubber
feed
Ash pond liquor
Scrubber sludge
Scrubber liquor
Make-up water for
scrubber
Coal ash leachate
Flue gas desulfurization
sludge leachate
1 2
0.028 0.05
0.19 0.41
0.39 1.4
0.28 0.24
-
0.0005
0.40
0.006b
0.0004b 0.0004b
0.001 0.0025
0.0005
3
0.30
0.86
5.3
0.92
0.0001
0.0009b
0.01
4
0.11
1.1
4.2
0.90
0.001
1.1
0.002b
o.ooib
0.001
0.001
5
7.9
1.6
0.65
0.04
0.25
0.009b
0.0007b
0.0011
0.002
Source: Holland et al., 1975.
Concentration in ppb.
1-13
-------
Summary of Cadmium Input to the Environment
As shown in Table 1.3, Sargent and Metz (1975) estimate the current
total quantity of cadmium released to the environment to be about 1,800
MT/yr. Land-destined wastes constitute a major portion of the total
environmental emissions with more than 82 percent, followed by air emission
at 16 percent, and waterborne effluents only a little over 1 percent.
These numbers are based on limited measurements and estimates. Also
included in the table are estimates provided by Yost (1976).
Of the approximately 2,000 metric tons of cadmium emitted to the
environment in 1974, about 20 percent came from zinc mining and smelting;
50 percent was from fossil-fuel combustion, fertilizer use, and disposal
of sewage sludge; and 30 percent was from industrial uses including
remelting of cadmium-plated scrap, incineration of plastics containing
cadmium, and electroplating.
Since cadmium is used primarily dissipatively, the total destined
for introduction into the environment will approximately equal that
produced and used. Thus, the principal problem is determining to which
compartment—air, water, land—the emissions are consigned. Nevertheless,
at present, it appears that the overall trend in uncontrolled emissions of
cadmium to the environment are definitely down, spurred by the increasingly
complete application of pollution abatement controls. This trend is
expected to continue, although there will be some offset as a result of
natural growth in the economy. Also, there are further opportunities for
substitution of other materials for cadmium and its compounds and for
further reduction of the cadmium content of commercial zinc. On the other
hand, the cadmium contamination in fossil fuels and in fertilizer is only
partially controllable and these two sources may set the lower bounds of
attainable minimums in cadmium emissions to the environment.
1-14
-------
TABLE 1.3. REVISED CADMIUM EMISSION ESTIMATES'
(Metric Tons per Year as Elemental Cadmium)
Source
Zinc ore mining and beneficiation
Primary zinc industry
Total: Extraction, refining, and
production
Electroplating shops
Pigment manufacture
Stabilizer manufacture
Alloy manufacture
Battery manufacture
Total: Industrial conversion
Secondary nonferrous metals
Iron and steel industry
Steelmakingc
Coke production0
Galvanized products
Rubber tire wear
Incineration
Total: Consumption and disposal of
cadmium-containing products
Phosphate fertilizers
Phosphate detergents
Coal combustion
Diesel and fuel oil combustion
Lubricating oils
Sewage sludge
Total: Inadvertent sources
Grand totals
Airborne
Emissions
0.2
102
102
1.0
9.5b
2.7b
2.3h
O.?b
15.0
2.2
10.5
13.0 (1975)
13.0 (1980)
10.0 (1985)
7.0 (1975)
10.0 (1980)
10.0 (1985)
-0
5.2b
16.0
34.0
-0
-0
80.0 (1974)
80.0 (1980)
50. Ob
0.8°
20.0
151.0
300.0
Waterborne
Effluents
-0
10.0 (1971-72)
2.0 (1977)
1.3 (1983)
-7.0 (1974-75)
-2.0 (1980)
10.5 (1972)
49.4 (1976)c
4.0 (1977)
4.3 (1980)c
0 (1983)
0.96 (1985)c
0.75
-0
-0
0.3
-8.0 (1974-75)
-3.0 (1980)
-0
-0
6 (1975)
5 (1980)
3 (1985)
-0
-0
-0
-0
-0
10.2
-0
-0
-0
-0
-0
10.0
25.0 (1974-75)
15.0 (1980)
Land -Destined
Wastes
250
-0
250
73.5 (1972)
18.3 (1976)C
80.0 (1977)
160.7 (1980)=
0 (1983)
135.3 (1985)c
16.5
-0
-0
8.4 (1973)
11.4 (1977)
9.1 (1983)
-102.0 (1974-75)
- 75.0 (1980)
20
330
105 (1975)
290 (1980)
322 (1985)
40
-0
70
460
100 (1974)
130 (1980)
-0
370 (1974)
680 (1980)
-0
-0
250
720 (1974-75)
1,060 (1980)
1,500 (1971-75)
1,800 (1980)
Total Emissions
359 (1974-75)
354 (1980)
125 (1974-75)
93 (1980)
494
831 (1974-75)
1,221 (1980)
1,800 (1974-75)
2,100 (1980)
aSource: Sargent and Metz, 1975 (with additional data from Yost, 1976).
^Estimates unchanged from Fulkerson and Goeller (1973).
CYost, 1976.
1-15
-------
2. CADMIUM LEVELS IN THE ENVIRONMENT
Cadmium is a relatively rare element and is only a minor element in
U.S. technology. When total U.S. consumption is only of the order of 5,000
MT/yr, even total dispersion would not begin to compare to the quantities
of other metals, e.g., copper, lead, or zinc, entering the environment each
year. While the uses of cadmium are largely dissipative, the forms in which
it is utilized are fairly stable and so its dispersal is not rapid and total,
as it tetraethyl lead antiknock fluid, for example. Thus, cadmium is found
in the environment in ppm and ppb levels.
AIR
National Atmospheric Monitoring Program
In recent years the EPA has begun monitoring of cadmium on a national
level as part of the National Air Surveillance Networks (NASN). Since 1968,
the number of urban stations operating has been 164; the nonurban total is
30 (Figure 2.1) (U.S. Environmental Protection Agency, 1972). NASN also
compiles and reports data collected by state and local agencies. The EPA
maintains a record of most ambient air sampling performed in the U.S. on its
SAROAD (Storage and Retrieval of Aerometric Data) computer system.
Due presumably to the employment of emission spectroscopy instead of
atomic absorption, the atmospheric cadmium concentrations reported for 1970-
1974 NASN samples (Akland, 1976) have only a small fraction of positive
values which permit calculation of annual averages; for many states no
detectable atmospheric cadmium concentrations are reported for this 5-year
period. All urban stations with at least one reported annual average are
presented in Table 2.1. Analyses of samples taken at 46 nonurban stations
during the 1970-1974 period were uniformly below the limit of detection.
To appraise trends, the 50th percentile (the median) and the 90th
percentile of the annual averages were chosen by Faoro and McMullen (1977)
as the statistics to best describe the change in metals' concentrations over
time. This minimizes the influence of individual extreme values and simpli-
fies the characterization trends for metals having large amounts of data
below the detection limit. Also, these statistics can portray different
aspects of the yearly average distribution—the 50th percentile, the typical,
and the 90th percentile, the high concentration site.
Figure 2.2 graphically presents the urban cadmium concentrations for
the two broad emission categories (combustion and industry) in terms of the
2-1
-------
to
to
Figure 2.1. Map showing NASN stations for measuring cadmium.
-------
TABLE 2.1. ANNUAL AVERAGE URBAN ATMOSPHERIC CADMIUM CONCENTRATIONS
REPORTED BY NATIONAL AIR SURVEILLANCE NETWORKS, 1970-19742
(L.D. = Limit of Detection)
Location
Arizona
Douglas
Tucson
Colorado
Denver
Connecticut
Bridgport
Waterbury
Georgia
Atlanta
Illinois
Chicago
East St. Louis
Peoria
Indiana
East Chicago
Indianapolis
Kentucky
Ashland
Covington
Louisiana
New Orleans
Shreveport
Maine
Portland
Michigan
Detroit
Grand Rapids
Minnesota
St. Paul
Missouri
St. Louis
Montana
Helena
Station
Number
01
01
01
01
01
01
01
01
01
01
02
01
02
01
02
01
01
01
01
01
3
Cadmium Concentration, yg/m
1970
0.0065
0.0102
0.0117
0.0251
L.D.
0.0067
0.0187
0.0066
0.0108
0.0048b
L.D.
L.D.
L.D.
0.0047
0.0060
1971
0.0251
0.0101
0.0048
0.0210
0.0065
0.0045b
0.008b
0.0063
0.0049
0.0184
0.0132
0.0086
L.D.
0.0116
0.0155
0.0150
1972
0.0132
0.0045b
0.0057
0.0174
0.0030b
0.0052
0.009b
0.0093
0.003b
L.D.
L.D.
L.D.
0.0086
1973 1974
0.0045b 0.0062b
0.0027b 0.0139
0.0056
0.006b
L.D.
L.D.
2-3
-------
TABLE 2.1. (Continued)
Location
New Jersey
Camden
Elizabeth
Jersey City
Newark
Perth Amboy
New York
New York City
North Carolina
Winston Salem
Ohio
Cincinnati
Cleveland
Youngs town
Pennsylvania
Allentown
Bethlehem
Hazleton
Philadelphia
Scranton
Texas
El Paso
Virginia
Lynchburg
Wisconsin
Kenosha
Racine
Station
Number
01
02
01
01
01
01
02
01
01
01
01
02
01
04
01
02
01
o'i
01
3
Cadmium Concentration, yg/m
1970 1971
0.0063
0.0167
0.0081 0.0056
0.0125
0.0055b 0.0128
0.0071
0.0076
0.0086
0.0088
0.0056
0.0081 0.0042b
0.0140 0.0191
L.D 0.0067
0.0618
0.0135 0.0040b
L.D.
L.D.
1972
0.0124
0.0159
0.0189
0.0060
0.0178
0.0068b
0.0057
L.D.
0.0442
L.D.
0.0143
0.0071
1973 1974
0.0052
0.0042b 0,0134
0.0068
0.0065
0.0038b
L.D.
0.0206 0.0242"
Source: Akland, 1976.
L.D./2 used for computation of annual average.
2-4
-------
003
002
0008
0001
A
Jt_4_4—1—I
CS 66 67 68 69 70 71 72 73 74 YEAR
4 indicates value below lower discrimination limit.
Figure 2.2. Trends in 50th percentile of annual averages for cadmium
associated with metal industry sources at urban sites
(Faoro and McMullen, 1977).
2-5
-------
50th percentile of annual averages. The 90th percentile plots are not shown
since they provided very similar results. Cadmium shows a sharp downward
trend, 1969-1970, and for the period 1970-1974, the reported cadmium metal
concentrations were below the lower discrimination limit (Faoro and McMullen,
1977).
Local Monitoring of Atmospheric
Cadmium Concentrations
As noted above, EPA also compiles atmospheric data submitted by
states; these are stored in the SAROAD data file. Cadmium results are
available for eight states over the period 1971-1976. Since the size of
sample is limited, it cannot be considered to delineate trends over the
entire U.S. However, most of the states reporting have data for an
extensive network of many stations. Arizona, for example, has data from
53 urban and 14 nonurban stations. Also, several of the states are
included among the producers of lead and zinc (Missouri, Montana, Idaho,
Tennessee) so that some insight is provided on the importance of mining,
milling, and smelting of these ores on entry of metals into the environment.
Annual averages are given for only a small fraction of the stations. How-
ever, the results for odd-numbered deciles along with the maximum and
second maximum are given. The 50 percent decile approximates the median
value and was selected as the stand-in for the average where an annual
average was not reported. These analyses were by atomic absorption rather
than by emission spectroscopy. Beginning about 1970, the analytical method
of choice of the states' laboratories has almost universally been atomic
absorption.
The SAROAD 50 percent decile results for these eight states are
tabulated in Tables 2.2 (urban) and 2.3 (nonurban). Unlike the NASN
emission spectroscopic analyses, positive values were the rule and ND
entries were absent, even for nonurban areas. In areas remote from
cadmium sources, concentrations as low as 0.0001 to 0.0005 yg/m3 were
measured.
The midwestern section of the country has been the subject of several
atmospheric monitoring studies of trace metals. A study was conducted during
a 2-day period in 1972 in Chicago, Illinois (Harrison, 1973). Atomic absorp-
tion spectroscopy was the analytical method used for this investigation.
With these data it was possible to plot isopleths, as shown in Figures 2.2
and 2.4. The November 5, 1972, data, Figure 2.3, show a maximum concentra-
tion of 0.0083 yg/m on the north side of Chicago, in an area free of point
sources to which the high concentration could be attributed. On November 23,
1972, the area of maximum concentration, 0.0073 yg/m3, was located some miles
to the west, and concentration at the north side area had decreased to 0.002
yg/m . From these data, it is evident that mesoscale meteorological factors
were dominant in determining atmospheric cadmium distribution. However,
given adequate mesoscale meteorological data, it appears that with some
refinements the approach could be used to identify and locate point sources.
2-6
-------
TABLE 2.2. ATMOSPHERIC CADMIUM CONCENTRATIONS FOR URBAN
SAMPLING STATIONS IN EIGHT STATES, 1971-1976
Locnt ion
Ar i zona
A.jo
(];is;i Crande
Chandler
Claypool
Clifton
Cochise County
Cochise County
Cochise County '
Flagstaff
Gila County
Glendale
Creenlee County
Kingman
Maricopa County
Mesa
Mohave County
Mohavr Conn t y
Nava jo Conn Ly
Nava jo Count y
Noj;a 1 es
Paradise Valley
Paradise Valley
Phoenix
Phoenix
Phoenix
Phoenix
Phoenix
Phoenix
Phoenix
Phoenix
Phoenix
Phoenix
Piraa County
Final County
Pinal County
Pinal County
Prescott
Scottsdale
Scottsdale
Scottsdale
Scottsdale
Sierra Vista
Sierra Vista
South Tucson
Sun City
Superior
Tucson
Tucson
Tucson
Tucson
Tucson
Yav^n;l'' Cnnntv
Yuma
Idaho
Kellogg
Kellogg
Kellogg
Kellogg
Kellogg
Kellogg
Shoshone County
Slat ion
Number
01
01
01
01
03
01
02
04
01
01
01
91
01
09
02
06
01
02
07
02
01
02
02
04
05
06
08
09
10
11
13
14
11
01
02
03
01
01
02
03
01
02
01
02
03
02
07
08
12
13
01
02
04
06
07
08
09
10
04
Cadmium Concentration, vg/rn^ '
1971 1972
0.0001 0.002
0.0001 0.007
0.0001 0.005
0.119 0.012
0.008 0.002
0.0001 0.0001
0.0001 0.001
0.0001 0.002
0.001
0.003
0.001
0.004
0.004
0.016 0.002
0.004
0.006 0.001
o.ooifi n.oom
0.0001 0.0001
1973
0.0001
0.003
0.0001
0.003
0.01
0.001
0.009
0.003
0 . 000 1
0.003
0.003
0.002
0.005
0.0018d
0.0036d
0.0017d
0.0035d
0.0001
0.002
0.003
0.003
0.005
0.002
0.001
0.003
0.003
0.006
0.002
n.ooi
0.001
1974
0.001
0.003
0.0021d
0.006
0.006
0.001
0.01
0.0001
0.028
0.001
0.0001
0.0008d
0.0001
0.002
0.0001
0.003
0.001d
0.0039d
0.0019d
0.0023d
0.001
0.0001
0.0015d
0.0059d
0.0001
0.001
0.0001
0.005
0.0001
0.0001
0.0001
0.0001
0.001
0.003
0.0071d
0.003
o.noi
0.001
0.3
0.24
0.222
0.252
0.489
0.199
0.16
1975 1976
0.0001
0.0001
0.0001
0.001d
0.0001
0.0008d
0.0008d
0.003
0.004
0.0004d
0.0001
0.0003d
0.0006d
0.0001
0.0001
0.0001
0.0001
0.0001
0.0001
0.0001
0.0965d
0.1189d
0.126
0.122
0.247
0.104
0.1287d
2-7
-------
TABLE 2.2..(Continued)
Location
Idaho
Shoshone County
Shoshone County
Shoshone County
Shoshone County
Shoshone County
Shoshone County
Shoshone County
Shoshone County
Shoshone County
Shoshone County
Minnesota
An oka
Austin
Bemidj i
Bc'.mid j i
Bloomington
Brainerd
Carlton County
Cloquet
Dakota County
Dakota County
Dakota County
Duluth
Duluth
Duluth
Duluth
Duluth
Duluth
Dill H Ih
Duluth
Duluth
F.ust (irand Forks
Kly
Fa i rbaul t
Fergus Falls
Fergus Falls
Grand Rapids
Hastings
Hibbing
Hoyt Lakes
Hutchinson
International Falls
International Falls
International Falls
International Falls
Itasea County
Ltasea County
Mankato
Marshall
Minneapolis
Minneapolis
Minneapolis
Minneapolis
Minneapolis
Minneapolis
Minneapolis
Minneapolis
Moorhead
Moorhead
Moorhead
OrtonvJ lie
Station
Number 1971
16
17
18
19
20
21
22
23
24
25
01
01
01
02
04
01
01
11
07
20
21
02
03
04
05
06
13
13
15
17
O'l
01
01
01
10
03
05
01
01
01
01
02
03
05
01
02
OJ
01
05
07
14
20
22
27
31
32
03
04
05
01
Cadmium Concentration, pg/m^ >c
1972
0.003
0.001
0.001
0.001
0.001
0.001
0.001
0.007
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.003
0.001
0.001
0.001
0.001
0.001
0.001
0,001
0.004
0.001
0.001
0.001
0.001
0.001
0 . 00.1
1973
0.001
0.001
0.002
0.002
0.001
0.010
0.001
0.001
0.001
0.001
0.001
0.003
0.002
0,004
0.001
0.001
0 . 004
0.001
0.008
0.001
0.004
0.003
0.004
0.001
0.020
0.006
0.010
0.001
0.001
0.001
0.004
0.002
0.001
0.002
0.002
0.006
0.014
0.001
".-.."."I
0 .00 1
1974
0.07
0.08
0.03
0.06
0.12
0.37
0.174
0.125
0.146
0.095
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.002
0.001
0.001
0.003
0.001
0.001
0.001
0.001
0.002
0.002
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.002
0.001
0.002
0.002
0.001
0 . 00 1
1975 1976
0.0154d
0.0574d
0.0095d
0.0293d
0.0346d
0.2489d
0.137
0.071
0.108
0.073
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.00')
0.002
0.001
0.001
0.001
0.002
0.001
0.001
0.001
0.001
0.002
p. 001
0.001
0.002
0.003
0.002
0.001
0.001
0.001
2-8
-------
TABLE 2.2. (Continued)
Location
Minnesota
Red Wing
Red Wing
Rochester
Rochester
Rochester
Rochester
Rochester
St. Cloud
St. Cloud
St. Cloud
St. Cloud
St . Louis County
St. Louis County
St. Louis Park
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul
St. Paul Park
Shakopee
Silver Bay
Silver Bay
Silver Bay
Silver Bay
Silver Bay
Silver Bay
Stearns County
Stearns County
Stearns County
Stillwater
Virginia
Waite Park
Wayzata
Wayzata
Willmar
Winoma
Winoma
Winoma County
Worthington
Missouri
Camden County
Cape Girardeau
Chillicothe
Columbia
Columbia
Fulton
Hannibal
Jefferson City
Jefferson County
Joplin
Kirksville
Maryville
Mexico
Station
Number 1971
02
03
01
10
14
15
16
01
16
17
21
01
03
06
01
03
13
14
16
18
21
23
24
30
31
32
04
02
08
09
10
11
12
13
01
02
03
02
01
01
02
03
01
02
09
01
01
01
02
01
02
03
01
02
02
0505
01
01
01
01
Cadmium Concentration, pg/m-^ '
1972
0.001
0.005
0.002
0.001
0.003
0.001
0.004
0.008
0.001
0.001
0.003
0.001
0.001
0.001
0.002
0.001
0.012
0.003
0.001
0.001
0.004
0.0001
0.001
0.0001
0.001
0.002
0.001
0.001
0.006
0.001
0 . 002
0.001
0.001
0.001
0.001
0.001
1973
0.003
0.001
0.001
0.001
0.001
0.001
0.001
0.006
0.011
0.002
0.001
0.001
0.005
0.002
0.002
0.006
0.002
0 . 004
0.006
0.003
0.001
0.001
0.004
0.001
0.00 1
0.001
0.002
0.001
0.001
0.007
0.006
0.007
0.001
0.001
0.001
0.005
0.001
0.001
0.003
0.001
0.001
1974
0.001
0.001
0.002
0.001
0.001
0.001
0.001
0.008
0.001
0.002
0.001
0.004
0.003
0.001
0.001
0.001
0.001
0.009
0.006
0.001
0.001
0.002
0.001
0.001
0.001
0.001
0.004
0.003
0.003
0.001
0.001
0.001
0.001
0.002
0.001
1975 1976
0.001
0.004
0.001
0.008
0.001
0.002
0.003
0.004
0.001
0.002
0.001
0.001
0.001
0.001
0.001
0.006
0.002
0.002
0.001
0.002
0.002
0.002
0.001
0.001
0.004
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.001
0.0034
0.002
0.0032
0.0035
0.005
0.0039
0.002
0.11
0.004
0.003
0.003
0.004
2-9
-------
TABLE 2.2. (Continued)
Location
Missouri
Mexico
New Madrid
North Kansas City
Platte County
Poplar Bluff
Rolla
St. Joseph
St. Joseph
Sedalia
Sikeston
Montana
Anaconda
Anaconda
Billings
Billings
Butte
Butte
Butte
Butte
Butte
Butte
Butte
Butte
Cascade County
Columbia Falls
Deer Lodge
Deer Lodge
Deer Lodge County
Deer Lodge County
Great Falls
Hard in
Keiispull
Lewis and Clark
Libby
Miles City
Powder River County
Rosebud County
Sanders County
Silver Bow County
Oklahoma
Ada
Bartlesville
Bethany
Blackwell
Blackwell
Blac:kwell
Edmond
Edmond
Midwest City
Midwest City
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Station
Number 1971
04
01
04
01
02
01
02
03
05
02
05 0.0301d
06
05 0.001
08 0.0001
01 0.017
02 0.0221d
03 0.01
04 0.019
05 0.012
06 0.0176d
07 0.023
10
16 0.0001
02
01 0.008
02 0.002
01 0.046
21 0.017
07
01
02
06
01
01
06
21
01
07 0.0660
243 0.0070
216
14
591 0.0040
548 0.0140
549
16
16
06
10
01
01
15
15
17
17
18
21
Cadmium Concentration,
1972 1973 1974
0.003
0.013
0.009
0.013
0.003
0.014
0.1500
0.017
0.002
0.002
0.009
0.002
0.001
0.0020
0.0720
0.0010
0.0001
0.0001
0.0010
0.0020
0.0770
0.0060 0.0028
0.0005 0.0005
0.0130 0.0025.
0.0001
0.0005 0.0005
0.0005 0.0005
0.0005 0.0005
0.0001
0.0005 0.0005
0.0005 0.0001
0.0005 0.0005
0.0030
0.0020 0.0024
0.0030
0.0005 0.0020
0.0001
/ 3b'c
yg/m-"
1975 1976
0.0044
0.0018
0.0037
0.002
0.004
0.002
0.0059
0.0047
0.0065
0.0026
0.0005 0.0005
0.0005 0.0005
0.0005 0.0024
0.0005 0.0005
0.0005
0.0005
0.0005
0.0005 0.0005
2-10
-------
TABLE 2.2. (Continued)
l.ocat imi
Ok.lahoma
Oklahoma City
Oklahoma City
Oklahoma CiLy
Oklahoma City
()klalH>ma County
Oklahoma County
Ponci.1 City
Pryor
Sapulpa
Sapulpa
Tt-'iinusHL't.1
Columh in
K ingsport
Kingsport
Marion County
Morr is town
I'oIk CounLy
Korkwooil
TnIlahoma
1'u 1 I ahoma
Stat ion
Number
1971
Cadmium Concent rat ion,
'l9~72 1973 1974"
0.0250
0.0040
0.0005
0.0001
0.0005
0.0005
0.0001
0.0005
1975
0.0005
0.0005
0.0005
0.0005
0
0
0
0,
0.
ii
0
0.
0,
. 00 'j
.0001
.0020
.0020
.0020
. no.-o
.0020
.0020
.002(1
0
0
0.
0,
0,
0,
0,
0.
.0001
.0020
.0020
,0020
,0020
,0020
,0020
,0020
0
0
0,
0,
0,
0,
0,
0,
0.
.0020
.0020
.0020
.0020
.0020
.0020
.0020
.0020
.0020
1976
0.0005
0.0005
Sourri.': ('.:'•. Muv i roniin-nt a I 1'rol i-f I i on Agi'in-v SAIiDAI) l-'ili', Durham, North Carolina.
DcLc rm i iK'il hv .it'omii1 .ihsorpt ton on Iow-[ rmprr.it uri1 ashed -..imp I rs .
r>0 pi-rrcnl di-riU' valnr, i-xn-pl as nolrd.
