Mercury in the
Environment
GEOLOGICAL SURVEY PROFESSIONAL PAPER 713
A compilation of papers on the
abundance, distribution, and \
testing of mercury in rocks,
soils, waters, plants, and
the atmosphere
UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON: 1970
11
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UNITED STATES DEPARTMENT OF THE INTERIOR
WALTER J. HICKEL, Secretary
GEOLOGICAL SURVEY
William T. Pecora, Director
Library of Congress catalog-card No. 78-609261
For sale by the Superintendent of Documents, U.S. Government Printing Office
Washington, D.C. 20402 -
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Mercury in the Environment —• 0eological
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16. ak-"i. • This document is a compilation of papers on the. abundance, distribution, and
testing of mercury in rocks, soils, waters, plants and the atmosphere, The report dis-
cusses known facts about mercury — where, and in what forms and quantities mercury is
found; how it behaves in air, water, and earth materials; the impact of man's activities
on its distribution; and the effects of the element on our lives, Furthermore, mercury
is a strategic methal and because the United States has traditionally relied on imports
for approximately half of its requirements, there is obvious need for better understanding
of the occurrence and distribution of mercury in this country. This report is written
with the hope that the information will provide better understanding of the mercury prob-
lems wh:Lch confront us.
17. }U / v. m.i'. 'i 1 IX'4
mercury
rocks
air.
water kic
earth
soil
earth materials
plants
atmosphere
Am:,
I'm:. 3>tr-cr i!
industry
essential metal - mercury
domestic sources
geologic distribution
mercury ores
geochemistry
new reserves
mercury in fish
Colorado plateau region
stream sediments
m,. IJ r itt i I ii' rs /Opr iv K is J<-<1 'I'ctiv.
natural thermal and
mineral fluids
surface waters
plants
atmosphere
fluvial transport —
mercury
granite rocks
deep-seated igneous
alkalic rocks
igneous rocks
metamorphic rocks
1 inestones j
sandstones
shales and clays ;
sedimentary rocks j
oceanic and lacustrine
sediments i
Northern Calif, raercjury
d istrict J
rocks |
Yellowstone National
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Wilbur Springs, Caliif.
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FOREWORD
Current interest in the distribution of mercury in the natural environ-
ment stems from two related concerns:
1. Mercury is an essential metal for industry, the known domestic re-
sources of mercury ores are limited, and better knowledge of the
geologic distribution and geochemistry of the element is needed to
identify new reserves.
2. With the developing interest in environmental protection has come an
increase in awareness of and concern for the actual and potential
hazards of mercury wastes in the environment.
Abnormal quantities of mercury in fish and other foods have recently
raised many questions about its natural occurrence and behavior. Like all
other elements, this unusual metal has been part of our environment for
all time.
The Geological Survey has devoted much effort to the study of mer-
cury as part of its basic mission of determining the occurrence and dis-
tribution of mineral resources. This report discusses known facts about
mercury—where, and in what forms and quantities mercury is found; how
it behaves in air, water, and earth materials; the impact of man's activities
on its distribution; and the effects of the element on our lives. Further-
more, mercury is a strategic metal and because the United States has
traditionally relied on imports for approximately half of its requirements,
there is obvious need for better understanding of the occurrence and dis-
tribution of mercury in this country. This report is written with the hope
that the information will provide better understanding of the mercury
problems which confront us.
W. T. Pecora
Director, U.S. Geological Survey
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CONTENTS
Page
Summary of the literature on the inorganic geochemistry of mercury—by
Mercury content of rocks, soils, and stream sediments—by A. P. Pierce, J. M.
Mercury in sedimentary rocks of the Colorado Plateau region—by R. A. Cadigan 17
Mercury contents of natural thermal and mineral fluids—by D. E. White, M. E.
Mercury in the atmosphere—by J. H. McCarthy, Jr., J. L. Meuschke, W. K.