2-11
-------
TABLE 2.3. ATMOSPHERIC CADMIUM CONCENTRATIONS FOR NONURBAN
SAMPLING STATIONS IN EIGHT STATES, 1971-1976a
Station
Arizona
Coconino County
Coconino County
Coconino County
Kavapai County
Gila County
Maricopa County
Maricopa County
Maricopa County
Maricopa County
Navajo County
Pima County
Pima County
Pima County
Winslow
Minnesota
Lake County
Stearns County
Montana
Beaverhead County
Big Horn County
Billings
Deer Lodge County
Deer Lodge County
Jefferson County
Rosebud County
Rosebud County
Oklahoma
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Oklahoma City
Ottawa County
Section
Number
02
03
04
02
03
03
06
07
08
01
05
09
10
01
01
04
02
08
07
03
22
04
09
24
02
02
19
20
20
25
3b
Cadmium Concentration, yg/m
1971 1972
0.0001 0.001
0.0001 0.001
0.0001
0.0001 0.001
0.003
0.0001 0.001
0.0001 0.001
0.0001
0.0020
0.0001
0.0001
0.02
0.018
0.032
0.0001
1973
0.001
0.0001
0.0029C
0.001
0.0001
0.0001
0.0001
0.006
0.001
0.0020
0.0060
0.001
0.0001
0.0010
0.0019
0.0005
0.0005
1974
0.001
0.001
0.003
0.001
0.0005C
0.0016C
0.0045C
0.001
0.001
0.002
0.002
0.0020
0.0001
0.0001
0.0005
0.0005
0.0001
0.0005
0.0001
1975 1976
0.0006C
0.0006C
0.004C
0.0030
0.0005 0.0005
0.0005 0.0005
0.0005 0.0005
Source: U.S. Environmental Protection Agency SAROAD File, Durnham, N.C.
Determined by atmoic absorption on low-temperature ashed samples; 50 percent
decile value, except as noted.
°Annual average.
2-12
-------
p.., 11/5/7."
Cily AY.roge !i_i_i.
High _.'
low -JL
Wind Oi«»elion il5 V»l 10 • * mph
Figure 2.3. Ambient atmospheric cadmium concentrations, Chicago,
Illinois, November 5, 1972 [Reprinted from Advances in
Experimental Medicine and Biology, Volume 40 (Sanat K.
Dhar, Editor) by P. R. Harrison, by permission of Plenum
Publishing Company. Published 1973.]
2-13
-------
.0
Figure 2.4. Ambient atmospheric cadmium concentrations, Chicago,
Illinois, November 23, 1972 [Reprinted from Advances in
Experimental Medicine and Biology, Volume 40 (Sanat K.
Dhar, Editor) by P. R. Harrison, by permission of Plenum
Publishing Company. Published 1973.].
2-14
-------
As a part of a broad-scale investigation for the National Science
Foundation (NSF) examining the environmental flow of cadmium and other trace
metals, Yost et al. (1975) have studied northwestern Indiana and the metro-
politan Chicago area in considerable detail. A statistical study of Chicago
atmospheric dust concentrations (TSP) and meteorological data including wind
speeds and precipitation led to the conclusion that the generally overlooked
phenomenon of reflotation of dust appeared to account for approximately 20
percent of the annual TSP value in Chicago, and that daily values of TSP may
be increased by as much as 40 to 50 percent due to winds and traffic on a
dry day. The possibility of reducing TSP by street sweeping and washing was
suggested. Although no such specific conclusion was drawn, it is inferred
that urban Chicago atmospheric cadmium concentrations could be similarly
reduced.
Trends in Cadmium Atmospheric Concentrations
Cadmium concentrations in the atmosphere of the U.S. are, with very
few exceptions, of the order of a few hundredths or thousandths of micrograms
per cubic meter of air. Principal exceptions to the above generalization are
found in a few areas where zinc or lead mining and smelting is or has been
conducted. The most notable exceptions are in Idaho and Montana, as
evidenced by the 1971-1976 state data (Tables 2.2 and 2.3). Both median
values and annual averages exceeding 0.1 yg/m3 of cadmium were reported for
Kellogg, Idaho, and the surrounding Shoshone County for 1974 and 1975.
Kellogg is the site of a lead smelter; and an electrolytic zinc plant, which
is one of the principal producers of primary cadmium metal, is located in
nearby Wallace, Idaho. Data prior to 1974 are not available for these
stations, so long-term trends are indeterminate, although 1975 values are,
without exception, below the corresponding values for 1974 (Table 2.2).
The Butte (Jefferson County)-Anaconda (Deer Lodge County)-Helena
(Lewis and Clark counties) triangle in Montana is a center of copper and
lead mining, smelting and refining, and this is reflected in the atmos-
pheric cadmium concentrations reported for this area (Tables 2.2 and 2.3).
Although lower than in the Wallace-Kellogg area, they are as much as an
order of magnitude higher than average U.S. cadmium concentrations.
Jefferson County, Missouri, is the site of a lead smelter, Hercu-
laneum, and the highest median concentrations of cadmium, 0.100 yg/m3,
in the 1975 tabulation is in this county (Table 2.2).
An information resource which has to date been overlooked or
neglected is the filters from the numerous local monitoring programs which
are conducted by various state and local agencies. Many of these are
routinely collected and stored in state agency headquarters. As a result
of staff and funding problems, many of these filters are stored for long
periods before analysis, which frequently consists only of particulate
determination. These filters, if they have been carefully handled and
stored, could supply a large mass of data on heavy metal concentrations
if analyzed. Now that atomic absorption spectrometry (AAS) is so
2-15
-------
universally available and so utilitarian, the retrieval of this information
from old filters is a practical possibility. Consequently, some of the gaps
in atmospheric cadmium data for prior years could be filled in by the
adoption of this scheme.
The uncertainties in the NASN data, the changing analytical proce-
dures, the lack of sufficient series of comparable continuous data, and
the generally barely detectable cadmium concentrations preclude the
identification of definite quantitative trends in ambient atmospheric
cadmium concentrations.
A definite downward trend is apparent for atmospheric cadmium
concentrations associated with metal industry sources at urban sites
(Figure 2.2) (Faoro and McMullen, 1977). With the exception of an
unexplained increase in 1969, the concentrations declined from 1965 through
1970. For the period 1970-1974, the concentrations were below the lower
discrimination limit. Possible causes given by Faoro and McMullen for this
downward trend are reduced particulate emissions from metals industries and
improved incineration and waste-burning practices.
No apparent trends are evident in the eight-state data, in spite of
the precision of the analytical procedure used. Part of the difficulty in
assessing these preliminary results arises from the fact that most of the
tabulated data are 50 percent decile values, since averages were computed
in,only a few cases. These median values were generally lower than
arithmetic averages, where both were reported, and more closely approxi-
mated than the geometric means. Although the decile values cannot be
summed and averaged, it is evident by inspection that the median value of
these data, smelting areas expected, is approximately yg/m3. Whether this
truly represents a decreasing trend from past years is obscured by the lack
of analyses of comparable accuracy for previous years.
WATER AND SEDIMENT
National Monitoring Programs
In the autumn of 1970, a nationwide reconnaissance of selected minor
elements in the surface waters of the 50 states and Puerto Rico was con-
ducted by the U.S. Geological Survey in cooperation with the U.S. Fish and
Wildlife Service (Durum et al., 1971). More than 720 samples were analyzed
for arsenic, cadmium, chromium, cobalt, lead, mercury, and zinc. Samples
were taken from three sources: (1) benchmark stations (located in headwaters
of tributary streams); (2) surface water sources for cities greater than
100,000 pouplation (or largest city in state); and (3) water courses
downstream of major municipal and/or industrial complexes. Samples were
filtered through a 0.45-micron filter and were acidified when collected to
stabilize the trace pollutants present. Thus, results reported are for
dissolved metal only and provide no information on total concentrations
present. Such results may be low, since cadmium tends to be associated with
the particulate matter. The detection limit given for cadmium was less than
1 ppb by AAS.
2-16
-------
The benchmark station analyses have been abstracted from these results
and are presented in Figure 2.5 grouped by drainage basin. Of the 49 bench-
mark station samples analyzed, cadmium was detected in only 24 (49 percent).
In none was the 10 ppb U.S. Public Health Service limit for potable water
exceeded. There were some differences in basins. Even though the benchmark
stations were presumably near headwaters and above sources of man-made pollu-
tion, the more industrialized areas and the down-gradient areas had the
higher cadmium levels. Highest values were found in the Lower Mississippi
River Basin(7), the Ohio River Basin(3), and the North Atlantic Basin(l).
Cadmium was detected in 42 percent of the total group of 720 samples
in concentrations ranging from 1 to 10 ppb. This included not only the
benchmark stations but also several hundred public water supplies and
industrial complex samples. The regional distribution of percentages of
water samples containing detectable cadmium concentrations has been
presented in a subsequent paper by Durum (1974), and is illustrated by
Figure 2.6 and summarized as follows:
Maximum, Minimum, Median, <1 ppb, >1 ppb,
ppb ppb ppb % %
New England and northeast 32 <1 2 36 64
Southeastern 90 <1 <1 55 45
Central 40 <1 <1 55 45
Southwestern 130 <1 <1 65 35
Northwestern 21 <1 <1 78 22
The association of detectable correlation of cadmium concentrations
with regions of higher population density is evident upon comparing the New
England and northeastern area, 64 percent, with the Northwestern area, 22
percent. About 4 percent of the river samples had cadmium in excess of the
10 ppb Public Health Service limit for drinking water, and these occurred in
about one-third of the states. The maximum concentration found was 130 ppb,
near Ray, Arizona, evidently near a highly mineralized area, since the same
sample had 42,000 ppb of zinc and 4,500 ppb of cobalt.
The USGS maintains a computerized data bank for six toxic substances,
cadmium, lead, mercury, PCB's, Silvex, and Toxaphene, in water and stream
sediments. A summary of these data was submitted by the USGS to the Commit-
tee on Merchant Marine and Fisheries, U.S. House of Representatives
(Pickering, 1976). The data for cadmium in surface waters (streams, lakes,
reservoirs) and in groundwaters (wells and springs) have been extracted from
this summary and are presented in Tables 2.4 and 2.5, and summarized in
Table 2.6.
Dissolved values shown are based on the analyses of water passed
through a 0.45 micrometer filter; "total" values are for unfiltered samples
containing suspended sediment. Dissolved values are compared with the 10
ppb maximum cadmium level contained in the National Interim Primary Drinking
Water Regulations (U.S. Environmental Protection Agency, 1975a). For "total"
values the comparison is with the 30 ppb criterion recommended in Water
Quality Criteria 1972 for freshwater aquatic life and wildlife (Rooney,
2-17
-------
ND1
Range (1) 1
~ ^^fcf
ND2
Range (1J 1 ppb
"*-^. ^ ^*~-
ND 2
Range (1) 1 ppb
*_^_
H1
oc
ND1
Range (4) l-6_
ND4
Range (4) 1-5 ppb
Figure 2.5. Cadmium concentrations in surface waters at USGS benchmark stations
in 1970 (Durum et al., 1971).
ND = Not detected. The number following ND is the number of stations,
( ) = Number of stations with detectable cadmium concentrations.
-------
Figure 2.6. Percent of river water samples containing cadmium
>1 ppb in five U.S. regions (Durum, 1974).
-------
TABLE 2.4. CADMIUM LEVELS IN SURFACE WATERS OF THE UNITED STATES
a,b
Dissolved
(Filtered
Cadmium
Sample)
Total Cadmium
(Unfiltered Sample)
N >10 Max,
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Hawaii
Idaho
Illinois
Indiana
Iowa
Kansas
Kentucky
Louisiana
Maine
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Carolina
South Dakota
Tennessee
Texas
Utah
Vermont
Virginia
Washington
West Virginia
Wisconsin
Wyoming
United States
N
97
69
21
37
154
495
63
10
280
136
9
76
26
45
33
24
103
271
' 14
21
25
125
41
20
72
101
99
11
5
62
53
185
67
78
44
52
24
218
8
11
47
28
162
43
4
17
21
53
38
64
3,755
N >0
90
26
15
29
78
221
50
10
105
68
5
57
16
23
22
15
79
157
10
21
15
80
29
12
51
65
70
6
3
40
58
179
56
63
34
36
20
175
8
11
37
18
135
29
4
15
15
39
15
28
2,423
ppb
14
1
0
1
3
47
32
0
2
0
0
11
4
0
6
0
6
11
5
0
0
3
0
1
10
5
6
1
0
27
19
137
6
5
10
2
0
20
4
0
3
1
3
8
0
7
1
5
0
3
430
ppb
90
140
10
14
340
910
78
2
13
5
2
1,400
16
10
40
8
18
25
<2,000
6
6
20
8
11
80
55
89
20
2
<2,400
714
220
50
26
100
30
5
100
10
7
14
190
30
270
6
50
10
25
10
38
1,400
N
34
51
12
128
118
197
2
0
293
9
48
39
13
19
5
9
72
71
9
13
9
38
29
66
14
74
16
10
19
38
26
122
44
65
33
60
13
198
4
11
15
47
29
15
1
4
17
51
14
59
2,283
N >0
32
34
12
118
83
190
2
0
210
7
12
39
8
13
4
9
63
69
4
4
9
31
26
41
14
72
16
10
15
31
26
57
41
62
15
60
13
184
4
10
15
35
29
15
1
4
17
38
10
55
1,869
N >30
ppb
0
2
0
3
20
53
0
0
1
0
0
5
0
0
0
0
0
1
0
0
1
0
0
0
1
3
2
0
0
0
3
7
. 32
2
1
6
0
14
4
0
2
1
1
0
0
0
2
0
0
1
168
Max,
ppb
10
360
20
111
80
960
10
35
5
10
440
20
10
20
20
23
60
1
1
550
10
20
25
60
30
211
20
16
12
40
230
80
30
76
100
10
420
210
16
30
840
50
20
1
2
40
22
3
30
960
Cadmium in
Bottom Material
N
5
0
1
13
26
0
38
0
52
11
3
1
6
14
0
1
39
169
2
1
7
0
20
51
2
5
0
0
2
10
1
6
18
3
1
7
4
35
0
5
0
1
3
0
0
0
0
15
13
0
591
N >0
4
0
1
12
22
0
22
0
52
11
1
0
4
10
0
0
39
143
1
0
7
0
20
50
0
5
0
0
2
2
1
3
17
2
1
6
4
27
0
4
0
0
2
0
0
0
0
0
10
0
485
Max,
ppb
10
1
10
10
9
20
20
1
0
4
10
0
20
10
2
0
300
10
10
0
10
2
1
1
3
20
10
1
8
3
10
10
0
1
0
10
300
aSource: Pickering, 1976.
N = Number of stations for which data are available.
N >0 = Number of stations with detectable cadmium.
Max = Maximum value found.
2-20
-------
TABLE 2.5. CADMIUM LEVELS IN GROUND WATERS OF THE UNITED STATES
,a,b
Dissolved
(Filtered
Cadmium
Sample)
Total Cadmium
(Unfiltered Sample)
N >10 Max,
State
Alabama
Alaska
Arizona
Arkansas
California
Colorado
Connecticut
Delaware
Florida
Georgia
Idaho
Indiana
Iowa
Kentucky
Louisiana
Michigan
Minnesota
Mississippi
Missouri
Montana
Nebraska
Nevada
New Hampshire
New Jersey
New Mexico
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
Pennsylvania
Rhode Island
South Dakota
Tennessee
Texas
Utah
Virginia
Washington
West Virginia
Wisconsin
Wyoming
United States
N
54
69
21
25
30
354
22
0
232
192
10
50
13
' 14
24
17
40
4
0
41
211
90
0
24
99
258
2
77
0
9
4
146
0
60
0
50
43
6
41
19
31
52
2,431
aSource: Pickering,
b
/if c> t- 1
N >0
31
12
7
3
12
141
8
75
102
3
32
13
10
9
5
14
3
8
40
79
18
36
28
0
29
1
1
86
28
20
13
2
33
12
13
13
940
1976.
.
ppb
1
0
0
0
3
6
2
7
7
0
I
0
1
0
1
9
0
0
1
65
14
8
0
0
0
0
0
16
8
0
0
0
0
0
0
0
150
.
ppb
32
4
9
10
1,400
690
21
21
18
1
60
10
<10
4
100
2
4
5
13
900
500
51
8
0
3
1
1
120
28
1
10
5
10
1
9
9
1,400
N
7
14
0
0
7
20
0
1
338
0
0
0
0
12
0
23
145
9
17
0
0
0
16
39
8
188
6
11
2
0
11
3
12
9
18
0
0
0
0
19
0
54
859
N >0
5
14
7
20
0
192
9
8
145
7
17
2
12
8
26
6
10
1
10
0
10
9
4
2
54
448
«vi „
N >30 Max,
ppb
0
1
0
6
0
0
0
0
0
0
0
0
0
3
0
6
0
0
0
0
0
0
0
0
2
18
ppb
7
60
10
<7,500
0
20
5
21
10
- 4
10
8
10
750
8
170
20
1
10
0
1
12
2
1
60
750
N >0 = Number of stations with detectable cadmium.
Max = Maximum value found.
2-21
-------
TABLE 2.6. SUMMARY OF CADMIUM CONCENTRATIONS IN U.S. WATERS
Surface Waters Groundwater
Dissolved Total Dissolved Total
Number of states sampled 50 49 36 25
Number of sites sampled 3,755 2,283 2,431 859
Positive values
Number 2,423 1,869 940 448
Percent 64.5 81.0 38.7 52.2
Values >10 ppb
Number 430 150
Percent 11.5 6.2
Values >30 ppb
Number 168 18
Percent 7.4 2.1
Maximum value, ppb 1,400 960 1,400 750
1973). In 6 to 12 percent of the samples dissolved cadmium exceeded
the 10 ppb limit recommended for drinking water, and in 2 to 7 percent
total cadmium exceeded the 30 ppb water quality criterion recommended for
cadmium by the National Academy of Sciences. The USGS data indicate that
on the average, groundwater quality with respect to cadmium exceeds that of
surface waters.
Although the ocean is the final sink for most of the cadmium
dispersed to the environment, the present concentration of cadmium in the
oceans, approximately 0.11 ppb, is much lower than that which would be
calculated from the cumulative natural input, suggesting that cadmium is
being continuously deposited from ocean waters (Fleischer et al., 1974).
James of Stanford University suggests that one vehicle for bioaccumulation
of cadmium in polluted waters might exist because of the metal's strong
propensity to form chloride ion complexes. These complexes would make
cadmium more available to marine organisms, because it is less removable
than, say, lead and zinc, through oxide and carbonate sedimentation
(Anonymous, 1977). There is no national program for monitoring sediment
concentrations of cadmium.
Local Monitoring of Cadmium Concentrations
Results of an unpublished EPA study (U.S. Environmental Protection
Agency, 1976b) present information on the cadmium contents observed in
2-22
-------
395 sediment samples collected from harbors along the shores of the Great
Lakes between Erie, Pennsylvania, and Duluth, Minnesota. As shown in the
frequency distribution curve in Figure 2.7, over 90 percent of the samples
contained less than 10 ppm and over 80 percent contained less than 5 ppm.
The median was below 2 ppm. Eight samples, all from Michigan City,
Indiana, exceeded 35 ppm; these would appear to represent gross contamina-
tion from a point source.
The Ohio River Valley Water Sanitation Commission has monitored for
cadmium on the Ohio River and its major tributaries. Some of the recent,
1975-1976, results are presented in Table 2.7 to illustrate typical surface
water cadmium concentrations in an industrial area. It is apparent that
there is no consistent trend of increasing cadmium concentration with
downstream distance; if anything, the lower values are found closer to the
junction of the Ohio River and the Mississippi River at Cairo, Illinois.
Cadmium concentrations above 2 ppb are typically found in the upstream
reaches, above Cincinnati, Ohio. These data suggest that dilution (or
precipitation) is occurring as the river proceeds downstream.
The Coeur d'Alerie region of Idaho is an important lead-zinc district
in which mining and smelting operations have been conducted for many years.
The South Fork of the Coeur d'Alene River passes the mining and smelting
operations at Kellogg and Wallace on its way to Coeur d'Alene Lake, approxi-
mately 60 km to the west. Elevated cadmium concentrations have been
measured in this river. Mink et al. (1971) reported cadmium concentrations
as high as 450 ppb. Roberts et al. (1975) reported mean concentrations
ranging between 150 and 300 ppb for 100 samples taken from the river in 1970
and 1971; the range of individual concentrations was from 1 to 3,600 ppb.
These data are believed to be total cadmium, i.e., the samples were unfilter-
ed. Maxfield et al. (1974), investigating the sediments in the lake,
observed cadmium concentrations in the sediments ranging from 30 to 90 ppm.
Concentrations were greatest in silt, typical of mine tailings.
Cadmium is found to concentrate in sediments, and whereas water
concentrations are in the ppb range, cadmium concentrations in sediments
are in the ppm range. A number of investigations of cadmium concentrations
in sediments have been frequently conducted in connection with the study of
a known or suspected point source. Perhac (1974) investigated heavy metal
concentrations in the aquatic environment in a region of Tennessee which was
highly mineralized, including sphalerite (ZnS). He found cadmium concentra-
tions of 3 to 8 ppm in local stream sediments. In this same region of
Tennessee, Perhac and Tamura (1977) found cadmium concentrations approaching
100 ppm in bottom sediments downstream from a zinc mill. Even so, the
dissolved cadmium in the overlying river water was only 3 ppb, which is
typical of the region.
Yost et al. (1975) found high cadmium contents in the sediments of
Palestine Lake, a small lake in Indiana which had received effluents from a
plating operation for a period of years. Contents ranged from 0.7 to 19.8
ppm, with a mean concentration of 9.1 ppm. Similarly, they found sediments
2-23
-------
100
90
80
0)
3
rH
cO
s70
cfl
4-1
C/3
g
60
c
0)
o
•H
4-1
CO
iH
40 -
30
10 15 20 25
Cadmium in Sediment, ppm
30
35
Figure 2.7. Frequency distribution of cadmium
in Great Lakes sediments.
2-24
-------
TABLE 2.7. CADMIUM CONCENTRATIONS IN THE OHIO RIVER AND SOME OF ITS TRIBUTARIES
I
IS5
Location
Illinois
Ohio River at Joppa
Indiana
Ohio River at Evansville
Ohio River at Uniontown
Kentucky
Licking River, Kenton County
Ohio River at Louisville
Ohio River at West Point
Green River at Sebree
Ohio
Ohio River at East Liverpool
Ohio River at Shadyside
Muskingum River at Marietta
Ohio River at Belleville
Ohio River at Kyger Creek
Ohio River at Kenova
Scioto River at Lucasville
Ohio River at Meldahl
Ohio River at Cincinnati
Little Miami River
Great Miami River
Pennsylvania
Allegheny River at Oakmont
Monongahela River at South Pittsburgh
Ohio River at South Heights
Beaver River at Beaver Falls
West Virginia
Ohio River at Pike Island
Ohio River at Willow Island
Date of Data
Collection
9/75-4/76
11/75-4/76
11/75-4/76
9/75-4/76
10/75-4/76
11/75-4/76
9/75-4/76
9/75-3/76
9/75-10/75
9/75-4/76
9/75-4/76
10/75-4/76
11/75-4/76
10/75-4/76
10/75-4/76
10/75-4/76
9/75-4/76
10/75-4/76
9/75-3/76
9/75-3/76
9/75-3/76
9/75-3/76
9/75-4/76
9/75-4/76
Number of
Samples
7
6
6
8
7
6
7
8
2
8
8
7
6
7
7
7
8
6
7
7
8
8
8
8
Frequency of
Detection, %
57
50
50
25
43
83
57
100
50
100
100
100
83
71
86
43
50
100
86
86
88
63
88
75
Concentration, ppb
Mean
0.86
0.50
1.0
0.25
0.57
1.5
0.57
2.13
2.5
2.13
2.13
1.57
1.33
0.86
1.14
0.43
0.63
1.0
2.14
1.86
2.25
1.13
2.00
2.38
Range
0-2
0-1
0-3
0-1
0-2
0-2
0-1
1-4
0-5
1-4
1-4
1-3
0-4
0-2
0-2
0-1
0-2
0-1
0-4
0-6
0-6
0-3
0-4
0-5
Source: Ohio River Valley Water Sanitation Commission, 1975, 1976.
-------
in the Grand Calumet River in the highly industrialized Chicago area to
range from 1 to 20 ppm, with means in the 6 to 7 ppm range. Kneip et al.
(1975) found, in Foundry Cove, near Cold Springs on the Hudson River in
New York, extremely high cadmium contents in sediments immediately below
the effluent outfall of a nickel-cadmium battery plant. In 1971, values
ranging from 33 to 60,700 ppm were detected; in 1973, the range was from 3 to
48,000 ppm. These reports are illustrative of the cadmium concentrations
which can be reached in sediments exposed to cadmium sources and are
confirmed by other studies in similar environments. However, they repre-
sent localized problems and cannot be considered representative of average
cadmium concentrations in sediments.
Sediments not exposed to industrial or mining wastes are lower in
cadmium and may contain only fractions of a ppm. Illustrative are the
results of Proctor et al. (1975) in the Meramec River Basin of Missouri.
In nonmineralized areas, mean cadmium concentrations in river sediments were
0.3 to 0.4 ppm, whereas in the mineralized area near Viburnum, the range was
from 0.2 to 18 ppm, with a mean of 4 ppm.
Cadmium concentrations in marine sediments have been investigated
at a number of U.S. locations in harbors, estuaries, and offshore. Harbor
sediments can carry appreciable contents of cadmium. Villa and Johnson
(1974) determined concentrations of less than 1 to 654 ppm, with an
average concentration of 6.3 to 6.6 ppm in Baltimore Harbor. Roberts
et al. (1975) found 3.3 to 29 ppm, mean 12.5 ppm, in the inner portion of
Boston Barbor, and 0.8 to 13 ppm, mean 6.2 ppm, in the outer harbor.
Moyer and Budinger (1974) found values ranging from 0.7 to 1.5 ppm in
San Francisco Harbor.
Cadmium concentrations in offshore sediments appear to be much lower
than harbor concentrations, even in the vicinity of dumpsites, presumably
as a result of large dilution provided by ocean dumping. Szucs and Oostdam
(1975), investigating heavy metals in sediments of ocean dumpsites found,
for example, that around the present and former dumpsite used by Philadel-
phia for sewage sludge, mean cadmium concentrations ranged from 0.05 to
0.13 ppm, with a maximum concentration of 0.37 ppm in a slough close to the
former dumpsite.
Information describing the long-term fate of cadmium in nonmarine
sediments appears to be lacking. The presumption is that the cadmium is
fairly well immobilized, and barring physical disruption, such as by
dredging, will remain so. River bottom sediments are likely to be gradually
transported to the lake or marine estuary into which the river empties, but
it does not necessarily follow that a significant fraction of the cadmium
will be liberated in -this transit.
DRINKING WATER
One of the first broad-based investigations of cadmium concentrations
in drinking water was included as a part of the Community Water Supply
2-26
-------
Survey conducted in 1969 by the U.S. Public Health Service (U.S. Department
of Health, Education, and Welfare, 1970). The study was designed to give an
assessment of drinking water quality in urban and suburban areas in each of
the nine HEW regions. It included an entire Standard Metropolitan Statisti-
cal Area (SMSA) in eight regions; in Region I, the entire state of Vermont
was studied. As reported by Taylor (1971), in only 4 out of 2,595 distribu-
tion samples (0.15 percent) did cadmium content exceed the 10 ppb Drinking
Water Standard; these were found in 3 out of the 969 water systems investi-
gated. The three systems each served a population of less than 100,000
people. The average concentration was 3 ppb; the maximum sample contained
3.94 ppm. Method of analysis was atomic absorption (McCabe et al., 1970).
No data were presented by either Taylor or McCabe et al. on the number of
samples below the limit of detection, estimated to be 1 ppb. In a later
paper, McCabe (1974) described the average cadmium concentration determined
by the study as 1.3 ppb and also claimed that 63 percent of the samples were
above a 1 ppb detection limit.
At the time EPA was established (1970), it was assigned the responsi-
bility of certifying water supply systems serving interstate carriers,
formerly the responsibility of the Public Health Service, Department of
Health, Education, and Welfare. Analytical data for 735 sampling points
covering the U.S. and possessions through March 1, 1975, have been reported
and summarized by EPA (U.S. Environmental Protection Agency, 1975a). Out
of 594 analyses, none failed to meet the USPHS Drinking Water Standards of
1962 for cadmium (10 ppb), and for only seven samples (1.2 percent) were
detectable limits higher than the standards.
In areas not known to be polluted from mining, smelting, or other
industrial cadmium sources, the concentration of cadmium in water is
generally less than 1 ppb in both natural and drinking waters (Friberg et al.,
1971). These observed levels fall well below the World Health Organization's
recommendation of less than 5 ppb cadmium (Joint FAO/WHO Expert Committee on
Food Additives, 1972). Because dissolution of metals from pipes is most
likely to occur in areas having soft "acid" (pH 5-6) water supplies, EPA has
conducted special studies of water systems where the water is particularly
corrosive to the distribution system and plumbing. Results of two of these
studies indicate that in Boston none of the homes were found to exceed the 10
ppb USPHS standard while in Seattle, 7 percent of the homes exceed the
standard (Deane et al., 1976). While low levels of cadmium are found in
municipal water supplies, additional uptake may be occurring between the inlet
and the consumer. A study reported by McCabe et al. (1970) showed that 15
percent of water samples had picked up cadmium between the treatment plant
and the distribution system.
2-27
-------
SLUDGE
The sludge resulting from treatment of wastewater contains small
but useful concentrations of the fertilizer elements, nitrogen, phosphorus,
and potassium as well as useful organic matter. It also contains most of
the toxic elements, including heavy metals, present in the raw wastewater,
since these tend to distribute to the sludge. Disposal options for sludge
are fairly limited. Municipal sewage sludge disposition in 1975 in the U.S.
has been reported to be 15 percent in the ocean, 25 percent in landfills,
35 percent by incineration, and 25 percent by application to land (CAST,
1976).
There is a wide range in reported values for metal contents in
sludge. There appears to be a significant correlation between the degree
of industrialization and elevated metal levels in sludges; and cadmium also
follows this pattern. Electroplating has been a major source of cadmium in
wastewater heretofore, and other industrial processes have contributed.
Data on cadmium contents of sewage sludge from U.S. cities have been compiled
from various sources by the EPA Office of Solid Waste and are given in Table
2.8.
The extreme variability between cities is quite evident. The lowest
values are for cities with little or no industry, and cadmium contents as
low as 2 ppm are reported. At the other extreme are Frankfort, Indiana,
with 3,171 ppm and Owosso, Michigan, with 1,100 ppm. Both are relatively
small (15,000 to 20,000 people) but fairly industrialized. Each has a large
battery manufacturer, and Owosso also has electroplaters.
Sommers et al. (1976) also obtained data on the variability over a
22-month period of the cadmium content of sludge from individual sewage
plants. As illustrated in Table 2.9, although the between-samples variations
were large, the between-plant variations were significantly larger. The
number of samples from each plant ranged from 5 to 7. Salotto et al. (1974)
reported the same conclusion from their study of about 100 samples collected
from 33 wastewater treatment plants in 13 states from the summer of 1971
through 1973.
Also reported in Table 2.8 are the cadmium:zinc ratios for the cities
where the cadmium content was greater than 25 ppm. Cadmium concentrations
ranged from 0.2 to 70 percent of the zinc concentrations. In 5 cities
out of the 60 reported the ratio was below the 1 percent advocated by the EPA
Draft Document on Acceptable Methods for the Utilization or Disposal of
Sludges (U.S. Environmental Protection Agency, 1974).
Even before the promulgation of EPA effluent guidelines regulations,
some cities had enacted ordinances to limit the discharge of heavy metals to
the sewer system. The Metropolitan Sanitary District of greater Chicago has
had such an ordinance since 1969 for the purpose of protecting the biological
processes utilized in sewage treatment (Zenz et al., 1975). The Chicago
ordinance, which limits cadmium concentration in incoming sewage to 2 ppm,
has produced a significant downward trend in cadmium concentrations, as
2-28
-------
TABLE 2.8. SEWAGE SLUDGE DATA ON U.S. CITIES (COMPILED OCTOBER 1976)'
City
New York NY
(Metropolitan Area)
Hampstead-Bay Park
Long Beach
Bowery Bay
Coney Island
Hunts Point
Jamaica
Newton Creek
Owls Head
Port Richmond
Rockaway
Tallmans Island
26th Ward
Wards Island
Hempstead-West
Long Beach
Yonkers
Chicago IL
North Side
Calumet
Hanover Park
Lemont
W. Southwest
Los Angeles CA
Philadelphia PA
N.E. Plant
S.W. & S.E.
Detroit MI
Year
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1975
1976
1976
1976
1976
1976
1976
1972-73
1976
1976
Cadmium
Content ,
ppm
70
18
47
8
18
4
71
18
3
16
6
17
6
4
163
35
180
42
10
16
210
171
90
25
290
Cd/Zn
Ratio, Present
T- C
% Disposition Source of Information
Ocean
6.3 Interstate Sanit. Com., 1975
n
0.9
"
"
11
1.9
"
n
"
11
n
11
n
8.2
3.0 Land application Ehorn (n.d.)
8.1 Give away "
1.8
11
"
7.8
3.7 Ocean, compost Furr et al., 1976
2 . 0 Ehorn (n.d.)
1.0
2.5 Incineration "
-------
TABLE 2.8. (Continued)
I
U)
o
City
Houston TX
North Side
Simms
Baltimore MD
Back River
Patapsco
Dallas TX
Washington DC
Cleveland OH
Southerly
Westerly
Indianapolis IN
Belmont
Southport
Milwaukee WI
Jones Island
South Shore
San Francisco area
Boston MA
Denver CO
Seattle WA
Atlanta GA
Newark NJ
Miami FL
Tampa FL
Little Ferry NJ
Grand Rapids MI
Year
1972-73
1976
1976
1976
1975
1972-73
1975
1973-75
1972-73
1972-73
1972-73
1975
1972-73
1975
1975
Prior to 1974
Cadmium
Content,
ppm
112
17
22
, . 2.5
7
9
59
22
390
578
240
260
444
107
50
15
82
46
64
104
173
149
10
240
480
Cd/Zn
Ratio,
%b
4.4
0.2
0.5
5.7
10.0
8.0
17.0
17.0
32.0
9.0
1.5
1.6
3.5
3.7
4.1
10.0
5.1
Present
Disposition
Fertilizer-soil
conditioner
Landfill
Lagoon
Land application,
landfill
Landfill
Incineration, land
application
Miloganite-soil
conditioner
Landfill , land
application
Ocean
Land application
Landfill or soil
conditioner
Landfill or soil
conditioner
Incineration
Soil conditioner
Land application
N.A.
N.A.
c
Source of Information
Furr et al. , 1976
Public Works Director
ti
Ehorn (n.d.)
ii
ii
Public Works Director
Camp et al., 1975
Ehorn (n.d.)
ii
ii
ii
Furr et al. , 1976
Ehorn (n.d.)
ii
Brown and Campbell, 1975
EPA (n.d.)
Furr et al. , 1976
it
ii
Interstate Sanit. Com.,
Furr et al. , 1976
1975
Greenley and Hansen, 1975
Interstate Sanit. Comm.
Blakeslee, 1973
(1975)
-------
TABLE 2.8.(Continued)
City
Flint MI
Syracuse NY
Madison WI
Warren MI
Macon GA
Elizabeth NJ
Camden NJ
Springfield MO
Saginaw MI
Pontiac MI
Kalamazoo MI
Ann Arbor MI
Anderson IN
Kokomo IN
Wyoming MI
Bay City MI
Jackson MI
Danville VA
Muskegon MI
Linden NJ
Battle Creek MI
Port Huron MI
East Lansing MI
Ithaca NY
Easton PA
Midland MI
Columbus IN
Holland MI
Ypsilanti MI
Sayreville NJ
Hopkinville IN
Cadmium Cd/Zn
Content, Ratio,
Year ppm %b
Prior to 1974
1972-73
Prior to 1974
1976
1975
1976
Prior to 1974
n
"
"
1972-74
1972-74
Prior to 1974
11
1976
Prior to 1974
1975
Prior to 1974
"
"
1972-73
Prior to 1974
1976
Prior to 1974
"
1975
1976
20
200
73
110
6
72
601
54
48
12
12
4
170
806
14
80
520
18
166
65
8
8
6
66
16
10
2
10
166
39
18
11.0
3.1
3.1
6.0
56.0
1.2
6.5
5.0
5.0
6.0
8.0
5.0
1.5
4.0
2.0
1.1
Present
Disposition
N.A.
Solvay process
N.A.
N.A.
Land application
N.A...
N.A.
Land application
N.A.
N.A.
N.A.
N.A.
Land application
Land application
N.A.
N.A.
N.A.
Land application
N.A.
N.A.
N.A.
N.A.
N.A.
Soil conditioner
Land application
N.A.
Land application
N.A.
N.A.
N.A.
Land application
Source of Information
Blakeslee, 1973
Furr et al. , 1976
Ehorn (n.d.)
Blakeslee, 1973
SCS Engineers, 1976
Interstate Sanit. Com., 1975
Ehorn (n.d.)
SCS Engineers, 1976
Blakeslee, 1973
"
11
ii r
Sommers et al., 1976
n
Blakeslee, 1973
n
n
SCS Engineers, 1976
Blakeslee, 1973
Interstate Sanit. Com., 1975
Blakeslee, 1973
"
"
Furr et al. , 1976
Blakeslee, 1973
SCS Engineers, 1976
Blakeslee, 1973
"
Camp et al. , 1975
SCS Engineers, 1976
-------
TABLE 2.8. (Continued)
City
Xenia OH
Monroe MI
Marquette MI
Muskegon Heights MI
Mt. Clemons MI
Trenton MI
Sault Ste. Marie MI
Logansport IN
Traverse City MI
Adrian MI
Owosso MI
Mt. Pleasant MI
Benton Harbor MI
Escanaba MI
Dixon IL
Frankfort IN
Las Virgenes CA
Peru IN
Crawfordsville IN
Iron Mountain MI
Albion MI
Niles MI
Grand Haven MI
Menominee MI
Cadillac MI
Lebanon IN
Noblesville IN
Marshall MO
Wilmington OH
Charlotte MI
Ironwood MI
Year
1976
Prior to 1974
n
n
n
11
n
1972-74
Prior to 1974
n
n
n
n
it
1976
1976
1976
1972-74
1972-74
Prior to 1974
"
n
n
ii
n
1972-74
1972-74
1976
1976
Prior to 1974
11
Cadmium
Content,
ppm
80
8
2
150
12
8
2
663
10
260
1,100
14
220
10
16
3,171
5
154
15
6
48
14
14
4
36
40
12
16
15
14
4
Cd/Zn
Ratio,
%b
0.6
1.0
4.0
5.0
20.0
1.7
70.0
6.0
1.5
3.0
1.6
Present
Disposition
Land application
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
Land application
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
Land application
Land application
Land application
Land application
Land application
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
Land application
Land application
Land application
Land application
N.A.
N.A.
Source of Information
SCS Engineers, 1976
Blakeslee, 1973
n
n
n
n
it
Sommers et al . , 1976
Blakeslee, 1973
n
n
n
n
n
SCS Engineers, 1976
n
"
Sommers et al., 1976
"
Blakeslee, 1973
"
"
"
n
ii
Sommers et al., 1976
"
SCS Engineers, 1976
"
Blakeslee, 1973
11
-------
TABLE 2.8. (Continued)
I
OJ
CO
City
Hancock MI
Three Rivers MI
Chippewa Falls WI
Litchfield IL
Kendallville IN
Marshall MI
Gladstone MI
Howell MI
Manistique MI
Tipton IN
Milford MI
Essexville MI
Norway MI
St. Ignace MI
Constantine MI
Dexter MI
Lanse MI
Cadmium
Content,
Year ppm
Prior to 1974 4
44
1976 7
1976 6
1976 28
1976 16
Prior to 1974 4
18
4
1972-74 . 11
Prior to 1974 . 2
" 4
n 2
4
16
36
8
Cd/Zn
Ratio, Present
%b Disposition
N.A.
1.0 N.A.
Land application
Land application
0.6 Land application
N.A.
N.A.
N.A.
N.A.
Land application
N.A.
N.A.
N.A.
N.A.
N.A.
2.5 N.A.
N.A.
Source of Information
Blakeslee, 1973
SCS Engineers, 1976
ii
"
Blakeslee, 1973
n
n
Sommers et al . , 1976
Blakeslee, 1973
n
"
n
n
n
Source: U.S. Environmental Protection Agency, Office of Solid Waste Management, 1976. Includes
the references listed in Footnote (c).
DThe Cd/Zn ratio is only listed when the Cd content is greater than 25 ppm.
"Sources of Information:
Blakeslee, Paul A. 1973. "Monitoring Considerations for Municipal Wastewater Effluent and Sludge
Application to the Land", Recycling Municipal Sludges and Effluents Joint Conference, Champaigne IL.
Brown and Caldwell. 1975. San Francisco Bay Area Municipal Wastewater Solids Management Study
(May 1975).
Camp, Dresser, and McKee. 1975. Alternative Sludge Disposal Systems for the District of Columbia
Water Pollution Control Plant at Blue Plains (December 1975) .
-------
TABLE 2.8. (Continued)
rt
Sources of Information (Continued)
Ehorn, Douglas. Personal communication. EPA-Region V; and Albert Montague, EPA-Region III. 1976,
EPA, Region I Office, Solid Waste Staff communication. 1976.
Furr, "AvK. ,"et al. 1976. Multielement and Chlorinated Hydrocarbon Analysis of Municipal
Sewage Sludges of American Cities. Journal of Environmental Quality (July 1976).
Greeley and Hansen. 1975. Report on Management and Disposition of By-Product Solids
Hookers Point Sewage Treatment Plant, City of Tampa, Florida (June 1975).
Interstate Sanitation Commission. 1975. Phase One Report of Technical Alternatives to
Ocean Disposal of Sludge in New York City. By Camp, Dresser, and McKee for New Jersey
Metropolitan Area (1975).
Public Works Directors, [n.d.] Personal Communication.
SCS Engineers. 1976. Environmental Assessment of Municipal Wastewater Treatment Sludge
Utilization Practices. EPA Contract No. 68-01-3265. Work ongoing.
Sommers, L. E., D. W. Nelson, and K. J. Yost. 1976. Variable Nature of Chemical Composition
of Sewage Sludges. Journal of Environmental Quality. 5(3).
~
-------
TABLE 2.9. VARIABILITY OF CADMIUM CONTENTS
IN SEWAGE SLUDGES3
Cadmium Content, ppm V.,
Minimum Maximum Median Mean %
Anderson
Crawfordsville
Kokomo
Lebanon
Logansport
Noblesville
Peru
Tipton
109
4
483
3
24
12
22
11
372
39
1,177
150
756
163
256
32
170
15
806
40
663
12
154
11
210
19
846
53
503
42
136
16
45
67
27
95
63
160
69
54
Average 72
Source: Sommers et al., 1976.
V. = Standard deviation expressed as a percentage
of the mean.
evidenced by typical sludge concentrations from the Calumet Sewage Treatment
Plant:
Cadmium Concentration,
Year
Sludge Source
1969 Lagoons
1972 Anaerobic digester
1974 Anaerobic digester
190
100
54
Cadmium concentrations reported in digested sludges from this plant in
Chicago have been reduced by 72 percent during the period 1969-1974. Data
for 1976 were similar to those for 1974, indicating that industrial pre-
treatment has reached its level of effectiveness (CAST, 1976).
Simultaneously, zinc concentrations have also dropped markedly, from
5,500 to 2,800 ppm, and the cadmium:zinc ratio has steadily decreased from
3.4 to 1.9 percent. It is still a long way from the 1 percent ratio proposed
in the EPA draft guidelines.
There has been some controversy over the need for a cadmium:zinc
ratio of 1 percent or less, especially in view of the fact that most sludges,
from all but essentially unindustrialized areas, will not achieve this ratio
2-35
-------
(Zenz et al., 1975). They note that the EPA discussion of the draft guide-
lines stated that more than 50 percent of the 188 sludges examined would not
qualify.
In view of the variability of sludges, as indicated above, only very
approximate estimates of input to the environment from this source can be
made. Fulkerson and Goeller's (1973) estimate assumed a cadmium content in
sludge of 15.6 ppm, based on some Swedish data. On the basis of recent U.S.
data such as described above, 15.6 ppm appears to be low for the more indus-
trialized wastes of this country. Sargent and Metz (1975), using an assumed
average cadmium content of 75 ppm, derived an estimate of 300/MT yr from
sludge. They further assumed that 60 percent is applied to land, 10 percent
is dumped at sea, and 30 percent is incinerated, producing 20 metric tons of
air emissions, at an incinerator scrubber efficiency of 80 percent.
ROCKS AND SOILS
Cadmium is one of the minor nonferrous metals, ranking 57th in
abundance in the earth's crust, between mercury and silver, 0.1 to 0.5 ppm
(Howe, 1964). Illustrative of the cadmium concentration in rocks and
geologic formations are the data summarized by Fleischer et al. (1974),
shown in Table 2.10. Igneous rocks appear to fall in the lower end of
the cadmium concentration range, with the average concentration being 0.25
ppm or below. Of the sedimentary rocks, limestone is also low in cadmium,
shales are higher on the average; and the cadmium content appears to
increase with increasing carbonaceous content.
Since rocks are the precursors of soils, cadmium concentrations in
soils undisturbed by man would be expected to approximate those found in
rocks. This appears to be the case. Fleischer et al. (1974) noted that
recent analyses of uncontaminated soils indicate that normal contents of
cadmium are less than 1 ppm, perhaps about 0.4 ppm on the average. Connor
and Shacklette (1975) have analyzed a large number of soil samples from
rural Missouri farmland (Table 2.11), finding a mean cadmium concentration
of less than 1 ppm.
Additional data on cadmium concentrations in U.S. soils are supplied
by the results of EPA's 1972 National Soils Monitoring Program, which, in
addition to the regular pesticide analyses, also analyzed soil samples for
four heavy metals: lead, mercury, cadmium, and arsenic. Five Standard
Metropolitan Statistical Areas (SMSA) were selected at random, and one 2.56
km2 site within city limits (urban) and one 51.8 km2 site outside city limits
(suburban) were randomly selected for each SMSA. Each site was classified
as "lawn", mowed or cultivated, or "waste", uncared for. Results of
cadmium analyses are shown in Table 2.12 (Gowen et al., 1976). The
comparison of lawn and waste sites indicated no statistically significant
differences, supportive of the hypothesis that the deposition is from
airborne fallout, which would fall equally on both types of sites within a
given urban or suburban area. These data were not normally distributed as
shown by tests for skewness and kurtosis, but. tended to fit a lognormal
distribution, and the geometric mean is consequently regarded as providing
a more meaningful estimate of central tendency.
2-36
-------
TABLE 2.10. CADMIUM CONTENT OF ROCK TYPES3
Concentration, ppm
Rock Type Mean Range
Igneous Rocks
Alkalic rocks 0.25 0.004-0.90
Basalts, diabases, gabbros 0.13 0.01-1.00
Dunite 0.005-0.154
Eclogites 0.1 0.03-1.6
Granitic 0.2 0.01-1.6
Intermediate 0.02-0.32
Peridotite 0.3 <0.001-0.029
Rhyolite 0.23 0.03-0.57
Sedimentary Rocks
Limestone 0.10
Sandstone <0.03
Shales 1.4 <0.3-4.0
Organic content <0.5% 0.35 O.3-0.8
Organic content 0.5%-1.0% 0.8 <0.3-1.8
Organic content >1.0% 2.0 0.5-8.4
aSource: Fleischer et al., 1974.
TABLE 2.11. CADMIUM CONCENTRATIONS IN MISSOURI SOILS
(in ppm)
Number of Concentration, ppm
Soil Horizon Samples . Mean Range
Plow zone, corn field
Oak-hickory forest 10 <1 <1-1.5
Plow zone, soybean field
Glaciated prairie 10 <1 <1-1.0
Unglaciated prairie 10 <1
-------
TABLE 2.12. CONCENTRATIONS OF CADMIUM IN URBAN AND SUBURBAN SOILS—1972'
NJ
I
CO
Cadmium, ppm
SMSA
Des Moines IA
Fitchburg MA
Lake Charles LA
Pittsburgh PA
Reading PA
Number of
Samples
59
25
26
10
16
54
51
138
10
41
Urban
Suburban
Urban
Suburban
Urban
Suburban
Urban
Suburban
Urban
Suburban
Arithmetic
Mean
0.89
0.28
0.13
0.13
0.36
0.01
1.21
0.90
0.63
0.25
Geometric
Mean
0.640
0.124
0.059
0.051
0.015
0.002
0.743
0.454
0.261
0.039
Extremes
0.1-3.56
0.00-1.76
0.00-0.70
0.00-0.38
0.00-5.32
0.00-0.11
0.00-4.95
0.00-8.03
0.00-1.70
0.00-2.45
Percent of
Positive
Detections
100
80
62
60
25
7
98
93
90
44
Source: Gowen et al., 1976.
Sensitivity 0.5 ppm.
-------
In an investigation of the distribution of metals in the soils of a
mining district, in this case the Coeur d'Alene lead-zinc district in Idaho,
Cannon (1969) reported that the pattern of zinc-soil concentrations over 600
ppm correlated well with the occurrence of ore. Cadmium-high (greater than
5 ppm) areas in the eastern part of the district were found to be related to
mineralized ground, but the values near Kellogg were thought to be affected
by smelter contamination.
The possibility that cadmium mobility in soil is pH dependent has
been suggested by Munshower (1972) in his discussion of an investigation of
the region around the East Helena, Montana, smelter (Table 2.13). In his
opinion, the pH variations between sites may account for some of the
differences; and he noted that the correlation between cadmium mobility in
the soil and pH was strong. Whenever any horizon reached or exceeded a pH
of 7, the cadmium concentrations in lower horizons dropped to normal or near
normal levels. The soil reservoir of introduced cadmium is restricted
essentially to the top 2 to 5 cm (1 to 2 in.), is geographically distributed
in relation to distance from the smelter and the prevailing winds, and is
normally not transferred to lower horizons. Therefore, the only exit from
the system by cadmium is by erosion or cropping, and not by leaching.