Analytical methods for the determination of mercury in rocks and soils—by
ILLUSTRATIONS
Page
Figure 1. Diagram showing percentile ranges of mercury distribution in rocks, soil, and sediments 15
2. Map showing location of Colorado Plateau region 17
3. Frequency histogram of percent of samples plotted over mercury content 18
4. Diagram showing fields of stability for solid and liquid mercury species at 25°C and 1 atmosphere pressure 20
5. Diagram showing' fields of stability for aqueous mercury species at 25°C and 1 atmosphere pressure 22
6. Simplified representation of the flow of materials through an aquatic food chain 32
7. Diagram showing mercury in air as a function of altitude, Rlythe, Calif 37
8. Diagram showing daily variation of mercury in air at the ground surface, temperature, and barometric
pressure, Silver Cloud mine near Battle Mountain, Nev 38
TABLES
Page
TABLE 1. Determinations of mercury in U.S. Geological Survey standard rocks 53
2. Analyses for mercury in basalts, gabbros, diabases, andesites, dacites, and liparit.es 53
3-7. Determinations of mercury in—
3. Granitic rocks 54
4. Ultramafic and deep-seated igneous rocks 54
5. Alkalic rocks 55
6. Igneous rocks of areas of very high content 55
7. Metamorphic rocks 55
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VI
CONTENTS
Table 8-12. Analyses for mercury in— Page
8. Limestones 56
9. Sandstones 56
10. Shales and clays 56
11. Miscellaneous sedimentary rocks 57
12. Oceanic and lacustrine sediments 57
13. Analyses of soils for mercury 57
14. Mercury content of natural waters 58
15. Mercury in air and in volcanic emanations 59
17. Statistics on the mercury content of selected rocks, soils, and stream sediments 60
18. Mercury content of some sedimentary stratigraphic units in the Colorado Plateau region of the United
19. Equilibrium constants and standard potentials 61
20. Standard free energies of formation of certain mercury species 62
21. Mercury concentration in thermal waters, Northern California mercury district 62
22. Mercury concentration in thermal waters from Yellowstone National Park 63
23. Mercury concentration of petroleum from the Wilbur Springs area, northern California - - - 63
24. Mercury in selected rivers of the United States, 1970 63
25. Mercury levels in natural waters outside the United States 65
26. Mercury consumption in the United States 65
27. Lethal concentrations of mercury compounds for various aquatic organisms and man 66
28. Maximum mercury concentration in air measured at scattered mineralized and nonmineralized areas of the
Western United States 67
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MERCURY IN THE ENVIRONMENT
SUMMARY
Mersury, commonly called quicksilver, is one of
the elements that make up the planet earth. In its
elemental state at the earth's surface it is a silvery
liquid metal, approximately Id1/* times as heavy as
water, and it is the only metal which occurs in liq-
uid form at ordinary earth surface temperatures.
Like other liquids, it vaporizes and condenses in a
pattern determined by its own vapor pressure and
by the temperature and barometric pressure of the
environment in which it exists. It is absorbed and
held tightly by a variety of materials such as plant
fibers and soils. Like other metallic elements, it
reacts with a great variety of inorganic and organic
compounds to form simple and complex molecules
ranging from cinnabar, a mercury sulfide and the
most common ore mineral, to the metallo-organic
complexes which have received recent world wide
attention as potential water pollutants and biologic
toxins.
The compounds of mercury, like many other
chemical compounds, are dispersed throughout
rocks, soil, air, water, and living organisms by a
complex system of physical, chemical, and biological
controls. Particular combinations of these controls
have developed interesting patterns of mercury and
its compounds in the world around us.
MINERALS AND HOCKS
Although there are more than a dozen mercury-
bearing minerals, only a few occur abundantly in
nature. Cinnabar, the sulfide, is the most important
and contains 86 percent mercury by weight; it is
usually formed geologically at low temperatures
(less than 300°C). It is generally found in mineral
veins or fractures, as impregnations, or having re-
placed quartz, in rocks near recent volcanic or hot-
spring areas.