Interpretation of long-term changes indicate a half-life for this introduced
cadmium in the grassland habitat in excess of 1,000 years; it would be
shorter in cultivated lands.
Fleischer et al. (1974) have summarized the results of a number of
investigations of cadmium soil concentrations around smelters, including
the extensive study of the East Helena smelter from which came the estimate
of a total deposition of up to 236 metric tons (260 short tons) of cadmium
within a radius of 16 km of the smelter stack. Other studies have been
conducted around smelters, with similar findings of increased soil concen-
trations, including those of Cannon and Anderson (1971), Roberts et al.
(1975), and Ratsch (1974).
Higher than normal (>0.4 ppm) cadmium soil concentrations can result
from sources other than smelters—i.e., from use rather than production. Yost
et al. (1975) in their study of northwestern Indiana, in the Gary and East
Chicago area, have shown that cadmium soil concentrations are higher close
to concentrated industrial areas than in rural areas removed from such
sources (Table 2.14). Additionally, even in areas of normal soil concen-
trations, they confirmed the observations of Bolter et al. (1975) that
concentrations in litter were significantly higher than in the underlying
soil.
Fertilizers are a source of cadmium additions to soil. The small
concentrations of cadmium associated with phosphate ores carry through the
processing to fertilizer. There is a good deal of variability in cadmium
content. Florida and South Carolina rock phosphate typically contains 8
to 16 ppm cadmium (Yost et al., 1975). Western rock phosphate, which will
be drawn upon more in future as the eastern deposits are depleted, may
contain several times as much cadmium, up to 50 ppm.
2-39
-------
TABLE 2.13. CADMIUM CONCENTRATIONS IN SOIL
NEAR EAST HELENA, MONTANA3
Soil Horizon, Concentration,
cm ppm pH
2.4 kmb
0.0-5.0
5.0-17.0
17.0-30.0
30.0-60.0
4.0 km
0.0-5.0
5.0-11.0
11.0-19.0
19.0-25.0
>25.0
5.3 km
0.0-3.5
3.5-7.0
7.0-15.0
15.0-35.0
8.1 km
0.0-7.5
7.5-26.0
26.0-37.0
37.0-42.0
27.3
11.3
0.6
0.3
8.1
7.1
7.0
0.6
0.3
4.7
7.2
0.2
0.2
4.2
1.4
0.2
0.2
6.0
7.0+
7.0+
6.0
7.0
7.5
7.0+
6.5
6.5
7.4
5.2
5.4
8.2
8.2
Soil Horizon, Concentration,
cm ppm pH
11.3 km
0.0-4.0
4.0-7.5
7.5-18.0
18.0-33.0
16.9 km
0.0-3.0
3.0-9.5
9.5-18.4
>18.4
23.3 km
0.0-6.5
6.5-10.0
10.0-18.0
18.0-21.0
33.8 km
0.0-2.5
2.5-5.0'
5.0-8.0
8.0-23.0
23.0-30.0
2.5
0.7
0.4
NDC
3.4
0.9
0.8
ND
1.8
0.8
0.3
0.3
1.5
0.4
0.1
0.2
ND
5.4
7.6
7.6
7.6
7.8
7.8
6.6
6.8
7.2
6.4
6.7
6.9
7.4
o
Source: Munshower, 1972.
Distance from smelter.
CND = Not detected.
2-40
-------
TABLE 2.14. CADMIUM SOIL CONCENTRATIONS
IN NORTHWESTERN INDIANA3
Soil Horizon, cm
Concentration, ppm
Remarks
0-2.55
9.4
10.9
12.2
Litter
0-2.5
2.5-10.2
>10.2
Litter
0-2.5
2.5-10.2
>10.2
Litter
0-15.2
East Chicago, Indiana
2.5-14.0
2.51 Dunes
5.40 Marsh
5.95 Floodplain
Q
Willow Slough Fish and Game Area
1.03 Grassland
0.30
0.20
0.14
1.21
0.23
0.08
0.08
1.16 Marsh
0.36
Jasper — Pulaski Fish and Game Area
Black oak forest
Litter
0-15.2
1.1
0.4
Source: Yost et al., 1975.
Less than 8 km from concentrated heavy industrial area.
Approximately 80 km south of East Chicago.
2-41
-------
The Yost team (1975) performed a study to determine the extent of
cadmium buildup in soils associated with long-term application of known
quantities of phosphate fertilizers, using "fertility plots" at the Purdue
University Agronomy Farm. Soils from plots which, over a 20-year period,
had received a variety of levels of fertilizer application were analyzed
for cadmium. Soybeans and corn raised on these plots were also analyzed to
determine whether or not there was a significant correlation between.
cadmium levels in soils and crops. No significant correlation was detected.
Definitive analytical data are relatively sparse on the effects of
fertilizer application on soil cadmium contents; some data have been
reported on Virgin Islands soil, as measured at the surface:
Cadmium, ppm Treatment
0.15 Unfertilized soil
0.8 Fertilized
3.38 Phosphate fertilized
Overall, it appears that the cadmium concentrations in U.S. soils
not excessively disturbed by man approximate those found in rocks, i.e.,
0.2 to 0.5 ppm. The application of fertilizers does not appear to have
generally raised this level above 1 ppm. Highest soil concentrations are
found in the vicinity of smelters. These are proportional to the distance
from the smelter. Several ppm of cadmium may be found in surface soils in
the vicinity of major urban industrial areas.
Since the land and ocean sediments are the ultimate sinks for most
of the cadmium annually dispersed to the environment, it appears inevitable
that their concentrations will slowly increase. Except for the pockets of
high concentration represented by landfills, the increase in average soil
cadmium concentrations should proceed at an almost unmeasurable rate, espe-
cially as atmospheric emissions from past major point sources such as
smelters are brought under control. Most of the increase may come from
inadvertent sources such as fertilizers and the combustion of coals.
TERRESTRIAL BIOTA
Vegetation
Cadmium has been reported in plants over a large area of the United
States. There is notj however, a national monitoring program or agriculture
reporting program. Sargent and Metz (1975) reported that cadmium concentra-
tion in plants has an approximately 1:1 relationship with that of the soil.
However, existing data show that cadmium is concentrated in plant tissues to
varying degrees depending upon the species and the amount of cadmium in the
environment. In laboratory studies by Page et al. (1972), the amount of
cadmium in plant leaves varied between 9 ppm (beans) and 90 ppm (corn) when
the concentration of culture solution was 0.1 yg Cd/ml (0.1 ppm) and from
2-42
-------
35 ppm (beans) to 469 ppm (turnip) at a solution concentration of 1.0 yg/ml
(1.0 ppm).
Yost and his associates (1975) found varying cadmium concentrations
in herbaceous plants from industrial regions of northwestern Indiana with
a range between 0.24 and 7.70 (Table 2.15). Similarly, they found tree stems
to exhibit cadmium concentrations between 0.11 and 0.48 ppm. Hammons and
Huff (1975) report mean cadmium concentrations in Alaskan grasses of 0.10
ppm. Shacklette (1972) reports plant concentrations in the Colorado Rockies
which range from 0.03 to 1.50 ppm in stems and 0.07 to 0.97 ppm in leaves
(Table 2.16).
The magnitude of species difference in ability to absorb cadmium
appears to increase with increasing cadmium content in the environment.
John (1973) has demonstrated a dramatic increase in cadmium content,
particularly in the root portions of some plants grown on cadmium-contami-
nated soils (Figure 2.8). He reported cadmium concentrations of 1.8 to
12.2 ppm in various parts of 8 crops in control experiments as opposed to
a range of 19.7 to 6,121.5 ppm when soil cadmium concentrations were
increased to 200 mg cadmium per 1,000 g soil, air-dry basis. Hemphill et
al. (1973) have shown that the main concentrations of cadmium in the roots
of lettuce and radishes'from less contaminated areas in Missouri were in
the same range (0.7 to 1.6 ppm), while in samples from a small town where
a smelter was located the cadmium concentration in lettuce (28.1 ppm) was
about six times higher than that of radishes (4.7 ppm).
The work of numerous researchers has shown that different plant
species, varieties, and plant tissues, when exposed to similar levels of
cadmium, will contain different concentrations. For example, cadmium
concentrations in corn grain are usually only 3 to 15 percent of those
found in the leaf. In comparison, grain of soybeans, wheat, oats, and
sorghum may contain 30 to 100 percent of the foliar levels. Additional
studies have shown that leafy vegetables, such as lettuce, chard, spinach,
and turnip greens, can accumulate levels undesirable to man (in excess of
100 ppm) without showing toxicity symptoms (CAST, 1976).
Many studies have been conducted to determine the cadmium content
in plants as a function of distance from metal sources. For Kay County in
Oklahoma, the cadmium contents of tree leaves were 32.9 and 5.8 ppm for
samples collected at 1.6 and 7.2 km, respectively, from the cadmium source
(Benenati, 1974). In Galena, Kansas, Lagerwerff et al. (1973) found that
the cadmium concentrations in native grasses diminished from 8.6 to 1.4
ppm (dry weight) as the distance from the cadmium source increased from
0.3 to 2.4 km, and from 5.7 to 9.6 ppm with increasing distance from 1.7
to 0.3 km, even though cadmium was no longer being released at the time of
sampling. In Tacoma, Washington, however, Ratsch (1974) found that cadmium
levels in plants increased with increasing distance from cadmium sources,
in this case smelters, up to 4.8 km (3 mi) and then decreased afterward.
The mean cadmium concentrations of herbaceous grasses were 3.4 ppm at 0 to
1.6 km (0 to 1 mi), 6.6 ppm at 3.2 to 4.8 km (2 to 3 mi), and 2.4 ppm at
8 to 9.6 km (5 to 6 mi).
2-43
-------
TABLE 2.15. CADMIUM CONCENTRATIONS IN PLANTS
OF AN INDUSTRIAL REGION3>b
Species
Whole
Herbaceous
Andropogon sp.
Anemone cylindr-iao
Apios americana
Aster sp.
Carex stricta
Coreopsis lanceolate.
C. tripteris
llquisctiw arvenpc
E. hyemale
Eryngiwn yuacifo liwn
Euphorbia corollata
Fra.ga.ria virginiana
Galiwri obtusum
Helianthus divarieatus
H. ocoidentalis
Hypoxis hirsuta.
Juncus sp.
tioeleria crista.ta.
Liatris spicata
Liparis Ulifolla
Lithosperum canesceris
Lupinus perennis
Monarda fistulosa
Pedicularis canadensis
Phlox pilosa
Woody
Sweetgum, Liquidambar styraciflua
White oak, Quercus alba.
Willow oak, Q. phellos
Winged sumac, Rhus copallina
No. of Cadmium Concentration,
Samples ppm dry weight
Plant0
13
1
1
4
14
1
8
3
17
6
5
7
1
10
9
1
20
7
11
1
17
1
3
1
2
Stem
0.55
1.20
4.40
2.42
0.47
4.40
4.85
2.00
0.87
0.37
0.86
0.89
1.80
1.72
5.16
7.70
0.39
1.01
4.79
1.90
0.94
0.70
0.93
2.50
0.75
0.41
0.16
0.28
0.11
aYost et al., 1975. Data collected June, 1974.
Sampling location south of East Chicago—no lead smelters in the area.
Q
Whole above-ground plant unless specified.
.2-44
-------
TABLE 2.16. CADMIUM CONCENTRATIONS IN PLANTS
REMOTE FROM INDUSTRIALIZATION
Organism
Mean Concentration,
Organ ppm dry weight
Alaskan grasses
Colorado blue spruce
Douglas fir
Englemann's spruce
Juniper
Kinnikinnik
Limber pine
Lodgepole pine
Mountain maple
Ponderosa pine
Snowberry
Sticky laurel
Quaking aspen
Wild gooseberry
Willow
Pioea pungens
Pseudotsuga menziesii
Piaea englemannii
Juniperus communis nana
Arctostaphylos uvo-ursi
Pinus flexilis
Pinus contorta lati folia
Aoer glabrum
Pinus ponderosa scopulorwn
Symphoricarpus oooidentalis
Ceanothus velutinus
Populus tremuloides
Ribes sp.
Salix sp.
Entire
Plant
Stem
Stem
Leaves
Stem
Leaves
Stem
Leaves
Stem
Leaves
Stem
Leaves
Stem
Leaves
Stem
Leaves
Stems
Leaves
Stems
Leaves
Stem
Stems
Leaves
Stems
Leaves
Stems
Leaves
o.ioa
0.03b>c
0.20
0.07
0.22
0.05
0.26
0.11
0.23
0.21
0.14
0.10
0.38
0.21
0.17
0.09
0.22
0.11
0.09
0.12
0.03
0.77
0.45
0.08
0.07
1.50
0.97
Hammons and Huff, 1975. Alaska.
Shacklette, 1972. Colorado, Rocky Mountains.
"Cadmium concentrations in stems range from 0.03 to 1.50 ppm while in
leaves the range is 0.07 to 0.97 ppm.
2-45
-------
20 Pea seeds
28 Pea pods
30 Carrot tubers
34 Oat grains
96 Oat husks
117 Oat stalks
• 117 Pea vines
- 123 Radish tubers
— 177 Oat leaves
•• 199 Cauliflower leaves
mmm 239 Spinach leaves
•— 269 Broccoli leaves
294 Carrot tops
398 Radish tops
- 491 Spinach roots
—— 663 Oat roots
__ 668 Lettuce leaves
_____________ 1357 Cauliflower roots
—_____ 1571 Pea roots
" 1628 Lettuce roots
———•-»• 1647 Broccoli roots
/ f M22 Carrot roots
o
o
ts
o
o
1
o
o
o
o
o
o
1
0
0
o
0
o
o
o
o
0 '
o
f !
1 i
o
o
o
o
-------
Hemphill et al. (1973) have shown that plants along traffic routes
were higher in cadmium concentration but diminished with increasing distance
from the road. Connor et al. (1971) found that the cadmium concentration
in cedar trees along the lead-ore truck route near Centerville, Missouri,
was more than three times the amount found in cedars from off-road sites
(9.3 vs. 2.8 ppm, ash weight). However, they also found no significant
difference between average cadmium content in on-road and off-road samples
of cedar trees from 16 locations elsewhere in Missouri off the ore truck
routes.
Table 2.17 and Figure 2.9 summarize, cadmium concentrations in
Spanish moss (Tillandsia usenoides) from eight states along the Atlantic
and Gulf coasts in a U.S. Geological Survey study (Shacklette, 1972). Samples
having extremely high cadmium content (above 20 ppm in ash) were from Limona
and Panama City, Florida; Natchez, Mississippi; and East Baton Rouge Parish,
Louisiana, These areas were considered to be affected by considerable
industrial and automotive contamination. Low cadmium concentrations (less
than 5 ppm in ash) were found in samples from areas where minimal airborne
cadmium pollution is expected, such as Paradise Key, Everglades Park in
Florida, and Monticello, Mississippi.
Distributions of cadmium in crops were studied in 19 states east of
the Rocky Mountains by Huffman and Hodgson (1973). As shown in Table 2.18,
the cadmium content in wheat and perennial grasses was relatively low, with
less than 0.5 ppm in ash weight. They found no distinct geographic pattern
for observed cadmium concentration.
Crops Grown on Sludge-Treated Land
The application of sewage sludge to croplands and the potential
uptake of cadmium by food crops is a matter for concern. In 1976, EPA
commissioned 30 scientists from the Council for Agricultural Science and
Technology (CAST) to develop a state-of-the-art concensus on the application
of sludge to croplands as it relates to heavy metal activity, including
cadmium. Land disposal offers the opportunity of utilizing the fertilizer
value of sludge, if there are not adverse effects from its metals content.
the CAST study reports that metal levels may be a principal factor in
determining acceptable rates of application of sludge to land, and cadmium
is.one of the metals governing the utilization of sludge. Repeated
applications of sludge to land may lead to undesirable concentrations of
cadmium in crops.
The chemistry of cadmium in soils is not yet well understood, but
its lability in soil is reduced by organic matter, clay, hydrous iron
oxides, high pH, and reducing conditions. The CAST committee identified
the following land management options which can minimize the mobility of
cadmium in soil/sludge or which can minimize the concentration in food
plants. These include: (1) maintenance of soil pH at 6.5 or above; (2)
choice of crops which accumulate relatively low concentrations of cadmium;
(3) making only small annual sludge applications when food crops are to be
2-47
-------
TABLE 2.1.7. CADMIUM LEVELS IN SPANISH MOSS, TILLANDSIA USNEOIDES*
Concentration, ppm
Location
Alabama
Baldwin County, beach at Josephine
Cirrington County, 11.2 km (7 mi) west of Opp
Lowndes County, 4.8 km (3 mi) south of Letohatchee exit U.S. 65
Florida
Bay County, Panama City
Broward County, Ft. Lauderdale
Collier County, Coximba area, Marce Island
Dade County, Paradise Key, Everglades
Dixie County, Cross City
Hillsboro County, Limona
Indian R. County, Vero Beach
Jefferson County, Monticello
Palm Beach County, West Palm Beach
Georgia
Emanuel County, 4.8 km (3 mi) west of Stillmore
Lowndes County, 3.2 km (2 mi) north of Valdosta
Louisiana
East Baton Rouge Parish
Franklin Parish, 1.6 km (1 mi) northeast of Winnsboro
Point Coupee Parish, near Batchelor
Tangipahoa Parish, Robert
Terrebonne Parish, Gibson
Vernon Parish, Rt. 8 at Sabine River Bridge
Mississippi
Adams County, Natchez
Hinds County, 3.2 km (2 mi) south of Jackson
Lawrence County, 9.6 km (6 mi) south of Monticello
Walthall County, Rt. 27 at state line
Yuk,oo County, 9.6 km (6 mi) west of Yazoo
North Carolina
Onslow County, Verna
Washington County, 12.8 km (8 mi) east of Roper
South Carolina
Beauford County, Hunting Island State Park
Charleston County, Charleston
Dillon County, near Latto
Florence County, near Lake City
Georgetown County, Georgetown
Texas
Fort Bend County, Sugar Land
Harris County, 8.0 km (5 mi) east of 1-16 and 1-10 junction
Jasper County, 1.6 km (1 mi) east of Neeches River on Rt . 190
Jefferson County, Beaumont
Polk County, 1.6 km (1 mi) east of San Jacinto
Ash Weight
5.2
3.4
4.4
23.0
3.0
4.3
2.0
4.8
25.0
2.2
15.0
2.0
13.0
13.0
21.0
3.6
19.0
3.6
5.0
4.2
27.0
13.0
2.0
4.8
16.0
17.0
19.0
5.2
13.0
14.0
14.0
4.2
15.0
14.0
4.6
13.0
3.8
Dry Weight0
0.23
0.15
0.20
1.04
0.14
0.19
0.09
0.22
1.13
0.10
0.68
0.09
0.59
0.59
0.95
0.16
0.86
0.16
0.23
0.19
1.22
0.59
0.09
0.22
0.72
0.77
0.86
0.23
0.59
0.63
0.63
0.19
0.68
0.63
0.21
0.59
0.17
aSource: Shacklette, 1972.
Data taken from 123 locations in eight states during the period 1965-1970; 122 samples
Converted from ash weight using geometric mean of ash in percentage of dry weight, 4.5
were analyzed.
inverted from as
(ppm dry weight = ppm in ash x 0.045).
2-48
-------
800 KILOMETERS
20 -
SYMBOL AND PERCENTAGE OF TOTAL SAMPLES
17
16 23
21
>
17
•
15 -
u
2
LJJ
D 10-
O
LJJ
QC
5 -
J~l_
•- in co CN r-.
IN CN CM' ("i (")
incoroo) cooin
-------
TABLE 2.18. CONCENTRATION OF CADMIUM IN WHEAT AND GRASS
GROWING UNDER NORMAL CONDITIONS IN 19 STATES
EAST OF THE ROCKY MOUNTAINS3
Location
Alabama
Colorado
Connecticut
Georgia
Idaho
Illinois
Iowa
Indiana
Kansas
Kentucky
Louisiana
Massachusetts
Mississippi
Montana
Nebraska
New York
North Carolina
North Dakota
Ohio
Oklahoma
Oregon
South Carolina
Texas
Virginia
Summary Data:
East of Mississippi River
West of Mississippi River
All data
Number of
Samples
8
11
7
24
2
9
7
2
13
1
3
1
7
2
1
8
2
6
8
3
8
3
3
4
23
1
Mean Concentration, ppm
Wheat
NAb
0.19
NA
0.18
0.04C
0.34
NA
0.03C
0.16
0.01C
0.12
NA
NA
NA
0.06C
0.32
0.13C
NA
0.22
0.06C
NA
0.12
0.05
NA
0.14
0.25
0.22
0.20
0.20
Grass
0.17
0.27
0.13
0.16
0.21
0.26
0.15
0.11
0.18
0.13
0.44
0.25
0.14
0.20
0.17
0.14
0.18
0.15
NA
0.17
0.18
0.17
Source: Huffmann and Hodgson, 1973. Measurements were made in
1969 and 1970.
Not available.
:Source: D. R. Buhler, 1976 (unpublished data).
2-50
-------
grown; (4) use of sludges low in cadmium on croplands; and (5) growth of
nonedible crops, e.g., biomass or fiber crops, on sludge-treated lands.
Sludge has a tendency to lower soil pH, and cadmium uptake by plants
is higher in acid soils, so pH control is a fundamental requirement for
proper management of sludge-treated soils. Numerous investigators have
studied the effect of pH on cadmium uptake by various plants. Data presented
by Chaney and Hornick at the first International Cadmium Conference in
February, 1977, illustrate the pH effect very well (Figure 2.10). These
data show a decline in the cadmium content of soybean leaves as the soil
pH is increased to near neutrality. Figure 2.10 also shows the significant
effect of increasing the cadmium concentration of the soil. However, other
work involving repeated annual applications of sludge to soil cropped to
corn show that the amounts applied in a given year influence the cadmium
uptake to a greater extent than the total cumulative amounts of cadmium
applied (CAST, 1976). The proper management involves not only the use of
sludges low in cadmium on croplands, but the making of only small sludge
applications each year.
Another important consideration is the fact that crops differ
greatly in the ability to take up cadmium. The cadmium contents of a
variety of crops grown on sludge-treated soil containing 10 ppm of cadmium
are given in Table 2.19. The leafy vegetables in these studies were high
in cadmium content (e.g., 161 ppm for spinach), whereas the edible portions
of grains such as corn and rice were low (less than 1 or 2 ppm). The same
crops grown on control soil containing only 0.1 ppm of cadmium exhibited
significantly lower cadmium contents.
It has also been suggested that rates of application of sludge
should be limited by the ratio of cadmium to zinc in the sludge. A cadmium
concentration below 1 percent that of zinc is advocated in the EPA Draft
Document on Acceptable Methods for the Utilization or Disposal of Sludges
(U.S. Environmental Protection Agency, 1974). One premise for this concept
is that it would result in high enough zinc concentrations in soil to kill
plants before cadmium could accumulate to levels in foods considered
hazardous to animals and humans (CAST, 1976). However, the CAST committee
cautions that this premise often is not correct, and they advocate that the
concept be abandoned or used only in combination with other criteria.
Invertebrates
Little information has been documented on the cadmium content in
terrestrial invertebrates even though they play an important role in the
vertical transport of trace elements in the environment (Table 2.20).
Gish and Christensen (1973) found that cadmium concentrations in
earthworms along the Baltimore-Washington, D.C., Parkway were approximately
ten times the cadmium levels in the soil (6.9 to 12.6 ppm in worms vs. 0.68
to 1.2 ppm in soil). The earthworms near the highway seemed to have a
higher concentration of cadmium than those further from the road. In
Tennessee, Anderson et al.(1974) found approximately 17 times more cadmium
2-51
-------
TABLE 2.19. CADMIUM CONTENT OF CROPS GROWN IN THE GREENHOUSE
ON CALCAREOUS DOMINO SILT LOAM WITH AND WITHOUT
SEWAGE SLUDGE TREATMENTS
Cadmium per Gram of
Crop
Paddy rice
Upland rice
Sudangrass
White clover
Alfalfa
Bermudagrass
Field bean
Wheat
Zucchini squash
Soybean
Tall fescue
Corn
Carrot
Cabbage
Radish
Swiss chard
Table beet
Romaine lettuce
Tomato
Curlycress
Spinach
Turnip
Control
Diagnostic
Leaf
<0.1
0,4
0.2
0.2
0.3
0.3
0.6
<0.1
0.6
0.4
1.4
3.9
1.4
0.7
4.2
1.4
0.8
0.8
2.6
2.4
3.6
1.8
Soilb
Edible
Tissue
<0.1
<0.1
0,2
0.2
0.3
0.3
<0.1
<0.1
<0.1
0.7
1.4
<0.1
0.9
0.2
0.3
1.4
0.2
0.8
<0.1
2.4
3.<6
<0.1
Dry Plant Tissue
Sludge-Treated
Diagnostic
Leaf
<0,1
0.9
5.7
6.0
8.2
9.4
10.3
11.6
12,5
15 ..6
1.7.3
27,0
38.0
39.0
40.0
42.. 0
47, 0
62.0
71.0
89,0
161,0
162.0
, yg
Soiic
Edible
Tis.sue
'.0.2
0.4
5.7
6.0
:8.3
9,4
0.7
5. .'8
,0.7
10.7
17.3
1.4
16.0
1.8
4,0
42.«0
4.5
.62,0
2,4
89.-0
161.0
9.2
a
Source: Bingham et al., 1975, 1976;; CAST, 1976.