Mercury content of broad categories of rocks in
the earth's crust range from 10 to 20,000 ppb1
(parts per billion); 1 ppb is equivalent to 1 pound
of mercury per billion pounds of rock. Less than 20
percent of recorded rock samples have more than
1,000 ppb. Igneous rocks—those formed by melting
1 See end of "Summary" for discussion of units used in this report.
and cooling—are the basic sources of mercury.
These generally contain less than 200 ppb of mer-
cury and average 100 ppb. The mercury content of
soils averages about 100 ppb and varies within rela-
tively narrow limits. Sedimentary rocks resulting
from weathering and deposited by physical, chemi-
cal, and biological processes also generally average
less than 100 ppb of mercury and seldom exceed 200
ppb except for certain crganic-rich shales which
may reach concentrations cf 10,000 ppb or more.
In addition to organic-rich shales, other rocks
with abnormally high mercury contents are known
to exist. The Donets Basir., Kereh-Taman area, and
the Crimea of the Union of Soviet Socialist Repub-
lics where both igneous rocks and sedimentary
rocks commonly contain 100 times the normal maxi-
mum (up to 20,000 ppb), probably are the best ex-
amples, but similar anomalies can be found else-
where. For example, Green River shale samples of
the western Colorado Plateau have yielded mercury
values as high as 10,000 ppb.
Background concentrations of soils in California
are 20 to 40 ppb. The Franciscan Formation of Cal-
ifornia, in which most of the state's mercury mines
are located, has background values of 100 to 200
ppb; anomalies in soils around these mercury de-
posits are in the range of 10,000 to 100,000 ppb.
ATMOSPHERE
Because of mercury's tendency to vaporize, the
atmosphere measured at ground level near mercury
ore deposits may contain as much as 20,000 ng/m3
(nanograms per cubic meter) of mercury in air. One
nanogram is one billionth (1/1,000,000,000) of a
gram, or 0.035/1,000,000,000 of an ounce, and 1
cubic meter equals about li/t. cubic yards. Ex-
pressed on a weight basis rather than on a volume
basis (for comparison with contents of rocks)
20,000 ng/m3 represents almost 16 pounds of mer-
cury per billion pounds of air. Because of similari-
ties in the mineral systems, the next highest near-
ground levels of atmospheric mercury occur over
precious metal ores (up to 1,500 ng/m3) and copper
ores (20 ng/m3) in that order.
l
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2
MERCURY IN THE ENVIRONMENT
Whatever the source of natural atmospheric mer-
cury, its pattern responds to meteorological controls
and other natural laws. Thus, the maximum amount
of mercury in air is found at about midday with
much smaller amounts found in the morning and in
the evening-. In both cases, vapor density, like the
density of the atmosphere, is greatest near the sur-
face of the land and diminishes with altitude. For
example, a concentration of 20,000 ng./m3 of mer-
cury at ground level near a mercury mine was ob-
served to diminish to only about 100 ng/m3 at 400
feet altitude, and a ground-level concentration of
600 ng/m3 at noon has been observed to drop to only
20 ng/m-! at 2:00 a.m.
RAIN
Rain washes mercury from the atmosphere just
as it does certain other atmospheric components.
Even near mercury ore deposits, tests have shown
the mercury content of the atmosphere to be essen-
tially zero immediately after a rainstorm. Such
scrubbing accounts for the fact that the mercury
content of rainwater averages about 0.2 ppb. Tests
in Sweden have shown that mercury carried down
by rain adds to each acre of land per year about the
same amount of mercury one would expect to be
added by mercury-bearing seed dressing for fungal
control of cereal crops. Mercury from either source
is held tightly by the upper 2 inches or so of soil.
SURFACE WATER, GROUND WATER, ANB SEDIMENTS
Contact of water with soil and rock during storm
runoff, percolation into the ground, and movements
under the ground where different geochemical
stresses prevail, results in a natural distribution of
mercury in water. The pattern of such distribution
depends on the dispersion of mercury in the
earth's crust and a great variety of earth processes
already mentioned. Surface waters, except where
they are influenced by special geologic conditions, or
more recently by manmade pollution, generally con-
tain less than 0.1 ppb of mercury. This reflects the
relatively low concentration of mercury in rain-
water and the relatively tight bonding of mercury in
organic and inorganic materials over which the
water passes in its travel through the environment.
A recent reconnaissance of river waters in 31 states
showed that (1) 65 percent of the samples tested
had mercury contents below 0.1 ppb, (2) 15 percent
exceeded 1.0 ppb, and (3) only 3 percent were more
than 5.0 ppb—the maximum considered safe for
drinking water.
Higher concentrations of mercury are likely to
occur in underground waters because of the longer
and more intimate contact with mineral grains and
other environmental factors. Limited sampling of
oil-field brines in California showed them to contain
from 100 to 200 ppb of mercury. Hot springs in the
same state appear to range from 0,5 to 3.0 ppb, and
one measurement as high as 20 ppb of mercury lias
been recorded for such water. Vapors issuing from
fumaroles and steam condensing from hot springs
also have relatively high mercury contents—as
much as 6 ppb and 130 ppb, respectively. Fine-
grained muds from pots and mud volcanoes in Yel-
lowstone National Park yield mercury contents up
to 150,000 ppb and measurements as high as
500,000 ppb have been made on enriched sediments
from springs and pools in Yellowstone. Thermal
waters of this kind have probably formed mercury
ore deposits in the past. Some 5,000 tons of the
metal have been mined from deposits around Sul-
phur Bank Spring in California.
Because of mercury's tendency to sorb readily on
a variety of earth materials, particulate matter sus-
pended in water and bottom sediments of streams
are more likely to contain high concentrations of
mercury than the water itself, whatever the source
may be. The best estimate is that suspended matter
may contain from five to 25 times as much mercury
as the water around it in areas of industrial pollu-
tion. Sediments immediately downstream of mer-
cury ore deposits and mercury-contaminated in-
dustrial discharges may contain from a few
hundred to as much as several hundred thousand
parts per billion of mercury.
Persistence and movement of mercury in surface
streams also must be considered in evaluating envi-
ronmental effects. Although a normal stream water
of pH 5 to 9 saturated with mercury should contain
about 25 ppb, the concentration downstream from a
mercury source is likely to be much lower because
of dilution, vaporization, precipitation, sorption and
chemical reaction. For example, the mercury con-
centration in river water near a mercury anomaly
was found to decrease from 135 ppb to 0.04 ppb in
30 miles of travel, and sediment in a Wisconsin
river near a source of industrial pollution had a
mercury content of more than 500,000 ppb, whereas
sediment 20 miles downstream from the source of
pollution had a content of only 400 ppb. The tend-
ency of mercury to sink rapidly and combine with
sulfide in anaerobic bottom sediments to form cinna-
bar, which is slightly soluble, appears to be a major
scavenging mechanism. Another mechanism which
keeps content of dissolved mercury low is the rela-
tively high reactivity of mercury with organic sub-
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SUMMARY
3
stances and the resulting uptake by living and non-
living organic matter.
Because they serve as sediment traps and habi-
tats for aquatic organisms, lakes and ponds are
likely to serve as traps for mercury which enters
them. 'J'he significance of such accumulations de-
pends upon the solubility of the final mercury form
in the particular environment.
PLANTS AND ANIMALS
Inorganic chemicals in soil and water are basic
substances for living things. In an aquatic environ-
ment, such inorganics generally are utilized by low
forms of life which in turn serve as steps in the
food chon for higher forms of life up the ladder to
the vertebrate species, including man. Although
mercury is not known to be an essential part of the
food chf.in, it is assimilated by organisms living in
environments which contain it. This process is
thought to be enhanced through conversion of inor-
ganic mercury by certain anerobes to methyl mer-
cury, a more soluble form. However, there still is no
proof th sit proper energy gradients exist to promote
such reactions. Mercury tends to concentrate in liv-
ing tisste once it has been assimilated, and there is
some evidence that the extent of concentration in-
creases with each step up the food chain, from
plankton to fish to man. If the supply is cut off, the
organism tends to purge itself of mercury, but the
efficiency of recovery varies from organ to organ
and organism to organism. One study of fish after
10 days of exposure to water with nonlethal concen-
trations of ethyl mercury showed mercury concen-
trations ranging from 4,000 ppb in muscle tissue to
22,800 ppb in the blood; almost complete elimina-
tion of mercury occurred within 45 days, except for
that in the liver and kidneys. Similar studies have
shown concentration factors of 250 to 3,000 in
algae, 1,000 to 10,000 in ocean fish, and as much as
100,000 in other forms of sea life. Birds which feed
on fish combine high intake with high concentration
factors to yield extreme body residues. The eagle
owl is a prime example with mercury contents as
high as 40,000 ppb in its feathers.