^Domino silt loam containing 0.1 ppm of Cd,
cSludge treated with cadmium sulfa.te to supply 10 yg
-------
50.0
40.0
00
30.0
0)
4J
o
•H
iH
O
20.0
10.0
ppm Soil Cd
5.2
5.6
6.0
Soil pH
6.4
6.8
Figure 2.10. The effect of soil pH and cadmium concentration
on the cadmium content of soybean leaves
(Chaney and Hornick, 1977).
2-53
-------
TABLE 2.20. LEVELS OF CADMIUM IN TERRESTRIAL INVERTEBRATES
ho
I
Ol
Location
Maryland
Highway 1 and
Baltimore- Washington
Parkway
Montana
Deer Lodge Valley
Tennessee, East
Date of
Data
Collection
1970
1970
Not avail-
able
Concentration,
ppm dry weight
Organism
Earthworm
(whole
body)
Grasshoppers
(whole
body)
Earthworm
(whole
body)
Mean Range
12
8
8
6
1
5
2
2
5
2
0
5
.6
.8
.3
.9
.1
.0
.1
.7"^- -7— — _
.2 •*•--...
.2
.4
.1 3.1-9.3
Reference
Gish & Christensen, 1973 3
6
12
24
48
Munshower, 1972 4
24
5
6
' -••- •^-— — ^_ 14
"~~~""' ^-^_ 201
Anderson et al., 1974
.1
.1
.2
.4
.8
.0
.1
.6
.1
.5
.1
m
m
m
m
m
km
km
km
km
km
km
(10
(20
(40
(80
(160
(2.
(15
(3.
(3.
(9.
Remarks
ft) from highway
ft) from highway
ft) from highway
ft) from highway
ft) from highway
5 mi) from zinc
.0 mi) from zinc
5 mi) from zinc
8 mi) from zinc
0 mi) from zinc
smelter
smelter
smelter
smelter
smelter
(125.0 mi) from zinc smelter
-------
in earthworms (5.7 ppm dry weight) than in soil (0.35 ppm). Grasshoppers
in Montana contained slightly higher cadmium concentrations than their food
(Munshower, 1972).
Mammals
Data pertaining to cadmium levels in terrestrial mammals are
available from locations in eight states (Figure 2.11). No national or
comprehensive regional monitoring program exist. Many of these studies
are related to highly contaminated regions and none was continued for a
period long enough to allow trends to be established.
There appears to be no difference between cadmium concentrations in
domestic and wild animals. Munshower (1972) found that mean cadmium levels
in the kidneys of cattle from Deer Lodge Valley in Montana (1.67 to 3.04 ppm)
were in the same range as those in their wild counterparts—red fox, badger,
and ground squirrel (1.35 to 3.47 ppm).
More marked differences were shown in the cadmium values found in
domestic rabbits and cottontails. Cadmium levels in the kidneys of rabbits
from Missoula, Montana (control), and from East Helena, Montana (near a
lead smelter), were 0.3 and 35.6 ppm, respectively (Gordon, 1972). Cotton-
tail rabbits in Ohio contained 1.3 to 1.6 ppm of cadmium (Bachant and
Schumann, 1971; Lynch, 1973), while mountain cottontails in East Helena,
Montana, had as high as 53.0 ppm (Gordon, 1972).
Cadmium levels in the milk of cattle ranged from less than 0.0005
ppm in samples from Missouri (Dorn et al., 1973) to 0.2 ppm in those from
an area near the smelter in East Helena, Montana (Lewis, 1972). The cadmium
content in the blood of cattle from southern Missouri was less than 0.01 ppm.
Concentrations of cadmium in blood appear to be affected by seasons, with
the highest levels being found in the fall (Dorn et al., 1973) (Table 2.2.).
However, in cattle as in other domestic and native animals, cadmium levels
are highest in the kidneys, hair, and secondarily in the liver. Cadmium
levels are at or near background levels in other internal organs, indicating
that these organs do not accumulate cadmium from the environment.
Unlike plants, the species-dependency of the cadmium level in
animals has not been demonstrated. Most of the animals from the same
geographical areas seemed to have approximately the same levels of cadmium
in their bodies except for those of rabbits found in the polluted Helena
Valley, Montana. Cadmium levels in domestic rabbits and mountain cotton-
tails were 7 to 16 times higher than those of cows, ground squirrels, and
mice (Munshower, 1972). No clear indication of any differences in the
cadmium content of herbivorous and carnivorous animals was observed from
the data presented in the literature.
Age could be a contributing factor in bioaccumulation of cadmium in
animals. Mature ground squirrels and gray squirrels had about 4 to 5 times
greater cadmium concentrations than their immature counterparts (Munshower,
2-55
-------
Vermont
1-0
i
Ol
a*
New Hampshire
B
Maryland
A
Earthworms (Gish & Christensen,
1973: Anderson et al., 1974)
Mice and Shrews
(Schlesinger & Potter, 1974)
C. Cottontails and deer
(Bachant and Schumann, 1971;
Devendorf, 1975; Lynch, 1973)
D. Rodents, r'abbits and livestock
(McKinnon et al., 1976; Dorn
et al, 1973; Gordon, 1972;
Munshower, 1972; Lewis, 1972)
E. Insects, squirrels, livestock
and predators (Munshower, 1972)
F. Deer and Rodents (Schroeder
et al., 1976)
G. Moose (Franzmann et al, 1975)
Figure 2.11. Locations of study areas for cadmium levels in
terrestrial animals, excluding birds.
-------
TABLE 2.21. CADMIUM LEVELS IN CATTLE3'b
(ppm, dry weight)
1971
1972
1973
Organ
Blood
Milk
Hair
Fall
0.0174
0.02163
0.0030
0.0043
Winter
0.0038
0.0038
0.0042
0.0040
Spring
0.0060
0.0080
0.0030
0.0030
Summer Fall Winter
0.0076
0.0036
0.0020
0.0030
1.29 1.74
0.06 0.13
Spring Summer
2.80 0.67
0.05 0.04
Liver
Kidney
Diaphragm
1971-1972
0.90
0.24
3.70
1.40
0.10+
0.10+
Note each number pair in table. Top number represents environmentally
exposed animals—bottom number represents controls.
Source: Dorn et al., 1973.
2-57
-------
1972; McKinnon et al., 1976). However, in most cases, the ages of animals
studied were not known.
Birds
Data on cadmium levels in birds from national monitoring programs
are limited to starlings collected at 56 sites from 44 states (Figure 2.12)
during 1971 (Martin and Nickerson, 1973) and 1973 (White et alt, 1976).
The levels of cadmium for both years ranged from less than 0.05 ppm to 0;2
ppm, but a light increase in overall values was observed in 1973 (Table 2.22).
In 1971, 32 of the 50 samples contained less than 0.05 ppm^ with only 14
samples exceeding 0.05 ppm. In 1973, however cadmium levels in 2-1 of 51
samples were higher than 0.05 ppm, with 18 samples being less than 0.05 ppm.
Cadmium levels at all 6 sites which had more than 0.1 ppm during 1971
dropped to less than 0.07 ppm in 1973, while the concentrations in 6 other
sites were nearly doubled from less than 0.06 ppm in 1971 to more than
0.11 ppm in 1973. Locations where more than 0.1 ppm of cadmium was found in
starlings were Phoenix, Arizona; Stuttgart, Arkansas; Bakersfield, California;
Farmington, New Mexico; and Elkins, West Virginia, in 1971; and Brighton,
Colorado; Evansville, Indiana; Gary, Maine; Maiden, Missouri; Pittsburgh,
Pennsylvania; and Salt Lake City, Utah, in 1973.
Lynch (1973) conducted a statewide study on cadmium levels in ring-
necked pheasants in Ohio and found that the mean cadmium level in kidneys
was 7.45 ppm, while edible portions, leg and breast muscle, contained 0.08
to 0.17 ppm, respectively.
Studies of the common tern from Long Island, New York, and from
Hamilton, Lake Ontario, failed to show any significant differences in
cadmium in the kidneys, 21.3 to 29.5 ppm (Connors et al., 1975). Brown
pelicans from California had much higher cadmium in the liver than those
from Florida, but the cadmium level in other parts of the body (breast and
bone) were in the same range for both groups (Fleischer et al., 1974)*
The highest cadmium concentration reported from birds, 53.2 ppm, was found
in the ashy petrel from the California coast (Anderlini et al.j 1-972) s
Comparisons between ecologically equivalent species of different
species occupying the same locality were possible for the ring-necked
pheasant and mourning dove from Ohio. The breast muscle of mourning dove's
had much higher concentrations of cadmium than the ring-necked pheasants.
This may be attributed to a number of factors, including migratory behavior
and the kinds of food eaten.
AQUATIC BIOTA
Plants and Algae ;
In a study of the environmental flow of cadmium and other trace
metals in northwestern Indiana, Yost et al. (1974) found tha't filiime'ntoiis
!': 2-58
-------
1 Ring-necked pheasants
2 Wild common terns
Starlings
4 Abnormal young terns
5 Jerpms amd egrets
6 Chipping sparrows
7 Domestic chicken
8 American kestrel eggs
9 Coopers hawk eggs
10 Ruddy ducks
11 Brown pelicans
12 Ashy petrels
13 Ruffed grouse
Figure 2.12. Locations for cadmium sampling in birds.
[*Exact location(s) in state not indicated.]
-------
TABLE 2.22. CADMIUM LEVELS IN STARLINGS MEASURED IN 1971 and 1973'
Alabama, Mobile
Arizona, Phoenix
Arkansas, Stuttgard
California, Bakersfield
Los Angeles
Sacramento
Colorado, Brighton
Greeley
Connecticut, Connecticut River Valley
Delaware, Dover
Florida, Gainesville
Georgia, Atlanta
Idalio, lioise
Illinois, Chicago
Indiana, Kvansville
Ca ry
Iowa, Des Moines
Kansas, Garden City
Louisiana, Baton Rouge-
Maine, Cray
Maryland, Patuxent
Annapolis
Massachusetts , Quincy
Michigan, Lansing
Minnesota, Twin Cities
M i ss i ss ipp i , Starkville
Missnur i , Maiden
Nebraska, North I'latte
Nevada, MrCil 1
Keno
New Jersey, Brunswick
New Mexico, Carlsbad
Farmington
New York, Albany
Jamestown
Nortli Carolina, Raleigh
North Dakota. Bismarck
Ohio, Columbus
Oklahoma, Tishomingo
Oregon, Corvallis
Wilsonvil le
Pennsylvan ia, Pi ttsburgh
South Carolina, Columbia
South Dakota, Pierre
Tennessee, Nashville
Texas, Hillsboro
San Antonio
Utah, St. Lake City
Vermont, Champlain Valley
Virginia, Blackshurg
Washington, Spokane
Yakima
West Virginia, Elkins
Wisconsin, Horicon
Portage
Wyoming, Worland
n.-ir/i rpnrpsenf whole body analysis of
Concentration,
197lb
<0.05
0.11
0.10
0.18
0.06
<0.05
0.05
<0.05
0.09
'0.05
<0.05
<0.05
0.06
•'.0.05
0.05
<0.05
<0.05
-------
algae had relatively higher concentrations of cadmium, with mean values
up to 2.33 ppm, than rooted plants. Other aquatic plant samples contained
less than 1.0 ppm cadmium.
Aquatic plants from the more heavily contaminated area of the Coeur
d'Alene-Spokane River drainage system showed high concentrations of cadmium
in their tissues. Funk et al. (1973) measured cadmium levels from 30 to
270 ppm in algae, mainly Cladophora sp., indicating the ability of algae to
concentrate cadmium by factors of 102 to 103 in relation to water. Submer-
gent or emergent aquatic plants from Foundry Cove in the Hudson River near
a nickel-cadmium battery plant were found to contain concentrations of
cadmium averaging up to 89.4 ppm, with a range from 1.8 to 269 ppm in their
leaves and stems. The roots of Spartina grass from the same area exhibited
a mean cadmium content of 1,100 ppm (range 247 to 2,960 ppm), whereas the
cadmium content in their leaves averaged only 13.6 ppm (Kneip et al., 1975).
Marine algae in southern California showed relatively higher
concentrations (with maximum levels up to 20.9 ppm) than the algae from the
northern coast, reflecting the cadmium contamination of the San Diego area
(Martin and Broenkow, 1975).
Invertebrates
Comparison of data on cadmium levels in aquatic invertebrates with
those for fish indicate a much greater concentration of cadmium in inverte-
brates. In general, the distribution of elevated cadmium levels in inverte-
brates is more uniform than in fish. Elevated levels were found most often
in whole organisms rather than in muscle tissue. The highest levels (5 ppm)
in Atlantic oysters were from the Housatonic River, Connecticut. Levels
greater than 2 ppm were found in scallops from Cape Kennedy, Florida; green
abalone from San Diego, California; and Pacific oysters from Puget Sound
(National Marine Fisheries Service, 1975).
In one of many local studies, Fleischer et al. (1974) indicated that
cadmium levels in marine invertebrates from unpolluted areas were in the
range 0.4 to 2.6 ppm (dry weight). Cadmium levels greater than 1 ppm were
found in clam, oyster, and scallop specimens from Long Island Sound, New
York; Cape Canaveral, Florida (Zook et al., 1976); West Bay and Nueces Bay,
Texas (Robe.rts et al., 1975); and the southern California coast (Vattuone
et al., 1976); probably reflecting higher cadmium levels in these waters.
Cadmium content in most of the commercial shrimp was less than 0.1 ppm,
except those in Trinity Bay, Texas (0.22 ppm). Mean cadmium concentrations
in oysters appeared to reflect the degree of industrialization in the
estuary in which they lived (Figure 2.13).
Marine zooplankton exhibited higher cadmium content than those from
freshwater. Freshwater zooplankton from Lake Michigan and vicinity had
average values greater than 0.4 ppm cadmium (Mathis and Kevern, 1973;
Martin and Broenkow, 1975), while marine zooplankton from southern California
waters had maximum levels up to 15.2 ppm and those from the northern
2-61
-------
NJ
I
N5
a. National Marine
Fisheries Service, 1975
b. Roberts et al., 1975
c. Zook et al., 1976.
Figure 2.13.
0.63
Mean cadmium concentrations (ppm) in Atlantic and Gulf of
Mexico oysters (Crassostrea virginica) and Pacific Ocean
oysters (C. gigas) .
0.388
-------
California and Oregon coasts about 6.2 ppm. Martin (1970) reported that the
cadmium concentration factor for zooplankton was approximately 6,000 times
that in water. This high concentration level was not common in most of the
zooplankton studied.
Cadmium levels in tubificid worms (Oligochaeta) varied greatly,
ranging from 1.1 ppm for worms in the Illinois River at Peoria (Mathis and
Cummings, 1973) to 230 ppm for those from the Palestine Lake in Indiana
(Yost et al., 1975). Oligochaete worms from highly contaminated water of
the Spokane River in Idaho contained a comparatively lower level of 4.3 ppm
cadmium, while other bottom-dwelling invertebrates such as midges, mayfly
larvae, and snails concentrated cadmium up to 97 ppm (Funk et al., 1973).
Fish
Fish are the most widely studied species among all aquatic organisms
and numerous local and/or statewide studies have been made throughout the
United States. The National Pesticide Monitoring Program compiled cadmium
levels in freshwater fish from 92 rivers and streams in 46 states, but data
are available only for 1972. From most of the rivers studied, cadmium
concentrations were within the range of less than 0.05 to 0.5 ppm with only
those from 10 rivers exceeding this limit. A maximum cadmium level of
greater than 1 ppm was found in fish collected from the Sacramento River in
California, Connecticut River in Connecticut, Wabash River in Indiana, Yazoo
River in Mississippi, and Columbia River in Washington. The highest cadmium
level recorded was 1.7 ppm in a northern squawfish from the Columbia River,
Washington. Other high values (greater than 1.0 ppm) typically occurred in
carp, suckers, and other bottom feeders.
The cadmium levels in the muscle or whole body of most freshwater
fish found in the localized studies were less than 0.1 ppm with a few
exceptions. Fish from Palestine Lake, Indiana, contained more than 0.5 ppm
in the muscle (Atchison, 1975). Mean cadmium residues in trout from Climax
Colorado, were relatively higher, reaching up to 4.2 ppm in muscle (Roberts
et al., 1975). Cadmium concentrations in fish from Foundry Cove in the
Hudson River, New York, were highest of all, averaging 9.1 to 12.3 ppm
(Schroeder, 1974). Of the organs surveyed in a study by Roberts et al.
(1975), bone and liver tissues of freshwater fish consistently showed
highest levels of cadmium (Table 2.23). Values in bone ranged as high as
46.6 ppm, liver to 25.9 ppms in these contaminated fish, where muscle
tissue cadmium concenterations were as high as 4 ppm. These data show some
indication-of a reduced cadmium burden in the trout of these areas over the
3 years of the study (Roberts et al., 1975).
Cadmium levels appeared to be lower in marine and estuarine fish
than in the freshwater fish. Data from the NMFS Microconstituent Resource
Survey indicate elevated concentrations in fish generally along the southern
Atlantic and the Pacific coastlines of the U.S. Highest concentrations
(greater than 0.2 ppm) were found in analyses of whole fish, mainly menhaden
and ballyhoo. High concentrations (greater than 0.1 ppm) in muscle tissue
2-63
-------
TABLE 2.23. FRESHWATER FISH—CADMIUM LEVELS IN TISSUES
Organ
Bone
Muscle
Liver
Whole fish
Species
Brook trout
Brown trout
Rainbow trout
Brook trout
Brown trout
Rainbow trout
Brown trout
Brook trout
Brown trout
Rainbow trout
Brook trout
Rainbow trout
Brook trout
Rainbow trout
Brook trout
"
Brook trout
Rainbow trout
Brook trout
Brown trout
Brook trout
Brown trout
"
Brook trout
Brook trout
Rainbow trout
Brook trout
"
Rainbow trout
Brown trout
Brook trout
Brown' trout
Rainbow trout
Brook : trout
Rainbow trout
Brook trout
n
Brook trout
Brown trout
Rainbow trout
Brook .trout
Brown -trout
Rainbow trout
Brown trout
Location
Climax area, CO
it
-
"
"
"
Lake City, CO
"
"
11
Silverton area, CO
"
"
"
M
n
Climax area, CO
"
"
"
"
Lake City, CO
n
Silverton area, CO
Climax area, CO
"
n
n
"
Lake City, CO
n
"
Silverton area, CO
"
it
"
"
Climax area, CO
"
n
tt
11
ti
Lake City, CO
Mean Concentration, ppm
1969 1970 1971
20. 3b
26. 4°
4.0
6.0
1.6
7.8
8.9
0.0
2.5
2.8
11.3
19.9
13.1
8.1
4.0
1.7
3.1
3.3
1.2
1.2
0.0
4.2
0.0
1.1
13. 5b
1.1
7.7b
7.0
2.1
0.0
4.5
8.1
2.6
4.2
7.4
0.0
0.4
6.5
3.0
3.0
0.0
2.3
2.7
0.0
Source: Roberts et al., 1975.
Calculated value.
2-64
-------
were found in blue marlin from Hawaii, petrale sole from Pidgeon Point,
California, and Pacific bonita from Coranado Island, California (Figure
2.14). Highest mean concentrations were less than 0.2 ppm (National Marine
Fisheries Service, 1975).
Sampling of yearling estuarine fish for pesticide and heavy metal
residues analyses was initiated in 1972 by the National Estuarine Monitoring
Program (Heath, 1976). Cadmium analyses of more than 540 samples (25 fish
per sample) showed no consistent trends between July, 1972, and June, 1976
(Heath, 1976). Geometric means of the positive residue ranged from less
than 0.02 to 0.15 ppm, wet weight of whole fish, for cadmium.
2-65
-------
0.019-0.119
aExtremes refer to a
of means.
"Single number indicates
only one data base, a
single mean.
cFar offshore values for
those states; all other
figures indicate estua-
rine and/or nearshore
organisms.
-0.116
0.031-0.157
0.046-0.074°
0.034
0.011-0.078
0.033-0.078C
0.027-0.053a
0.049-0.054
0.016-0.091
0.036
Figure 2.14.
Cadmium in marine fish—muscle tissue, ppm
[data averaged among various species along
whole coastline of indicated state (National
Marine Fisheries Service, 1975)].
-------
3. CADMIUM BEHAVIOR IN THE ENVIRONMENT
The routes of cadmium flow in the environment are presented in
Figure 3.1. The diagram shows the pathways from the sources through air,
soil, and aquatic (freshwater and ocean) environments and interactions
between the ecosystems. The cadmium in each environment has different
characteristics but the main flux through the system is to the soil
environment and then toward the ocean sediment.
Although the residence time of cadmium in the atmosphere varies
greatly depending upon the particle size and other meteorological factors,
presumably the airborne cadmium particles are eventually returned to the
land and aquatic environments by fallout, adsorption, agglomeration, or
inhalation. A major fraction of the cadmium emission accumulates mainly
in the proximity of the sources, varying from a negligibly small value
for submicron particles to practically complete deposition for particles
greater than 10 microns (Fleischer et al., 1974). Long-range transport of
cadmium may occur for the smaller particles by wind action, but it appears
to be within a limit of relatively small range, a radius of 16 km (Meisch
and Huffman, 1972) or up to 24 km from the smelter stack (Bolter et al.,
1975; Munshower, 1972). Thus it is estimated that about 254 metric tons
(93.5 percent) of cadmium emitted into the air are redeposited on soil and
180 metric tons (6.5 percent) on surrounding oceans within a 22 km limit
(12 nautical miles) from the shore.
Soil receives cadmium directly from the emission sources as land-
destined wastes and fallout deposition from the atmosphere. This amounts
to approximately 1,780 MT/yr, comprising nearly 96 percent of the total
environmental cadmium emissions.
Upon deposition, the cadmium sulfates and chlorides may be leached
or washed out from the soil by rainfall. But the majority of cadmium,
possibly in the form of oxides, accumulates in the soil (Fleischer et al.,
1974). Studies of cadmium transport in soil indicate that about 95 percent
of cadmium introduced in soil is retained, while only 5 percent exists via
the stream discharge (Andren et al., 1975; Huckabee and Blaylock, 1974).
Only a speculative estimate can be made for the cadmium flux from
freshwater to the ocean due primarily to the lack of information on the
sedimentation loss of cadmium in the freshwater environment. The rate of
sedimentation of cadmium would be controlled largely by the rate and mode
of river flows as well as by chemical and physical processes occurring in
estuaries. When freshwater reaches the river-estuary boundary, cadmium
associated with other organic materials tends to deposit rather rapidly
3-1
-------
CADMIUM SOURCES
Zn ores smelter refinery:
Industrial conversion use
disposal:
Coal & oil combustion fertilizer
sewage sludge
Total Input 1860 MT/yr
1500
_o
LU
Inhalation
|
A I R
1 Input: 300 MT/yr)
*
o 1
CO ^1
1
SOIL
(1 Input: 1780 MT/yr
Runoff
F
OJ
A Leaching
SO) x- '
" 3 |
O QJ t^ I. IN"
ro O i
g sl
k 1
RESH WATER
(X Input: 150-240 MT/yr)
Estuaries
X
^.J
-I
i !j-
CO '
^ i
OCEAN
i Input: 140-210 MT/yr)
Sediment
Fallout
^ 20
Dumping Outfalls
Evaporation _
: ^-
Evaporation
__ 20
Evaporation
^
I
Data used are cadmium emission estimates by Sargent and Metz(1975):
Fluxes from air compartment based on the ratio of U.S. land (including inland waters) vs. seas (12- mile
limit): 93.5 vs 6.5;
Flux from soil compartment estimated cadmium net flu« (output) as 5-10 percent of the total input;
Flux from freshwater based on net flux through river as 80 percent (20 percent sedimentation loss)
Figure 3.1. Environmental flow of cadmium emitted by man's activities.
3-2
-------
due to increased salinity (Windom, 1976) and is thus confined to estuaries
or to coastal waters.
Windom (1976) found that about 17 percent of cadmium is lost in the
southeastern U.S. salt marsh environment through sedimentation, and the net
flux of cadmium through the estuary was about 83 percent. Assuming that 80
percent net flux goes into the ocean environment, the cadmium delivered to
the adjacent U.S. oceans each year would be about 120 to 190 metric tons,
amounting to a total cadmium input of 140 to 210 MT/yr, including fallout.
AIR TRANSPORT
Cadmium in the atmosphere is mainly in the form of suspended aerosol
particles as oxides, chlorides, or sulfates (Hise and Fulkerson, 1973).