There is evidence also that each step in the food
chain has a certain threshold for mercury above
which permanent harm to the organism may occur.
In some cases, toxicity apparently is catalyzed by
synergistic effects of other heavy metals, such as
copper, chromium, zinc and nickel. Critical levels of
mercury in lower organisms, such as plankton, gen-
erally are thought to be in the range of 5 to 200
ppb, although some kinds of kelp appear to have
tolerance as high as 60,000 ppb. The tolerance of
fish is in the range of 20 to 9,000 ppb, depending on
the particular species of fish and mercury com-
pound. Human tolerance has not been thoroughly in-
vestigated, but is suspected to be comparatively low.
Terrestrial plants, like aquatic organisms, absorb
minor elements, including mercury, from the soils
in which they grow at rates depending on the qual-
ity of the environment and the genetic characteris-
tics of the plants. Unlike aquatic organisms, there
seems to be little tendency for terrestrial plants to
concentrate mercury above environmental levels.
Typical soils contain from 30 to 500 ppb of mercury
(average about 100 ppb) and most of the plants
which grow in them are likely to contain less than
500 ppb. When soil concentrations of mercury are ex-
tremely high-—say 40,000 ppb or more in the vicin-
ity of cinnabar deposits—plants growing in them
actually are likely to have mercury contents far
below the level of their environment; for example
1,000 to 3,500 ppb. Even in these instances, it is
primarily the plants which are rooted through the
surface soil into the mercury ore which have high
mercury contents; shallower- rooted plants are likely
to show much lower levels.
A few plants apparently have unusual capacity to
concentrate mercury and even to separate it in me-
tallic form. Droplets of pure mercury have been
found in seed capsules of members of the chiekweed
family and similar droplets of mercury occur under
moss covers of forest floors near mercury deposits.
In plants, as in animals, mercury tends to concen-
trate in fatty parts so that vegetable fats are rela-
tively rich in mercury whenever the metal is pres-
ent in the organism.
Toxicity of mercury to terrestrial plants
apparently depends more on the chemical state of
the element than on its concentration. Roses are so
sensitive to elemental mercury that florists have
learned by experience to avoid mercury thermome-
ters in greenhouses for fear of breaking them and
poisoning the plants. On the other hand, the same
roses can be sprayed with organic mercury fungi-
cide with little or no ill effects.
FOSSIL FUELS
Throughout eons of time, the products and resi-
dues of geochemical processes and the life cycles of
terrestrial and aquatic organisms have combined to
yield very appreciable mercury contents and dis-
tinct regional patterns in fossil fuel deposits upon
which the world depends for much of its energy.
Typical samples of bituminous coal from the United
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4
MERCURY IN THE ENVIRONMENT
States contain from 1 to 25 ppb of mercury and
many anthracite coals contain from 1,200 to 2,700
ppb. Concentrations in crude petroleum and related
tarry residues are even higher. Samples from Cali-
fornia crudes yield mercury values in the range of
1,900 to 21,000 ppb; related tars which have lost
much of their volatile hydrocarbons are known to
contain as much as 500,000 ppb.
INDUSTRY
The unique properties of mercury account not
only for its unusual pattern and behavior in nature,
but make it an attractive metal for a variety of sci-
entific and industrial uses. It is estimated that the
United States alone uses more than about 2,500 tons
of mercury per year—about 20 percent of the
world's total annual production. Current annual
production in the United States is about 1,000 me-
tric tons per year primarily from mines in seven or
eight western states although it occurs as a minor
eonstitutent in other ores mined and processed in
many states. During the past 40 years, the United
States has imported more than half the mercury
used. Losses to the environment of mercury and mer-
cury compounds from industrial processes in this
country are estimated at 600 tons per year and su-
perimpose a significant amount of manmade pollu-
tion upon the pattern established by nature. Bac-
teriaeides flowing down the sinks of hospitals,
pesticides and fungicides leaching or eroding from
agricultural land, and waste effluents from caustic-
chlorine plants and other industries add waste mer-
cury to the water and the air—often as point
sources of pollution which are particularly trouble-
some. Recent studies of an Interior Department
task force revealed mercury contents of many in-
dustrial outfalls and sludge banks to range from a
trace to 100,000 ppb. Several spectacular instances
of human poisoning 'have been reported in recent
years from consumption of fish exposed to local con-
centrations of mercury. The death of about 50 peo-
ple from eating mercury-tainted fish from Mina-
mata Bay, Japan, is the most renowned example
(Minamata disease). The source of the mercury was
reported to be methyl mercury in liquid outfall
from a plastic manufacturing plant. Such cases of
industrial contamination have led to intensified ef-
fort to develop better methods of detecting mer-
cury ; better systems for assessing its pattern in the
environment; better understanding of its behavior,
including its effects on human beings; better legisla-
tion for whatever control appears to be desirable
and practicable.
DETECTION
Although simple prospecting methods have been
available for a long time, advanced analytical meth-
odology and precision needed to detect the very
small concentrations now thought to be significant
to human health have been available for only the
past few years. The Geological Survey's analytical
methods have progressed from improved wet chemi-
cal dithizone colorimetric method, through a scries
of spectrographs, atomic absorption, and activation
analyses procedures, until it now is capable of
measuring with confidence mercury concentrations
as low as 1 part per trillion in the atmosphere
and 0.1 ppb in water or earth materials. Reduced to
its simplest description, the atomic absorption pro-
cedure, which presently is preferred for water anal-
ysis, consists of vaporizing the mercury into the
beam of an ultraviolet lamp and analyzing the light
pattern which results from this spectral screening
process. Activation analysis consists of bombarding
the sample with neutrons in an atomic reactor to
create a radioactive isotope of mercury which reads
out a characteristic fingerprint of photon radiation
as it undergoes decay.
RECOVERY AND CLEANUP
Improved analytical and surveillance techniques
and intense research on behavior of mercury are
making it possible for industries to recover and con-
serve valuable mercury which might otherwise have
escaped as waste and for environmental managers to
accurately monitor that which does escape. Process
improvement, waste water recycle, and a variety of
byproduct recovery schemes have made it possible
for many industries to trim mercury losses from
hundreds of pounds per day to 1 pound per day
or less. With growing awareness of the dangers of
mercury pollution and increasing vigilance of our
environmental monitoring, one can look to the future
with considerably more optimism than was possible
a year ago.
UNITS AND NOTATION
Throughout this publication, consistent units
have been used follows:
ppb (parts per billion). 1 ppb^i pound of substance in a total
of a billion pounds of material—in this case, 1 pound of
mercury per billion pounds of solid or water.
ppm (parts per million). 1 ppm — 1 pound of substance in a
total of a million pounds of material—in this case, 1
pound of mercury per million pounds of solid or water;
1 ppm —1,000 ppb.
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SUMMARY
5
p.g/1 (micrograms per liter). Equivalent to parts per billion
in dilute solution such as relatively pure water.
mg/I (milligrams per liter). Equivalent to parts per million
in dilute solutions such as relatively pure water. 1
mg/l — 1,000 ttg.'l ~1 ppm —1,000 ppb.
ng/m3 (nanogram per cubic meter (of air)). Generally used
for concentration in the atmosphere. 1 ng/maa:l/l,000
ppb,
> — greater than.