The size of particles varies considerably from submicron range to probably
greater than 50 microns, with the mass median diameter (MMD) being 1.54 to
3,1 microns (Lee and von Lehmden, 1973). Particles 1.5 microns in diameter
are the most abundant in fly ash (100 ppm), but much lower concentrations
of cadmium (less than 5 ppm) are associated with particles larger than 3.5
microns. Lee and von Lehmden (1973) indicated that larger particles (greater
than 50 microns) settle out very rapidly, and smaller ones remain airborne
for longer periods and are transported to greater distances by wind or
diffusion forces. Thus the concentrations and residence time of cadmium in
the air increase markedly with decreasing particle size (Davison et al.,
1974).
There are basically three phases of the air pollution cycle: (1)
pollutant release from the source; (2) diffusion and transport of the con-
taminant within the atmosphere; and (3) removal of the pollutant from the
air or the reception of the pollutant by animate and inanimate objects.
Data on the behavior and the movement of cadmium particles in the atmosphere
(2nd phase) are not yet available. Meteorological factors, such as wind
(direction, velocity, advection), precipitation, air masses, and turbulence
greatly influence this atmospheric pollutant cycle. Henmi and Reiter (1974)
emphasized the role of clouds as an important factor in controlling the
concentration of pollutants in rainwater. Newman et al. (1974) found that
the transport of cadmium and other aerosol contaminants around the southern-
most area of Lake Michigan was affected by terrestrial and topographical
features.
Although there have been a few studies on the atmospheric aerosol
composition and concentrations in industrial and urban air, data on spatial
distribution and concentration gradients of cadmium in the air are largely
lacking. Long-range aerial transport of cadmium has been estimated
indirectly from the studies of soil concentrations surrounding smelters.
Miesch and Huffman (1972) observed that cumulative deposits of emissions
from local smelters corresponded roughly with the amount accumulated in
surrounding soils, less small amounts taken up by vegetation and leaching.
Plant uptake of cadmium did not play a major role for cadmium removal from
the soil. Miesch and Huffman estimated that about 260 metric tons of cadmium
had been accumulated in the soils within a radius of 1 to 16 km from the
3-3
-------
smelter stack. Cadmium concentrations in uncultivated soil surrounding the
East Helena smelter stack decreased from 68 ppm to 4 ppm (0 to 2.5 cm depth)
as the distance from the stack increased from 1.8 km to 7.2 km (Table 3.1).
However, the estimates appear to be too approximate to identify or to
characterize pure atmospheric transport of the element.
TABLE 3.1. CADMIUM CONTENT AND ZN/CD RATIOS IN UNCULTIVATED
SOIL SURROUNDING EAST HELENA STACK3
Depth of Soil, 1.8 km from Stack 3.6 km from Stack 7.2 km from Stack
cm Cd, ppm Zn/Cd Cd, ppm Zn/Cd Cd, ppm Zn/Cd
0-2.5
5-10
15-25
68
30
3
16
33
70
17
7
2
14
25
42
4
2
1
12
15
33
aSource: Miesch and Huffman, 1972.
Cadmium aerosols in the air are removed by wet deposition through
rain and snow, sedimentation (dry deposition), and impaction on obstacles.
Andren et al. (1975) reported that the ratio of cadmium to manganese in
fly ash was comparable to that of rain, indicating wet deposition is a major
mechanism for the removal of cadmium from the air. Cadmium removal by dry
deposition at Walker Branch watershed, Oak Ridge, Tennessee, was less than
4.5 percent of the wet deposition.
More complex mechanisms in the atmospheric transport of cadmium were
observed by Yost et al. (1974, 1975), In their studies of the City of
Chicago and vicinity, they found the flushing of particulates as well as
their repeated refloatations, and thus repeated atmospheric transport. The
total suspended particulates (TSP) due to refloatation in the Chicago area
constituted 20 to 30 percent of the annual mean TSP under normal meteoro-
logical conditions. Daily values of TSP could be increased up to 50 percent
by refloatation due to winds and traffic on a dry day. Since the refloat-
ation of particulates is not a function of industrial emission sources,
studies directed at defining the source of refloated materials are highly
desirable.
SOIL TRANSPORT
The normal content of cadmium in uncontaminated soils is probably in
the range of less than 1 ppm with about 0.4 ppm on the average (Fleischer
3-4
-------
et al., 1974). However, the levels of cadmium in soils vary considerably
depending upon the extent of pollution and distance from the contaminating
sources.
Sargent and Metz (1975) estimated the total amount of land-destined
cadmium emission as about 1,500 MT/yr, which is over 82 percent of the total
release of cadmium to the environment. Major sources of cadmium in soils
are atmospheric fallout and man's input through use of fertilizer and sewage
sludge or leaking and dumping of industrial wastes.
The material flow model (Figure 3.2) has been used to simulate the
movement of cadmium in the Walker Branch watershed in Tennessee by Raridon
et al. (1974). The transported cadmium to the soil environment is absorbed
by biota, and adsorbed on soil particles by ion exchange. Most cadmium in
the soils is found in the top layer (Lagerwerff et al., 1973; Munshower,
1972; Matti et al., 1975) with downward migration reaching to a depth of
at least 30 cm (Kobayashi, 1972). Cadmium leaves the soil environment by
direct surface runoff, leaching, and solute interflow by underground path-
ways or through biochemical activities. Through testing a predictive model
of cadmium and lead ion transport in soil systems, Jurinak and Santillan-
Medrano (1974) found that cadmium content in soils is regulated mainly by
ion exchange or adsorption but not by precipitation except at higher
concentrations.
The availability and uptake of cadmium in soils are largely
determined by the pH, organic matter, other metals, and the cation exchange
capability of the soils. Bolter et al. (1975) reported that organic acids
from decaying leaf litter in the soils increase the solubility, and thus,
subsequent transport of heavy metals including cadmium. They found higher
than background concentrations of cadmium at distances up to 24 km from the
smelters.
For soils with an overlying well-decomposed organic litter layer,
Wixon and Downey (1977) report consistently low concentrations of cadmium
in the soil layers of even smelter-exposed soils. They hypothesize that
the litter layer effectively binds the cationic metals, so that even as the
organic matter continues to decompose the opportunities for horizontal
transport are sufficient to greatly reduce vertical transport to the soil
column.
Cadmium appears to be less mobile in the soil than other heavy metals
except lead. Huckabee and Blaylock (1974) found that 27 days after tagging
with 115mCdCl2, 94 to 96 percent of the initial cadmium added was retained in
the terrestrial portion of test microcosms, and less than 4 percent was
transported to the aquatic portion of the system (Table 3.2). Most of the
cadmium remaining in the terrestrial portion (68 to 77 percent) was bound in
the soil, with approximately 11 to 15 percent retained in the litter. Matti
et al. (1975) showed that about 56 percent of tagged cadmium (109Cd) leached
to the soil, and 42 percent adsorbed on the litter with less than 2 percent
retained by vegetation.
3-5
-------
LEAKS. DUMPING
FERTILIZER
DRY & WETFALL
DEPOSITION
/ V
DIRECT
DEPOSITION
VEGETAL
INTERCEPTI ON
ION EXCHANGE
AT
SOIL SURFACE
MATERIAL EROSION
AND
SOLUTE RUNOFF
SOLUTE
INFILTRATION
SOLUTE
INTERFLOW
INACTIVE
STORAGE
CHANNEL
MATERIAL
FLOW
Figure 3.2. Flow of cadmium in a land area segment
(Raridon et al., 1974).
3-6
-------
TABLE 3.2. DISTRIBUTION OF 284 yCi of 115mCd IN
MICROCOSM EXPERIMENTS AT 27 DAYS
AFTER TAGGING WITH 115mCdCl*
Percent of 115mCd
Component Microcosm AbMicrocosm Bb
Terrestrial
Moss
High plants
Litter
Soil
Aquatic
Water
Sediment
Fish
Snails
Watercress
Plastic liner
93.8
10.2
0.1
15.3
68.2
3.4
0.2
3.1
<0.1
<0.1
<0.09
2.8
95.9
8.2
0.3
10.6
76.8
3.2
0.2
3.0
<0.05
<0.05
<0.05
1.1
o
Source: Huckabee and Blaylock, 1974.
These are intact microcosms; A and B are
replicates.
3-7
-------
In an attempt to quantify the cycling of trace elements in Walker
Branch watershed, Andren et al. (1975) determined a complete input-output
budget for cadmium. During a 6-month period, the watershed retained about
94-95 percent of the total cadmium input, while less than 6 percent was
carried away through the streams. The retention efficiency of cadmium in
soils was next highest of the heavy metals, only that of lead being higher.
A considerable amount of cadmium appeared to be accumulated in the water-
shed, and the estimated doubling time was only 9 years for the soil profile
of the area.
WATER TRANSPORT
Cadmium occurs as the free ion in surface waters. As it moves
through the aqueous environment, it remains as dissolved solids, as parti-
culate matter, or in colloidal form, depending on pH and hardness, and
other soluble complexes of water. Some portions of the total cadmium in
water are taken up by aquatic life, some discharged, and some are adsorbed
or bound to particulate solids and tend to concentrate in the sediment.
Movement and distribution of this element in the aquatic environment
are complex and are influenced by the physicochemical and biological condi-
tions within the system. Studies of two streams in Tennessee by Perhac and
Tamura (cited in Fulkerson and Goeller, 1973) showed that most of the cadmium
in the stream waters, was found in the suspended sediment and bottom sediment
(3 to 230 ppm), while extremely small amounts (less than 0.003 ppm) were
dissolved in water (Table 3.3). Distribution of the tagged cadmium in the
aquatic portion of microcosms (Table 3.1) was mainly limited to the sediment,
while concentrations in the biota were minimal (Huckabee and Blaylock, 1974) .
In another study by Fulkerson and Goeller (1973) (Table 3.4), however, the
accumulation of the cadmium radioisotope was much greater in living organisms
than in the sediment, which consisted mainly of gravel and sand with low
organic materials. Initial concentrations (4-hour) in watercress, peri-
phyton, and snails were much higher than in fish, but they were reduced
greatly with time, whereas the fish slowly picked up 1(^9Cd, probably through
the food chain.
Removal of cadmium from water may be achieved by precipitation as an
insoluble salt, or by adsorption on the surface of solids. Gardiner (1974)
indicated that adsorption and possible desorption were major factors which
influenced the distribution and transport of cadmium in the waters. Hydroxy
and chloride complexes contribute to the mobilization of cadmium in waters
(Hahne and Kroontje, 1973). Other ligands, such as phosphate, cyanide,
carboxylic, hydrocarboxylic, and amino acids, may also contribute to the
distribution of cadmium, although these ligands will complex with cadmium
only if their concentrations are very high.
Organic materials play an important role in heavy metal mobility by
forming organo-metallic complexes (Baker, 1973; Bolter et al., 1975;
Schnitzer and Kahn, 1972) which retard precipitation (Rashid and Leonard,
1973). For several southeastern U.S. rivers and estuaries, the organic acids
3-8
-------
TABLE 3.3. CADMIUM CONTENT OF WATER, SUSPENDED SEDIMENT, AND
BOTTOM SEDIMENT IN TWO TENNESSEE STREAMS3
u>
VO
Suspended Sediment,
ppm
Water, ppm
Location
Cd
Zn
Zn/Cd
Coarse Fine Bottom Sediment,
Cd
Zn Cd
Zn Cd
Zn
.ppm
Zn/Cd
Joe Mill Creek
1.6 km (1.0 mi) above outcrop
0.08 km (0.05 mi) below outcrop
0.96 km (0.6 mi) below outcrop
2.4 km (1.5 mi) below outcrop
0.0031
0.0028
0.0016
0.0020
0.010
0.016
0.025
0.033
3.2
5.7
15.6
16.5
15
21
24
15
230 230
2,480 170
820 70
1,400
50 3
1,840 4
1,360 5
3.4
117
280
300
133
39
70
60
39
Holston River
2.4 km (1.5 mi) above Big Flat Creek
Junction with Big Flat Creekb
0.8 km (0.5 mi) below junction)
0.0008
0.003
0.003
0.020
0.138
0.039
25
46
13
32
61
9,000 460
5,000
9,400 66-87
31-41
12,000
3,500-
4,000
^150
^100
Source: Perhac and Tamura (cited in Fulkerson and Goeller, 1973).
Discharge of plant.
-------
TABLE 3.4. CONCENTRATION RATIOS3 OF 1Q9Cd IN A STREAM ECOSYSTEM1*
Time, days
Source 4-Hour 1 8 14 28 35 42
Sediments
Watercress
Periphyton
Snails
Fish
2.5
11.5
205
7.5
2
2.5
8
160
4.5
2.5
5.5
8
30
6
4
2
2.5
35
6.5
3
4.5
1.5
15
4.5
5
3
. 1.5
10
3.5
10.5
3
1.5
10
2.5
15.5
o
Concentration ratio = activity of Cd/g sample * initial activity of
Cd/ml water.
Source: Fulkerson and Goeller, 1973.
were to be significant factors in transportation of cadmium (Windom,
1976). Salt marshes, highly abundant in organic matter, act as a sink for
iron, manganese, and particulate cadmium.
Cadmium concentrations and their transport by U.S. rivers have not
been investigated utilizing reliable analytical techniques. However, older
studies suggest that highest cadmium flows were found in the mineralized
areas of the Mississippi-Missouri rivers (Durum et al., 1971). Cadmium
flow was also reportedly high in the Illinois River. These data further
suggest that mining drainage and industrial effluent were the major sources
of cadmium contamination in rivers. Sargent and Metz (1975) indicate that
the waterborne cadmium effluent from industry is approaching comparatively
negligible quantities due to improved technologies for wastewater treatment
and cadmium removal.
Table 3.5 summarizes data on the cycling budgets for cadmium in
several watersheds and salt marshes. Approximately 95 percent of the
introduced cadmium in the Walker Branch watershed in Tennessee was retained,
while only 17 percent of the total cadmium input (in rain) remained in the
Atlantic salt marshes. More variations in cadmium transport, ranging from
9 to 89 percent, were observed in the 8 small watersheds in Delaware (Biggs
et al., 1973). This may be due to the amount of stream discharge and
available organic acids in the ecosystems. Proportions of cadmium trans-
ported as dissolved and particulate species in the Walker Branch stream were
99.4 and 0.6 percent, respectively, and for the southeastern Atlantic salt
marshes, were 78.8 and 21.2 percent.
3-10
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TABLE 3.5. CADMIUM CYCLING BUDGETS IN SEVERAL WATERSHEDS AND SALT MARSHES
Total Stream Output
Total Cadmium Input,
Location Input Net Flux % Reference Remarks
<_0 Walker Branch Watershed 63.9 g/ha/6 months 3/5 g/ha/6 months 5.5 Andren et al, 1975 97.5 ha catchment
.)_, Oak Ridge, Tennessee (Range: 5-6)
M
Delaware Watersheds 1,387.1 kg/yr 285.1 kg yr 20.6 Biggs, et al., 1973 8 small watersheds
(Range: 9-89)
Southeast Atlantic Salt 52 x 103 kg/yr 43 x 103 kg yr 82.7 Windom, 1976 Coastal rivers and littoral-
Marshes—South Carolina, salt marsh estuaries
Georgia, Florida
-------
SEDIMENT TRANSPORT
The distribution patterns in the sediments appeared to be mainly a
function of water current, basin depth and slope, winds and shoreline
patterns (Browne, 1975; Klein and Russell, 1973; Peyton and Mclntosh, 1974).
In the vicinity of Erie, Pennsylvania, Browne (1975) found that the site
with the highest concentration of cadmium in the sediment was not associated
with a tributary, nor were the water concentrations significantly higher
than those at other stations. This may indicate that the area nearest the
emission source may not necessarily be the most severely affected area,
perhaps due to currents and wind activities. Cadmium in water may not
disperse evenly or settle out rapidly but be carried by currents or wave
action to other areas.
Generally, areas undergoing more mixing and having less vegetation
accumulate less heavy metals in the sediments (Browne, 1975). Accumulations
by vegetation and bacteria and subsequent decompositions affect the retention
of the metals in the sediments. The presence of other heavy metals, such as
lead (0.1 to 0.5 ppm) may inhibit bacterial decomposition and thus alter
cadmium content. Moyer and Budinger (1974) indicated that sulfur dioxide
might play an important role in precipitation of cadmium as greenockite
(CdS) from dissolved cadmium salts. This mechanism was suggested for higher
cadmium levels in tidal shoreline sediments in San Francisco Bay. Oxidate
sediments such as manganese nodules also adsorb significant amounts of
cadmium as do phosphorite deposits of organic origin. Selenium and cadmium
will precipitate as cadmoselite (CdSe) into the sediments.
Tidal effects on cadmium concentrations were observed in Foundry Cove
on the Hudson River, New York (Kneip et al., 1975). With rising ebb tide,
alkalinity and dissolved oxygen increased which resulted in increased
insoluble cadmium concentrations. Bondietti et al. (1974) found that the
carbonate-rich sediments of Foundry Cove stabilized the cadmium, thus
limiting its availab.ility for chemical and biological reactions. The
sediments of Long Island Sound appear to have become progressively more
enriched in cadmium over the past 100 years (Turekian, 1974) . The sediments
below about 2 cm become anoxic, allowing sulfate-reducing bacteria to
produce H2S, which reduces solubility and, therefore, mobility of most heavy
metals (Turekian, 1974) . Metals that do escape are sequestered by the
precipitation of iron and manganese oxide formation at the sediment/water
interface; therefore, there is little chance of metal escaping in the
estuary except for extreme perturbations. Disturbances by dredging,
turbulence, and biological activities of living organisms may induce
redistribution of the sedimented cadmium. The relative insolubility of
cadmium and its tendency to adsorb and complex with other particulate
matter appear to destine it to the sediments of the estuaries and oceans.
FOOD CHAIN TRANSPORT
Man depends on the following major trophic compartments for food:
3-12
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• Land plants
• Land animals and animal products
• Freshwater fish
• Marine fish and free-moving crustaceans
• Shellfish.
Using various references cited elsewhere in this report, potential dietary
pathways by which man can be exposed to cadmium were constructed (Table 3.6)
Mean concentrations of cadmium vary among the five major food groups.
Concentrations (ppm) in milk averaged <0.01; marine fish, freshwater pond
fish, and land plants <0.3; mammals, birds, and shellfish, about 0.7.
Finally, freshwater stream fish exhibited the highest average, 1.87.
TABLE 3.6. TRENDS OF ARITHMETIC AVERAGE CONCENTRATIONS (PPM) OF
CADMIUM IN DIETARY FOOD GROUPS IN TWO MAJOR FOOD
PATHWAYS TO MANa
Water-Based Food Chains to Man
Land-Based Food Chains to Man Marine Fish/
Plants Animal Freshwater Fish Crustaceans Shellfish
0.261 0.756 (mammals) 0.112 (pond) 0.102 0.889
0.496 (birds) 1.87 (stream)
0.008 (milk)
Various references—cited elsewhere in this report.
Marine and pond fish move freely in essentially standing-water
ecosystems where cadmium concentrations are relatively low compared to soil
and sediments. Fish in moving-water systems are exposed to the constant
flow of cadmium leached from the land, are near the stream/sediment inter-
face, and eat invertebrates which may contain up to 60 ppm of cadmium (see
Section 2). Sessile marine shellfish live at a water/sediment interface
where filter and sediment feeding exposes them to greater quantities of
cadmium than does the water column. Thus, the foods in the water-based food
chain with lowest concentrations are marine and pond fish. Higher exposures
may be involved by eating freshwater stream fish and shellfish.
In the land-based food chain to man, animals showed higher average
concentrations than did plants, although milk was very low. The matching
of plant species with those herbivores which specialize on those species and
man within food chains will be necessary to develop a defendable conclusion,
but it appears that animal parts would expose man to more cadmium than would
3-13
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plants. Foods produced by terrestrial ecosystems show intermediate concen-
trations of cadmium between (1) marine and pond fish and (2) stream fish and
shellfish.
The above observations should be tempered with the fact that uptake
of cadmium by plants and animals is insignificant compared to cadmium loads
in the soil, although some living organisms are known to accumulate cadmium
greater than their background levels by orders of magnitude. Munshower
(1972) reported that cadmium loads in plants and herbivore animals were less
than 0.1 percent of the soil cadmium load in an area about 15 miles from the
smelter near Deer Lodge Valley, Montana.
3-14
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4. CADMIUM IN FOODS
SOURCES OF FOOD CONTAMINATION
Incorporation of cadmium into foods can take place through a variety
of mechamisms. For grains and processed foods, several of these contamina-
tion mechanisms seem to operate simultaneously (Fishbein, 1974). Listed in
order of importance, they are:
(1) Uptake from soils by roots of plant foods.
This may occur:
a. Naturally as a normal constituent of soils
of marine origin
b. As an impurity (cadmium oxide) in phosphate-
treated soils, especially "superphosphate"
c. In soils fertilized by sludge containing
cadmium
d. As an impurity of zinc in certain zinc-
containing fungicides and herbicides
e. By deposition on plants and soil by cadmium-
containing pesticides
f. By soil contamination from runoff of mine
tailings or from electroplating washing process.
(2) Meat animals may accumulate cadmium from
a. Feeding on crops which have absorbed cadmium.
The organs of such animals may have very high
cadmium concentrations.
«
b. From cadmium-containing helminth killers,
used especially in swine.
(3) Molluscs and crustaceans normally concentrate
cadmium from ambient waters, as do most other
aquatic organisms.
4-1
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(4) Contamination of foods from use of zinc-galvanized
containers, cans, implements or cooking vessels,
or utensils used in food preparation, particularly
grinders, pressing machines, or galvanized netting
used to dry fish and gelatin.
(5) Contamination from absorption of cadmium contained
in -wrapping and packaging materials such as paper,
plastic bags, and tin cans.
(6) Use of cadmium-contaminated water in cooking or
processing operations.
For the general population, oral ingestion of foods may represent
the most important source of cadmium intake. Airborne sources constitute a
significant portion of cadmium intake only for those occupationally exposed,
particularly to cadmium oxide fumes, or those residing in areas heavily
polluted by cadmium-emitting industries (Friberg et al., 1973).
Continued, low-dose exposure to cadmium in foods is of great concern
because the long biological half-life of cadmium, 17 to 33 years, permits
substantial accumulation in the body (Deane et al., 1976).
CIGARETTES
Lewis et al. (1972) found that cigarette smoking provides a
surprisingly great contribution to cadmium intake and subsequent body burden.
After examining cadmium levels in liver, lungs, and kidney from autopsy
tissues, they estimated body retention levels of 1 yg/day or less from
nonsmokers compared to 2.5 yg/day for smokers:. Indicated in Table 4.1 is
the magnitude of the contribution to daily intake from cigarettes. The
respiratory intake from 2 packs per day ranges between 4 to 6 yg, supplying
over 30 percent of daily cadmium retention for the pack-a-day smoker and 56.6
percent of retention for the 3-packs-a-day smoker (Deane et al., 1976). The
amount of cadmium inhaled from 2 packs of cigarettes per day equals 10 to 20
times the estimated intake from air in lower Manhattan (Fleischer et al.,
.1974). Yet despite the possible exceptions mentioned—occupational exposure,
residents of heavily polluted areas, or heavy cigarette smokers—Table 4.1
illustrates that diet is generally by far the greatest source of cadmium.
FOODS
Unlike many other metals which are restricted to a narrow range of
foods, cadmium has an extremely generalized distribution. Of the 33 pesti-
cide residues detected in food composites by the National Pesticide Monitor-
ing Program in FY 1971, cadmium heads the list as the most frequently found
residue with two-thirds''of 360 composites reporting positive findings with
the range of values for.-the positive composites being 0.01 to 0.20 ppm
(Manske and Corneliussen, 1974). Cadmium is found in measurable quantities
4-2
-------
in all food groups, but it is uncertain whether the cadmium content of most
food is ubiquitous or "natural", or whether cadmium has been introduced into
foods and beverages as an industrial contaminant.
TABLE 4.1. MEDIA CONTRIBUTIONS TO NORMAL
RETENTION OF CADMIUM3
Daily Retention,
Medium Exposure Level yg
Ambient air
Water
Cigarettes
Packs /day
1/2
1
2
3
Food
3
0.03 yg/m
1 ppb
b
yg/day
1.1
2.2
4.4
6.6
50 yg/day
0.15
0.09
0.70°
1.41C
2.82C
4.22°
3.0
aSource: Deane et al., 1976.
Based on 0.11 yg per cigarette.
Assumes a 6.4 percent retention rate.
Friberg et al. (1973) have collected and reviewed extensive data on
cadmium in foods. There seems to be general agreement that foods average
about 0.05 ppm cadmium (wet weight); however, there is substantial variation
depending on the source (Fleischer et al., 1974).
Estimates derived from analysis of institutional diets (Murthy et al
al., 1971), school lunch studies (Murphy et al., 1971), and the continuing
Market Basket Program of the National Pesticides Monitoring Program (Friberg
et al., 1973; Manske and Corneliussen, 1974; Mahaffey et al., 1975) represent
further attempts to quantify cadmium intake in the context of a normal diet.
Table 4.2 presents estimates of daily cadmium obtained from six dietary
surveys in the U.S. Most studies coincide reasonably well with the 30 to 70
yg/day range which has been proposed by Friberg et al. (1973) as the typical
dietary cadmium intake for Americans.
4-3
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TABLE 4.2. ESTIMATED DAILY CADMIUM INTAKE FROM FOODS
IN VARIOUS LOCATIONS IN THE UNITED STATES3
Date of
Sample Concentration, yg/day
Collection Mean Range Reference Remarks
1966 39 <141 Murphy et al., 1971 School lunch survey
1967 92 32-158 Murthy et al., 1971 Institutional total
diet study
1969 170b Friberg, 1971
1973 51.2 Mahaffey et al., 1975 FDA total diet study
aSource: Mahaffey et al., 1975.
Assayed without preliminary extraction.
Studies of seasonal and regional variations have failed to reveal
any meaningful trends or geographic patterns (Murthy et al., 1971; Murphy
et al., 1971). This is illustrated in Figure 4.1 which shows the distribu-
tion of cadmium levels in institutional diets in the United States.
Table 4.3 contains Friberg's interpretation (1974) of data taken from
Corneliussen (1970) and Duggan and Corneliussen (1972) . Their work covers
studies made on samples collected from 30 markets in 24 cities in the United
States.
The FDA National Pesticides Monitoring Program's Market Basket
Program utilizes samples collected from 30 markets in 27 U.S. cities. Foods
are purchased according to a specified list of 117 items. Content and
portions are prepared to simulate the diet of a 16 to 19-year-old male,
statistically the largest eater. Market Basket Program data show that on a
national basis cadmium was: (1) found in composites from all food categories
and (2) present in greater than 10 percent of composites in all food groups
(Carroll et al., 1975). Composites of potatoes, root vegetables, garden
fruits, and oils, fats, and shortenings yielded positive findings in over
90 percent of composites.
Fish and shellfish typically have elevated cadmium concentrations, but
as a rule are not consumed in large quantities by most Americans. As shown
in Table 4.4, lower levels of cadmium in potatoes, fruits, and grains and
cereals may warrant greater concern, because these foods are consumed in
4-4
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SAN <^ic° w«)
\V! LMI NGTON
(0.055)
/ FALLS
(0.060)*
CARSOf
ALT LAK
CITY i
(0.029)
(0.056)
BOSTON
0 5 2)
LOS ANGELE
(0.033)
CHARLESTON
(0.048)
(TAMPA
(0.060)
Figure 4.1. Average values (in ppm) of cadmium content in institutional
total diets, 1967 (Murthy et al., 1971).
-------
TABLE 4.3. CADMIUM CONTENT IN DIFFERENT FOOD CATEGORIES IN THE U.S.A.
a,b
Cadmium, yg/g wet weight
1968-1969
Type of Food
Dairy products
Meat, fish, and
poultry
Grain and cereal
products
Leafy vegetables
Legume vegetables
Root vegetables
Garden fruits
Fruits
Oils, fats, and
shortening
Sugar and adjuncts
Beverages
Potatoes
No. >0.01
10
21
27
27
16
24
25
15
27
18
8
Maximum
0.09
0.06
0.08
0.08
0.03
0.08
0.07
0.38
0.13
0.07
0.04
1969-1970
No. >0.01
9
22
27
28
10
27
27
10
28
9
9
29
Maximum
0.01
0.03
0.06
0.14
0.04
0.08
0.07
0.07
0.04
0.04
0.04
0.08
aSource: Corneliussen, 1970; Duggan and Corneliussen, 1972.
Cadmium was analyzed by atomic absorption and/or polarography at
a sensitivity of 9.01 yg/g.
4-6
-------
vastly greater quantities than fish and, consequently, contribute a large
proportion of dietary cadmium. Two food classes, (1) meat, fish, and
poultry, and (2) dairy products, have positive findings for cadmium less
frequently than would be expected if food chain accumulation of cadmium were
significant (Table 4.5). Mean concentrations in these food groups ranked
eighth and twelfth out of 12, respectively (Mahaffey et al., 1975). Studies
of the Market Basket type, which analyze foods in composite categories
rather than performing cadmium determinations on individual foods, run the
risk of concealing foods which may contain unusually high cadmium concentra-
tions, by combining them into composites with other foods typically having
much lower cadmium content. Undoubtedly, this factor applies when meats and
poultry are composited with fish.
In 1973 the FDA initiated a new program called the Heavy Metals in
Foods survey designed to measure the content of lead, cadmium, and zinc in
individual foods rather than composites (U.S. Department of Health, Education,
and Welfare, 1975). Criteria for selection of foods to survey were (1) rela-
tive importance in the diet, both adult and infant, (2) past indication of
particularly high levels in the selected foods, and (3) balanced coverage of
raw and processed foods. The following is a summary of the mean levels of
cadmium found in the 41 foods surveyed. Foods are grouped as adult noncanned
foods, adult canned foods, and baby foods to provide an overview as to
whether canning might be a source of increased cadmium in foods:
Category Cadmium, ppm
All adult foods (32) 0.047
Canned adult foods (13) 0.029
Noncanned adult foods (19) 0.060
Baby foods (9) 0.024
It appears that cadmium levels are not affected by canning processes.
Comparing fruits and vegetables in jars and cans with raw vegetables shows
canned foods do not contain increased cadmium levels. Cadmium levels in
selected adult foods are presented in Table 4.5. Cadmium concentrations in
meats are generally higher and more than in most other foods.
Concentrations in grains and cereal items are also higher than in most other
foods. Among adult foods, raw liver had the highest mean cadmium level,
0.183 ppm. Sugar, hamburger, and eggs followed with mean levels of 0.100,
0.075, and 0.067 ppm, respectively. Milk and canned peas were lowest with
means of 0.008 ppm for both. Overall, 99 percent of adult samples had 0.68
ppm or lower and 35.3 percent had no detectable cadmium.
Results for the baby foods surveyed are presented in Table 4.6.
Spinach had the highest mean level, 0.057 ppm. Orange juice, mixed vege-
tables, and vegetables and beef were next in order, having means of 0.040,
0.034, and 0.026 ppm, respectively. Peaches, 0.003 ppm, and applesauce,
0.007 ppm, had the lowest baby food means.
4-7
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TABLE 4.4. FOOD GROUPS BY MEAN CADMIUM CONTENT AND THEIR
CONTRIBUTION TO DAILY CADMIUM INTAKE3
I
oo
Concentration, ppm Intake,
Food Group
Leafy vegetables
Potatoes
Fruits
Grains and cereals
Oils, fats, and shortening
Root vegetables
Garden fruits
Meats, fish, and poultry
Sugars and adjuncts
Legume vegetables
Beverages
Dairy
Mean
0.051
0.046
0.042
0.028
0.027
0.021
0.019
0.0093
0.0083
0.006
0.0057
0.005
yg/day
3.18
9.11
9.38
11.66
1.36
0.76
1.71
2.49
0.68
0.42
6.49
3.94
Percent of
Total
Daily Diet
2.0
7.0
7.4
12.6
1.8
1.2
3.0
9.9
2.8
2.5
23. 9b
25.9
Contribution to
Daily Cadmium
Intake , %
6.2
17.8
18.3
22.8
2.7
1.5
3.4 '
4.9
1.3
.0.8
12.7
7.7
Source: Mahaffey et al., 1975.
Includes water.
-------
TABLE 4.5. CADMIUM CONTENT OF SELECTED ADULT FOODS3
Commodity
Carrots, roots fresh
Lettuce, raw crisp head
Potatoes, raw white
Butter
Margarine
Eggs, whole fresh
Chicken fryer, raw
whole or whole cut up
Bacon, cured raw, sliced
Frankfurters
Liver, raw beef
Hamburger, raw ground beef
Roast, chuck beef
Wheat flour, white
Sugar refined, beet or cane
Bread, white
Orange juice, canned frozen
concentrate
Green beans, canned
Beans, canned with pork and
tomato sauce
Peas , canned
Tomatoes , canned
Diluted fruit drinks, canned
Peaches , canned
Pineapple, canned
Applesauce, canned
No. of
Samples
69
69
71
71
71
71
71
71
69
71
71
71
71
71
70
71
71
71
71
71
71
71
71
71
Average ,
ppm
0.051
0.062
0.057
0.032
0.027
0.067
0.039
0.040
0.042
0.183
0.075
0.035
0.064
0.100
0.036
0.029
0.018
0.009
0.042
0.042
0.017
0.036
0.059
0.020
Standard
Deviation,
ppm
0.077
0.124
0.139
0.071
0.048
0.072
0.088
0.160
0.111
0.228
0.122
0.034
0.150
0.709
0.063
0.095
0.072
0.000
0.113
0.113
0.052
0.061
0.153
0.027
a
Source: U.S. Department of Health, Education, and Welfare, 1975,
4-9
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TABLE 4.6. CADMIUM CONTENT OF SELECTED BABY FOODS'
Commodity
Vegetables and beef
Mixed vegetables
Spinach
Orange juice
Apple juice
Applesauce
Pears
Peaches
Apricots
No. of
Samples
71
71
69
71
71
71
71
71
71
Average ,
ppm
0.026
0.034
0.057
0.040
0.023
0.007
0.013
0.003
0.011
Standard
Deviation,
ppm
0.035
0.052
0.054
0.084
0.035
0.023
0.053
0.005
0.037
Range
Low
0
0
0
0
0
0
0
0
0
, PPm
High
0.24
0.401
0.43
0.43
0.264
0.18
0.520
0.04
0.32
Source: U.S. Department of Health, Education, and Welfare, 1975.
Table 4.7 shows yearly values in the cadmium content of U.S. foods,
as obtained from the FDA's total diet surveys. No trends of increasing or
decreasing cadmium levels were noted from 1968 to 1974.
Foods processed by grinding, milling, powdering, drying, or pressing
often appear to contain cadmium in larger amounts than in the original
ingredients. "Instant" products,, for example, coffees and teas, as well as
some condiments and spices appear to contain abnormally high levels of
cadmium. The precise mechanism of the possible transfer of cadmium from
processing equipment to these foods has not been investigated. In Table 4.8
Schroeder (1974) presents some speculations. In an analytical study of paper
products commonly used for packaging foods, Lagerwerff and Specht (1971)
found 0.22 ppm of cadmium in thin cardboard and 0.30 ppm in gloss paper,
presumably of the type used inside food boxes. Again, the mechanism for
the possible transfer of cadmium in packaging materials to foods remains
to be investigated.
4-10
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TABLE 4.7. CADMIUM CONTENT OF FOODS BY YEAR AND DAILY INTAKE3
(microgratns/day)
1968 1969 1970 1971 1972 1973 1974
26 61 38 29 37 51 34
Source: Mahaffey et al., 1975.
Estimated level.
TABLE 4.8. POTENTIAL EXPOSURES OF HUMAN BEINGS
TO CADMIUM FROM FOOD SOURCES3
Source
Remarks
Galvanized iron pipes
Galvanized iron roofs
Galvanized iron cisterns and tanks
Cola drinks
Instant coffees
Oysters
Some canned and dried fish
Pigment in candy
From plastic wrappings
Plated ice trays
Plated roasting pans
Pigmented pottery
Silver polish
Pork kidneys
Butter
Olive oil
Gelatin, dried fish
Many processed meats
Tin and aluminum cans
Soft and acid waters dissolve from zinc
coating.
Dissolved by rainwater.
Dissolved by soft water.
From processing, usually 10 yg/quart or
less.
From processing.
Up to 7 ppm, with much zinc.
From canning, dying, or smoking.
Galvanized wire netting?
"Luv beads" make children ill.
Absorbed by food.
Dissolved by acid sherbets.
Dissolved by roasting fats.
Dissolved by acid foods and juices.
Residue on eating utensils.
Cadmium used as a vermifuge.
Probably from galvanized milk cans.
From cans and presses.
From galvanized netting for drying.
From contact in processing machines.
Tin cans made of old cars, aluminum
from old aircraft.
Reprinted from The Poisons Around Us by H. A. Schroeder, by permission of
Indiana University Press. Year of publication 1974.
4-11
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5. CADMIUM IN MAN
Cadmium is a highly toxic element with no known useful biological
function except as might be indicated by Schwartz1 studies (1977). The need
for precautions in industrial operations in which workers are exposed to
dusts and vapors of the elements has long been known, and in recent years
concern has been expressed over the possible effects on human health of
chronic exposure to low concentrations of cadmium. This concern has been
triggered by (1) the steadily increasing industrial consumption and conse-
quent rise of cadmium levels in the environment and (2) the outbreak in
Japan of Itai-Itai disease in the late 1940's and early 1950's.
DISTRIBUTION OF CADMIUM
The average human intake of cadmium is about 50 to 75 yg/day,
chiefly from food. Intestinal absorption, which is governed by nutritional
factors, is about 6 to 10 percent. Absorption through the lungs, which
plays the major role in occupational exposures, ranges from 10 to 40 percent.
The significance of inhalation exposure depends upon the concentration,
particle size, solubility of the particulate matter, and the physiologic
parameters such as the rate and depth of the respiration. Threshold limit
values adopted by the American Conference of Governmental Industrial
Hygienists for cadmium dusts, fumes, and salts (as cadmium) are 0.05 mg/m .
Cigarette smoke is also a source of cadmium absorption via the pulmonary
route. Cadmium accumulates in the kidney cortex, where it can cause renal
tubular dysfunction at levels of approximately 200 ppm in outer cortex.
Autopsy studies show current levels of 15 to 50 ppm in kidneys of people
over 50 who were not occupationally exposed. The higher levels generally
were found in individuals who had been smokers. Cadmium accumulation in the
placenta during pregnancy has been reported as not more than 5 ppm; in the
neonate, 1 ppm. However, with years of nonindustrial exposure, the average
body burden at age 50 has been estimated in the U.S. at about 30 mg. This
is reflected by increased concentrations of cadmium not only in the kidney
and liver but also in the pancreas and blood vessels. About 5 percent of
ingested cadmium is retained in the body and its biological half-life in
humans is estimated to be about 15 to 50 years. Absorbed cadmium is
transported in the red blood cells. The normal cadmium blood level is
below 1 yg/100 ml; but in exposed workers, the range may be from 1 to 10 yg/
100 ml. Normal urinary levels of cadmium in the U.S. are in the range of
0.5 to 10 ppm. The urine is the primary route of excretion of absorbed
cadmium. Secondary routes of excretion occur in the feces and in hair.
5-1
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BODY BURDEN
Table 5.1 summarizes cadmium levels in various tissues of exposed and
nonexposed persons. "Nonexposed" refers to persons living under normal
environmental levels of cadmium in air, water, and food. "Exposed" refers
to persons having occupational contact with cadmium or to residents of areas
with elevated ambient levels of cadmium, or in the case of Lewis et al.
(1972), the exposed and nonexposed categories differentiate between persons
who are exposed to cadmium through cigarette smoking and nonsmoking indivi-
duals. The high levels in the kidney and liver are believed to reflect the
storage of cadmium in metallothionein (Hammons and Huff, 1975). However,
autopsy studies have revealed that smaller, yet significant, amounts of
cadmium may accumulate in the lungs, pancreas, adrenal glands, thyroid,
spleen, salivary glands, and testes.
Hammer et al. (1973) state that body burdens are best estimated from
the total cadmium content of the kidney and the liver. Noncigarette smoking
males, aged 40 to 70, have about 5.2 mg of cadmium in their kidneys and about
3.7 mg of cadmium in their liver or a combined total of 8.9 mg. Comparable
figures for males smoking one-half pack or more daily would be 11.4 mg in the
kidney and 7.5 mg in the liver for a combined total of 18.9 mg of cadmium in
these two organs. Since the amount in the kidneys and liver represents
approximately 50 percent of the adult body burden, this is estimated to be
about 17.8 mg of cadmium for male nonsmokers and about 37.8 mg of cadmium in
smokers.
As presented in Table 5.2, data reported by Lewis et al. (1972) show
that adult American male nonsmokers with mean age of 60 have, on the average,
a total body burden of about 13 mg of cadmium. In contrast, the adult
cigarette smokers have a total body burden of 30 to 40 mg. The difference
between the two groups suggests that more than one-half of the cadmium found
in the smoking group comes from cigarette smoking. Cigar and pipe smokers
yielded average cadmium values. Ex-smokers had mean total organ and
composite values similar to those of light cigarette smokers. The multiple
regression analysis of composite cadmium content of each organ for each
subject implicates cigarettes as a major source of the total body burden of
cadmium. Lewis et al. (1972) found that when control is made for smoking
habits, subjects with chronic bronchitis, emphysema, cancer of the bronchus
or lungs, and arterial hypertension do not have more cadmium in their tissues
than those without. Table 5.3 illustrates the contribution of the various
media to cadmium retention and subsequent body burden (Environmental Health
Resources Center, 1973). Intake levels of less than the given amounts would
result in body burden of less than 30 mg/45 years. Friberg et al. (1974)
suggest that currently the body burden of adults in the United States is in
the 15 to 20 mg range.
Placental Transfer
The effectiveness of the placental barrier in protecting the fetus
from cadmium varies with dose and with time during pregnancy. Normally in
5-2
-------
TABLE 5.1. SUMMARY DATA ON CADMIUM LEVELS IN VARIOUS TISSUES OF EXPOSED AND NONEXPOSED PERSONS
Ul
I
OJ
Concentration, ppm
Tissue
Renal
Cortex
Blood
Urine
Feces
Hair
Age Sex Nonexposed
50-75 25-503
0.01
10C
l-2e
3ie
Female 1.77
10 Male 1.3
Exposed
20-500b
0.01-0.1
0.41d
Up to 100 yg/day
f
NA
3.5
Reference Remarks
Friberg et al., 1974 About 2/3 of workers were
above 100 ppm average .
" Levels below 0.1 most typical.
"
11
Schroeder and Nason,
1969
Hammer et al, 1971 "Nonexposed" refers to resi-
Kidney
14.8
31.1
Wet weight.
"Upper limit approximate.
cNanograms per gram.
"Mean value.
eMicrograms per day.
fNA = Not available.
Lewis et al., 1972
dents of lowest two popula-
tion levels. "Exposed" were
residents of heavy pollution
area rather than industrial
exposure.
Exposure to cadmium from
cigarette smoking—not
industrial exposure.
Liver
Lung
1.38
0.33
2.05
0.56
-------
TABLE 5.2. CADMIUM CONCENTRATION IN WET TISSUE, SMOKERS AND NONSMOKERS'
Concentration, ppm,
ash weight^3
Date of
Data No. of
Collection ~ Source Samples
Nonsmokers
ca. 1971 Male 23
23
21
Female 11
11
9
Total 34
34
30
Cigarette Smokers
ca. 1971 Light, <1 pack/day 11
11
11
Moderate, >1 pack/day 57
but <2 packs /day 57
56
Heavy, >2 packs day 37
38
Total, cigarette smokers 105
106
103
Ex-Cigarette Smokers
21
21
19
Organ
Kidney
Liver
Lung
Kidney
Liver
Lung
Kidney
Liver
Lung
Kidney
Liver
Lung
Kidney
Liver
Lung
Kidney
Liver
Kidney
Liver
Lung
Kidney
Liver
Lung
Standard Error
of the Mean,
Mean ppm
13.2
1.06
0.30
18.0
2.06
0.41
14.8
1.38
0.33
24.3
1.79
0.51
32.5
2.02
0.59
30.9
2.16
31.1
2.05
0.56
21.6
1.69
0.70
2.33
0.11
0.05
2.83
0.29
0.10
1.86
0.24
0.04
3.00
0.32
0.11
2.49
0.17
0.59
2.28
0.22
1.63
2.05
0.03
2.49
0.18
0.13
Source: Lewis et al., 1972.
Data were collected at Boston, Massachusetts, Veterans Administration
Hospital and Providence, Rhode Island, Roger Williams Hospital.
5-4
-------
TABLE 5.3. CADMIUM BODY BURDEN MEDIA RETENTION3
Concentration
Cadmium Source yg/day mg/year mg/45 years
Food and water ingestion:
50 Mg/day x 0.025 1.25 0.46 20.1
Cigarettes: 0.067 yg/cigarette ,
x 10 cigarettes/day 0.67 0.25 4.9
3
Air: 20 m /day x 0.30 x
0.05 yg/m3 0.30 0.11 5.0
30.0
Q
Source: Environmental Health Resources Center, 1973.
Estimate based on 20-year period.
humans the placenta is an effective barrier. The total body content of
cadmium in newborn fetuses from West Germany was less than 1 yg (Hammons and
Huff, 1975). In areas where the normal daily uptake of cadmium is higher
than that in West Germany, Japan, for example, higher fetal cadmium levels
may occur (Chaube et al., 1973).
Placental and Fetal Levels
Baglan et al. (1974), in a study of human placentas as possible
indicators of environmental exposure, measured the levels of eight trace
metals, including cadmium, in placentas, maternal blood, and fetal blood.
In general, the placental levels of metals exceed both maternal and fetal
blood levels, and the maternal blood levels exceed the fetal blood levels.
Data for cadmium are shown in Table 5.4.
Dawson et al. (1968) investigated seasonal variations in nine
cations including cadmium in normal term placentas. Results from 554
placentas indicated a seasonal variation in mean monthly levels of sodium,
potassium, magnesium, and lead. Race, maternal age, and pregnancy had no
observable effect.
In areas where there is an abnormally high intake of cadmium,
elevated fetal levels of cadmium may occur (Chaube et al., 1973. These
investigators determined zinc and cadmium concentrations in 36 first-
trimester intact human embryos and in liver, brain, and kidney of 14 second-
and 1 third-trimester fetuses. Zinc increased sevenfold between the 31st
and 35th day of gestation. Cadmium was present in 57 percent of specimens
in concentrations from 0.032 ppm to 0.07 ppm of wet tissue. In second
5-5
-------
TABLE 5.4. MEAN CADMIUM LEVELS IN HUMAN PLACENTAS,
MATERNAL BLOOD, AND FETAL BLOOD3
Number of
Samples
Organ Site
Concentration, ppm
Mean
Remarks
135
Placenta
0.102 ± 0.077
Placentas obtained from
four large Nashville
hospitals.
83
123
Maternal blood
Fetal blood
0.093 ± 0.115
0.076 ± 0.109
Source: Baglan et al., 1974.
Samples were collected from September, 1971, to November, 1972,
in Nashville, Tennessee.
trimester specimens, mean zinc concentration in brain was 5.6 ppm, in
kidney 15.7 ppm, and in liver 167.7 ppm. Cadmium was present in 80 percent
of livers (mean, 0.113 ppm), 28 percent of kidneys (mean, 0.05 ppm), and 17
percent of brain specimens (mean, 0.140 ppm). Although mothers of these
fetuses did not live in areas of Japan'where endemic cadmium poisoning
exists, the higher cadmium content of the average Japanese diet may be
reflected in the cadmium concentrations of these specimens.
Cadmium Levels and Distribution in Blood
Studies of cadmium levels in whole blood in normal, nonexposed human
populations generally reveal whole blood cadmium levels of less than 1 yg/100
ml; but in exposed workers the range may be from 1 to 10 yg/100 ml. Friberg
et al. (1971) caution, however, that the analytical methods have not been
sufficiently perfected to enable accurate determination of cadmium in blood
because the usual quantities of cadmium observed in blood are so small.
Within the blood, more cadmium is in the plasma than in the cells in those
persons without known exposure to cadmium (Friberg et al., 1971). A ratio
of 1.9 between plasma and cell levels and a mean of 0.35 yg/100 ml was found
in healthy persons (Friberg et al., 1974). Similarly, Friberg et al. (1973)
reported a mean value of 0.49 yg/100 ml in normal, healthy children.
Bogden et al. (1974) assayed whole blood of inner-city children in
Newark, New Jersey, for cadmium, lead, and zinc and determined frequency
distributions for each metal. The mean concentration of cadmium (0.3 yg/100
ml) found in 369 analyses is somewhat lower than values found in other studies
5-6
-------
reported by Bogden (Table 5.5). Significant correlations were found between
whole blood concentrations of zinc and cadmium and between concentrations of
lead and cadmium. Paint is suggested as the major source of ingested lead
and cadmium and air as a respiratory contaminant for all three metals.
TABLE 5.5. WHOLE BLOOD ASSAYS3
Cadmium, yg/100 ml
Population Tested Mean Range
Hospitalized children 0.5 0.0-1.9
Children with suspected pica 0.6 0.0-7.9
Adult males 0.9 0.3-5.4
Inner city children 0.3 0.0-2.8
aSource: Bogden et al., 1974.
Glauser et al. (1976) found living normal humans to have a blood
cadmium level of 0.34 ± 0.05 yg/100 ml, while a matched group of living
untreated hypertensive humans had a blood cadmium level of 1.1 ± 0.15 yg/
100 ml. Workers chronically exposed to cadmium may not only have blood
cadmium levels elevated considerably in excess of those observed in "normals"
but also the distribution of cadmium within the blood may differ. In
contrast to normal persons in whom the majority of cadmium is in the plasma
fraction of the blood, exposed workers' blood contains more cadmium in the
cells than in the plasma. Friberg et al. (1974) reported a cell-to-plasma
ratio of 0.5 and a mean whole blood level of 4.1 yg/100 ml for an occupa-
tionally exposed group. Little can be generalized from the studies of
exposed workers except that their blood cadmium levels may be markedly
elevated. One difficult problem is that individual exposure conditions
usually cannot be specified adequately. Secondly, wide fluctuations within
some individuals are observed during exposures, while in other co-workers,
a more steady level is seen (Friberg et al., 1971). Piscator and Lind
(1972) studied a group of 25 workers in an alkaline battery factory in an
effort to relate cadmium concentrations in blood to exposure time. Results
were negative.
Friberg et al. (1973) have concluded that there were no consistent
relationships among the following: (1) between cadmium levels in blood and
exposure time, (2) between blood levels and body burden, (3) between degree
of proteinuria and blood levels, and (4) between levels of cadmium in blood
and urinary excretion of cadmium.
5-7
-------
Cadmium in the Renal Cortex
Friberg et al. (1973) reviewed several studies which estimated the
average cadmium levels in the renal cortex for United States adults aged
50 to 75. Most of these estimates lie in the range of 25 to 50 ppm wet
weight. These values are perhaps slightly higher than those reported by
Sweden, United Kingdom, and Europe; however, they are much lower than the
90 to 125 ppm wet weight which has been reported for comparably aged
Japanese in nonpolluted areas (Friberg et al., 1973).
Livingstone (1972) studied renal accumulations of zinc, cadmium, and
mercury to determine the distribution of the metals within the various tissue
layers of the kidney (Figure 5.1). The specimens were obtained from an
individual who died from a gunshot wound, not kidney disease. In all
samples, there was a decreasing concentration gradient from the outer
surface of the cortex to the medullary surface for zinc, cadmium, and
mercury. Such findings suggest that much of the variability in the reported
values may be due to lack of a standardized sampling technique and sampling
location among studies. Since the cortex is the area of the kidney which
would be expected to show the most variability, the sampling location within
the cortex may be an important factor. Because concentrations of all three
metals increase toward the outer surface of the cortex, analyses of samples
of gross kidney tissue, which included medulla or calices, may yield results
which are consistently low relative to cortical concentrations. This study
found a median concentration for renal cadmium in adults which was 900 times
that found in infant tissues.
Morgan (1972), in establishing the "normal" lead and cadmium content
of the human kidney, assayed kidneys which were collected at postmortem
examination from 100 unselected autopsies (32 blacks and 68 whites) between
October, 1967, and March, 1968, at the Birmingham, Alabama, Veterans
Administration Hospital. The mean age for the entire group was 62 years.
The mean cadmium concentration for all subjects was 2,359 ppm of ash (with
a range of 109 ppm); for blacks, 2,267 ppm, and for whites 2,667 ppm of ash.
On the basis of present data, Morgan concludes that 5,000 ppm of ash should
be considered the upper limit of "normal" for cadmium but that further
analysis might indicate that this figure is still too high.
Hammer et al. (1973) report as follows:
(1) Renal cadmium levels increased over tenfold from
infancy to middle age and then declined somewhat
thereafter (Table 5.6).
(2) Average renal cadmium and zinc levels increased
progressively with increasing smoking intensity
(Table 5.7).
(3) Average renal cadmium concentrations in males
generally exceeded those of females (Table 5.8).
5-8
-------
200
100
(a)-
(b)
(0
ZINC
•CADMIUM
-MERCURY
(a)
(b)
I
ki
CORTEX
-»«-
MEDULLA
I 234567
Loyer Number (from organ surface.)
•(0
i i i i i i i i i i i i i i i i
8
Figure 5.1. Zinc, cadmium, and mercury distributions in the
kidney of a 42-year-old female (cause of death:
gunshot wound to head). [Reprinted from
Proceedings of University of Missouri's 5th
Annual Conference on Trace Substances in
Environmental Health (D. D. Hemphill, Editor)
by H. D. Livingstone, by permission of
Environmental Toxic Substances Center,
University of Missouri. Published 1972] .
5-9
-------
TABLE 5.6. CADMIUM CONCENTRATIONS IN THE HUMAN
RENAL CORTEX, BY AGEa
Location
Date of Data Age,
Collection Mean
Number of
Samples
Concentration, ppm,
by weight"
Mean
Range
South Carolina
Carolinas
North Carolina
1970-1971
1970-1971
1970
17
23
34
45
55
65
75
85
91
14
12
7
16
13
17
12
3
1
188
1051
1408
2338
2063
2696
1768
1755
1267
596
21-489
551-1891
934-
1282-
710-
1230-
608-
455-
940-
3164
3350
3347
•3525
3000
4771
1512
Source: Hammer et al., 1973.
Tissue from adult autopsy materials was obtained from seven North
Carolina hospitals in 1970. Pediatric tissues were from the
Medical College of South Carolina in Charleston.
5-10
-------
TABLE 5.7. RENAL CADMIUM AND ZINC LEVELS IN 40- TO 79-YEAR-
OLD MALES, BY SMOKING CATEGORY3
Smoking Category
Never smoked
1 to 1-1/2 packs
daily
No. of
Samples
10
6
8
5
Concentration, ppm ash weight
Metal
Cadmium
Zinc
Cadmium
Zinc
Cadmium
Zinc
Cadmium
Zinc
Level
1286 ±
2511 ±
2132 ±
3052 ±
2795 ±
3513 ±
2812 ±
3551 ±
± SDC
404
544
592
345
1045
1931
946
2064
Median
1286
2519
2144
2923
2086
2980
2650
3237
Range
710-1823
1759-3278
1303-2891
2526-3429
1752-4771
2306-8050
1562-4000
1682-7000
Source: Hammer et al., 1973.
Smoking history was queried for the last 5 years of the patient's
life only.
>
~SD = Standard deviation.
TABLE 5.8. CADMIUM IN RENAL CORTEX, BY SEX AND AGEC
Cadmium in
Age
Interval
in Years
10-19
20-29
30-39
40-49
50-59
60-69
70-79
80-89
No. of
Samples
2
8
4
10
9
12
8
1
Males
Mean
1221
1469
2601
2064
2941
1743
1878
940
renal cortex , ppm
ash weight
Females
Range
551-1891
972-3164
1797-3350
710-3347
2000-4000
860-3450
768-4771
768-477
No. of
Samples
2
4
3
6
4
4
4
2
Mean
881
1285
1988
2062
2197
1804
1509
1431
Range
832-929
934-1622
1282-2530
1268-3200
1230-2850
608-3000
455-3700
1350-1512
Male to
Female
Ratio
1.39
1.14
1.31
1.00
1.34
0.97
1.24
0.66
Source: Hammer et al., 1973.
Excludes 15 subjects with cancer—one with schleroderma and one
with acute hepatitis and pancreatitis.
5-11
-------
(4) Increases in renal zinc concentration are related
to cadmium virtually on a one-to-one basis (Figure 5.2).
(5) As shown in Table 5.9, cancer patients had a
significantly more variable renal cadmium concen-
tration IF(16,57) = 3.18 p<0.005] and a significantly
less variable hepatic cadmium concentration [F(57,16) =
6.50 p<0.001].
(6) Hepatic cadmium increased four- to fivefold from
infancy to adulthood but remained relatively constant
thereafter (Table 5.10).
(7) Hepatic cadmium was significantly higher in 40 to 70-
year-old males with any smoking history when compared
to those with no smoking history.
Repeated exposures to cadmium among workers may cause accumulation
of cadmium in the organs, particularly the kidneys. Cadmium accumulation of
200 ppm in the renal cortex is believed to be the critical level needed to
produce renal tubular dysfunction (Friberg et al., 1973). Renal tubular
damage leads to an increase in urinary cadmium excretion. Adams et al.
(1969) found 0 to 168 ppb in urine in 56 workers exposed to cadmium oxide
dust. Generally, a large degree of individual variation has been observed
among exposed workers.
Table 5.11 illustrates cadmium concentration in renal cortex at
autopsy and the associated morphological changes observed in workers exposed
to cadmium oxide dust. Profound morphological changes occurred in persons
having greater than 15-year exposure. These same workers also tend to have
much lower levels in the cortex, probably reflecting the greater release of
cadmium from the kidneys following the onset of proteinuria (Friberg et al.,
1974). Adams et al. (1969) have reported that proteinuria frequently
persists after exposure to cadmium has ceased and urinary cadmium excretion
has decreased.
EXCRETION OF CADMIUM
Urinary excretion of cadmium is considered the major route for body
burden-related elimination (Friberg et al., 1974). Reported values for
cadmium are extremely variable; however, recent studies suggest an average
normal urinary excretion of cadmium of 1 to 2 yg/day (Friberg et al., 1974).
Table 5.12 summarizes the results of studies of urinary excretion in persons
without known industrial exposure. Cadmium levels reported in urine of
occupationally exposed workers range from 0 to 1,000 yg/day. There is no
evident relationship between urinary cadmium excretion in exposed workers
and the degree of exposure. Some workers had been exposed to cadmium in
sufficient quantity to cause considerable tissue accumulation, yet had
urinary levels of less than 2 ppb (Friberg et al., 1974). Due to the wide
individual scatter, Friberg et al. (1975) concluded that there were no data
which show that concentrations of cadmium in blood or urine can be used for
5-12
-------
in
v)
"
E
a.
c"
o
.{3
U
O
8
o
.5
N
0 10 20 30 40 50 60
Cadmium concentration, /imols/g. ash weight
Figure 5.2. Molar relationship of cadmium and zinc in
the renal cortex (Hammer et al., 1973).
5-13
-------
TABLE 5.9. SUMMARY OF TESTS BETWEEN PATIENTS WITH AND
WITHOUT CANCER, BY TISSUE AND METAL3
Average tissue level ,
ppm ash weight
Tissue
Kidney
Liver
Metal
Cadmium
Zinc
Cadmium
Zinc
Cancer (17)
3232 + 1744
3653 + 1368
248 + 99
5063 + 2871
Noncancer (58)
2061 + 960
3020 + 1165
244 + 53
4120 + 2181
Probability
of Observed
Difference
P < 0.01
0.10 > P > 0
P < 0.80
0.60 > P > 0
.05
.40
Source: Hammer et al., 1973.
Includes one patient with scleroderma and one with pancreatitis
and hepatitis.
Differences were tested by a student test of long-transformed
data.
TABLE 5.10. CADMIUM CONCENTRATION IN HUMAN LIVER, BY AGEC
Date of Data Age, Concentration, ppm
Location Collection years Mean Range
Remarks
South 1970-1971
Carolina
Carolinas 1970-1971
North 1970
Carolina
0-9
10-19
20-29
30-39
40-49
50-59
60-69
70-79
80-89
90-99
39
168
140
194
197
206
198
273
282
97
8-115
124-247
21-396
21-343
58-375
73-368
21-460
65-1720
168-684
21-173
Adult autopsy tissues
obtained from seven
North Carolina hospi-
tals in 1970. Pedi-
atric tissues were
obtained from Medical
College of South
Carolina in Charles-
ton.
Source: Hammer et al., 1973.
5-14
-------
TABLE 5.11.
Ui
i
CONCENTRATIONS OF CADMIUM IN KIDNEY CORTEX IN WORKERS EXPOSED
TO CADMIUM OXIDE DUST IN RELATION TO MORPHOLIGICAL KIDNEY
CHANGES SEEN AT AUTOPSY OR BIOPSY3
Morphological
Worker Changes^3
S.W.H. -H-
K.J. ++
K.N. e
H.B. -H-
A.B. ++
O.J. -H-
G.J. (+)
G.K. (+)
A.L.
E.Y.
E.H.
J.P.
N.U.
H.N.
K.N.
Reprinted from Cadmium
Cadmium in Cortex ,
Proteinuriac ^g/g wet weight
+ 83
+ 75
+ 20
+ 33
+ 174
+ 63
+ 321
+ 152
(+) 220
446
+ 320
+ 330
180
+ 21
190
in the Environment, 1st Edition, L.
Age
46
49
57
60
39
62
44
46
36
39
40
43
44
45
50
Years
Exposed
28
22
18
26
16
20
11
15
6
7
15
20
12
13
15
Friberg, L. M.
Years Since
Last
Exposure
1
9
6
3
4
1
12
0
0
0
10
6
0
0
2
Piscator, and
Year of
Autopsy
or Biopsy
Autopsy
1960
1951
1952
1949
1950
1967
Biopsy^
1959
1959
1959
1959
1959
1959
1959
1959
1959
G. Nordberg, (c) CRC Press, Inc., 1971. Used by permission of CRC Press, Inc.
= No morphological changes
(+) = Slight morphological changes
++ = Profound morphological changes.
= Negative results on repeated testing with trichloracetic acid
(+) = Varying results
+ = Positive results on repeated testing.
Underlined figures are based on cadmium concentrations in whole kidney, assuming that the cadmium
concentration in cortex is 1.5 times the average kidney concentration.
3
"Results from histological examinations not reported but in an examination in 1946, this worker
had the lowest kidney function tests of all. ' '
-------
TABLE 5.12. URINARY EXCRETION OF CADMIUM IN "NORMAL" SUBJECTS'
h-1
O
No. of
Country Samples
United States
Japan
Gifu
West Germany
Belgium
Sweden
Reprinted from
154
30
. 46
40
41
56
37
40
43
14
15
169C
44
10
88
10
10
10d
Cadmium
Age Group
4-6
9-10
14-15
20-29
30-39
40-49
50-59
20-47
50-59
15-16
15-16
34-63
Concentration
Mean SDb Range
1.59 <0.5-10.8
3.1 0.0-15.9
0.47 0.25
0.65 0.45
0.72 0.50
0.99 0.63
1.13 1.06
1.76 1.33
1.75 1.38
1.0
0.98 0.34-1.57
1.25 0-5
0.95 0.8
0.39 0.05-0.77
0.62 0.1-2.0
0.25 0.2-0.5
0.21 0.1-0.3
1.7 0.4-3.7
in the Environment, 2nd Edition, L.
Units
ppb
ppb
ppb
ppb
Ug/24 hr
ug/g creatinine
ug/g creatinine
ug/24 hr
jjg/g creatinine
ppb
ug/g creatinine
Ug/g creatinine
Method
Spectrographic after
dithizone extraction
Dithizone
Atomic absorption spectro-
scopy after extraction
Ditto
11
M
M
1 1
Dithizone
Atomic absorption spectro-
scopy after MIBK-APDC
extraction
Ditto
Atomic absorption spectro-
scopy after extraction
Atomic absorption spectro-
scopy after MTBK-APDC
extraction
Atomic absorption spectro-
scopy after extraction
Ditto
it
ii
Friberg, M. Piscator, G. Norberg,
c
and T. Kjellstrom, (c) CRC Press, Inc., 1974. Used by permission of CRC Press, Inc.
SD = Standard deviation.
Includes both children and adults; values for children did not differ on an average from those of adults.
Workers without known industrial exposure to cadmium but living in a cadmium-contaminated area.
-------
estimating levels of cadmium in human beings. It is not possible to use a
fixed level of cadmium in blood or urine to be used for analytical control
of (1) exposed workers or (2) populations exposed to cadmium in food or
ambient air. Concentrations of cadmium in urine above "normal" would
indicate that signs of cadmium-induced renal dysfunction had already
occurred, provided other reasons for the increased excretion could not be
demonstrated.
As shown in Table 5.13, a comparison of cadmium levels in the blood
and urine of 100 acculturated and 90 unacculturated individuals shows
markedly lower levels of cadmium in the unacculturated population (Hecker
et al., 1974). The technologically developed population consisted of 100
Red Cross donors, ages 18 to 58, from Ann Arbor, Michigan. The unaccultura-
ted population consisted of 137 Yanomamo Indians living in the area drained
by the Upper Orinoco River and its tributaries in southern Venezuela.
Cadmium was determined by anodic stripping voltammetry (Table 5.13).
TABLE 5.13. CADMIUM LEVELS IN ACCULTURATED AND
UNACCULTURATED POPULATIONS3
Population
Ann Arbor
Yanomamo
Matrix Statistic
Blood Number of subjects
Range
Mean
SDC
Blood Number of subjects
Range
Mean
SDC
Urine Number of subjects
Range
Mean
SDC
Cadmium
47
<0.1-9.6
1.71b
1.89b
90
0.07-3.72b
0.57b
0.51b
47
0.0-4.5d
1.2d
1.2d
o
Source: Hecker et al., 1974.
Values in yg/100 ml.
CSD = Standard deviation.
Values in yg or ppb.
5-17
-------
Fecal excretion of cadmium has been estimated at 31 yg/day by
Friberg et al. (1974) and 42 yg/day by Tipton and Stewart (1969). These
values include unabsorbed dietary cadmium. Tracer studies show that less
than 0.1 percent of a retained oral dose of 115mCd was excreted in feces
(Rahola et al., 1972). High concentrations of cadmium in bile from autopsy
samples suggests an enterohepatic circulation of cadmium in man. Animal
studies suggest also that less than 5 percent of fecal excretion could be
accounted for by this route (Friberg et al., 1974). At present, the
precise mechanisms for fecal excretion of cadmium in human beings are not
known (Friberg et al., 1974).
Other possible routes of cadmium excretion include milk, saliva,
and hair. Excretion of cadmium into milk of nursing mothers may be of
some significance in body clearance of cadmium. Pinkerton et al. (1973)
showed that cadmium concentrations in human milk ranged from 0.0088 to
0.1335 ppm with a median value of 0.0111 ppm. Cadmium may also be
secreted into human saliva. Friberg et al. (1973) reported concentrations
of up to 0.1 yg/g in human saliva. Hammer et al. (1971) have suggested
using hair as an indicator of exposure to various trace metals, including
cadmium. Ten-year-old boys from five cities ranked according to trace
metal contamination supplied the hair samples. As can be seen from Table
5.14, there is good agreement between exposure levels and cadmium levels
in hair. Another study conducted by Schroeder and Nason (1969) investigated
the influence of age, sex, and hair color on levels of cadmium in hair.
Their results showed differences in cadmium content related to hair color,
TABLE 5.14. CADMIUM IN HAIR FROM BOYS LIVING IN URBAN AREAS3
Exposure Ranking , Number of Geometric Mean,
city Determinations ppm
I High
II High
III Lowc
IV Low
V Low
45
25
37
21
37
2.1
1.5
1.0
1.0
0.7
Source: Hammer et al., 1971.
Ranking determined by combining aerometric, geologic, and
industrial data.
£
Low approximates usual U.S. urban level.
5-18
-------
sex, and age. Black-haired males had less cadmium in their hair than those
with brown, blonde, or red hair. In women, gray hair had less cadmium than
either natural-color hair or gray hair obtained from males. Also, cadmium,
nickel, and lead did not accumulate with age. The authors concluded that
concentration of cadmium in hair probably does not reflect tissue stores
under normal conditions (Schroeder and Nason, 1969). Petering et al. (1973)
investigated the relationship of age and sex to cadmium in human hair.
Regression analysis showed two groups of males with respect to cadmium
concentration in hair, namely those over and under 12 years of age.
Similar analyses indicated that hair cadmium distribution for females
delineated one group below and one group above 50 years of age. The
authors conclude that comparisons of metallic content of hair in humans
should be limited to a narrow age range and to one sex.
Table 5.15 presents findings from several studies of cadmium in hair,
showing the typical values and ranges observed. Analysis of metals in hair
also presents additional difficulties in that external contamination from
dust and from metals in hair sprays, hair coloring products, etc., must be
taken into account (Friberg et al., 1974).
Johnson et al. (1975) conducted an epidemiological survey in the
metropolitan area of Houston, Texas, on cadmium, lead, zinc, manganese,
and copper. Six groups, with 36 individuals in each group, were monitored,
three exposed, and three corresponding controls:
Exposed Control
I. Policeman on foot patrol IA. Office workers in downtown Houston
II. Garage attendants IIA. Orderlies and custodians
III. Females living within two IIIA. Females living away from a freeway.
blocks of a freeway
Each subject was sampled four separate times for blood, urine, and hair.
As shown in Table 5.16, there appeared to be wide variations in
cadmium content, particularly in hair. Statistical comparison of the data
indicated that there were significant differences in cadmium levels in urine
between Group I and IA and Group II and IIA at the 95 percent confidence
limits. No differences were seen in the female subjects. Conceivably, the
levels of cadmium in urine are related to the exposure to air pollutants.
BIOLOGICAL HALF-LIFE
The extremely long biological half-life of absorbed cadmium in the
body results in essentially continuous accumulation throughout life (Hammons
and Huff, 1975). Cadmium becomes bound to the protein metallothionein in
the kidney, and accumulates until the fifth or sixth decade of life, after
which it begins to diminish in concentration (Environmental Health Resource
Center, 1973). Estimates of half-life can be made on a group basis by
comparing body burden and excretion. In the United States, body burden has
5-19
-------
TABLE 5.15. "NORMAL" CONCENTRATIONS OF CADMIUM IN HAIRC
Ul
CO
O
Country
U.S.A.
Sweden
Yugoslavia
Reprinted
Sex
Male
Female
Male
children
Male
Female
Male
from Cadmium
No. of
Samples
82
47
45
25
37
21
37
7
8
17
Concentration, yg/g
Mean SDb
2.77 ± 4.37
1.77 ± 1.64
3.5 ± 4.94
2.0 ± 1.54
1.3 ± 0.99
1.3 ± 1.30
0.9 ± 0.8
0.44 ± 0.14
0.87 ± 0.26
0.54 ± 0.27
in the Environment, 2nd
Median
2.1
1.6
1.0
0.9
0.8
0.43
0.92
0.45
Edition,
Range Method
Atomic absorption; hair
treated with detergent
Atomic absorption; hair
treated with EDTA
0.24-0.60 Atomic absorption; hair
0.41-1.27 treated with detergent
0.20-1.48 Ditto
L. Friberg, M. Piscator, G. Norberg,
not
solution
pre-
pre-
and
T. Kjellstrom, (c) CRC Press, Inc., 1974. Used by permission of CRC Press, Inc.
SD = Standard deviation.
"Ten years of age from five areas with differing degrees of cadmium contamination.
-------
TABLE 5.16. CADMIUM IN BLOOD, URINE, HAIR, AND FECESC
Blood, yg/100 ml
Group
I
IA
II
I LA
III
IIIA
Mean
0.5
0.7
0.5
0.4
0.9
0.8
SDb
0.67
0.85
0.52
0.44
1.1
1.7
Urine, yg/& (ppb) Hair, yg/g
Mean
1.4
0.6
0.8
0.5
0.6
0.6
SD
1.05
0.44
0.63
0.23
0.67
0.40
Mean
1.1
1.1
1.0
2.2
0.6
0.7
SD
2.09
2.02
0.97
2.10
0.41
0.55
Feces
Mean
0.19
0.20
0.30
0.24
0.27
0.23
, yg/g
SD
0.07
0.11
0.21
0.13
0.16
0.13
Source: Johnson et al., 1975.
SD = Standard deviation.
been estimated to range from 15 to 20 mg of cadmium. Urinary excretion
amounts to 1.6 ppb, corresponding to a daily excretion of 0.012 to 0.015
percent of body burden. Such findings would place the biological half-life
somewhere between 13 and 47 years (Friberg et al., 1974).
Friberg et al. (1974) have computed similarly long biological half-
lives of 19 to 38 years, using mathematical models. The validity of some
of the assumptions of these models (i.e., excretion rates and body burden
values) is still open to question and, as Friberg et al. (1974) conclude,
the exact biological half-life of cadmium is still uncertain.
5-21
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TECHNICAL REPORT DATA
(/'lease read Instructions on the reverse before completing)
1. REPORT NO.
EPA-560/6-77-032
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
MULTIMEDIA LEVELS—CADMIUM
5. REPORT DATE
September 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
Battelle Columbus Laboratories
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
10. PROGRAM ELEMENT NO.
11.
68-01-1983
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Office of Toxic Substances
Washington, D.C. 20460
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report is a review of environmental levels of cadmium based on published reports
and other information sources. Cadmium levels are reported for the atmosphere, surface
and ground waters, drinking water, sediments, soil, sludge, terrestrial and aquatic
biota, and man. The behavior of cadmium in the environment is also discussed.
Although cadmium is present in measurable quantities in virtually all areas, for the
general population oral ingestion in foods can represent the most important source of
cadmium intake. Airborne sources appear to constitute a significant portion of
cadmium intake for those occupationally exposed or those residing in areas heavily
polluted by cadmium-emitting industries. Based on the information in this document,
current cadmium releases to the environment appear to be declining. However, the
cadmium content in fossil fuels and fertilizers is only partially controllable, and
these two sources may set the lower bounds of attainable minimums in cadmium emissions
to the environment. Most of the dissipated cadmium eventually becomes bound to soil,
sediment, and ocean sinks. Biological accumulations of cadmium are found in most
living organisms.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
COS At I Held/Group
Cadmium
Water
Sediment
Soil
Air
Biota
Human
Food
Behavior
8. DISTRIBUTION STATEMENT
Distribution unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
141
20. SECURITY CLASS (This page)
^Unclassified
22. PRICE
EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE
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