< = less than.
'c ~ approximately.
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SUMMARY OF THE LITERATURE ON THE INORGANIC GEOCHEMISTRY
OF MERCURY
By Michael Fleischer
SUMMARY
The mercury content- of most igneous rocks is
generally less than 200 ppb and probably averages
less than 100 ppb, except for alkalic igneous rocks
and deep-seated eclogites and kimberlites that aver-
age several hundred parts per billion Hg. Rocks
from a few areas in the world, notably Crimea and
the Donets Basin, U.S.S.R., show extremely high
contents of mercury, which makes general aver-
ages of abundance of doubtful significance.
Most sedimentary rocks have mercury contents
less than 200 ppb Ilg, except for shales, clays, and
soils, for which the data show considerable varia-
tion with average contents of a few hundred parts
per billion Hg. Shales rich in organic matter are no-
tably enriched in mercury, suggesting that some of
the mercury may be present as organic complexes.
The data show very high contents of mercury in a
few areas of the world, including those in which the
igneous rocks have high contents. Most of the analy-
ses of coals are from the Donets Basin, U.S.S.R.,
which again have high contents of mercury; a few
scattered analyses from other areas make it plausi-
ble to assume the presence of low concentrations of
mercury in most coals. Mercury has been reported
in large amounts in petroleum from one field in Cal-
ifornia.
Most natural waters (ground water, river wa-
ter, sea water) contain less than 2 ppb Hg. High
concentrations of mercury have been found in wa-
ters from hot springs and in brines from a petro-
leum field in California. Mercury is presumably dis-
solved by ground waters passing over rocks and is
added to waters in considerable amounts by in-
dustrial wastes, notably by alkali-chlorine plants
using the mercury cell method and by the paper
pulp industry. The mercury is apparently removed
in large part by adsorption on clays and on hydrous
oxides of iron and manganese, and also by algae
and plankton.
Mercury is present in the atmosphere, with back-
ground values of less than 1 to a few nanograms
(10~'' g") per cubic meter. Over metallic ore deposits,
the content of mercury is appreciably higher. Vol-
canic emanations including those of mud volcano
type, have high contents of mercury, and must con-
tribute a large amount of mercury to the atmos-
phere. In addition to such "natural pollution," one
must assume that mercury is added to the atmos-
phere by the burning of coal and petroleum ar.d
very likely from stack gases of smelters treating
copper, lead, and zinc ores. No data are available on
the amounts added by "man-made pollution" or on
the time of residence in the atmosphere of mercury
from "natural" or "mail-made" pollution.
GENERAL GEOCHEMICAL CHARACTERISTICS
OF MERCURY
Mercury has the atomic number 80 and atomic
weight 200.59. It has seven stable isotopes with per-
cent abundances 195, 0.15; 198, 10.1 ; 199, 17.0; 200,
23.3; 201, 13.2; 202, 29.6; and 204, 6.7. Mercury is
generally classed as a chalcophilic element, that is,
one that tends to concentrate in sulfides. There are
many minerals of mercury; the commonest are the
sulfides cinnabar and metacinnabar and native mer-
cury. Mercury is commonly present in tetrahedrite
(up to 17.6 percent in the variety schwatzite), in
sphalerite (up to 1 percent), and in wurtzite (up to
0.3 percent); it is present in small amounts in many
other sulfides and sulfosalts. The element's unu-
sually high volatility accounts for its presence in
the atmosphere in appreciable amounts. Its ionic
radius (Hg+-) is generally given as 1.06-1.12 ang-
stroms, so that in the lithosphere it might be ex-
pected to accompany Ba, Sr, and Ca; this probably
accounts for the high amounts of mercury found in
some barites, celestites, and in alkalic igneous rocks.
6
-------
SUMMARY OF THE LITERATURE
7
ABUNDANCE AND DISTRIBUTION OF MERCURY
Nearly all the data available have been obtained
during the past 30 years and most of it, during- the
past 10 years. As apparent from the summary that
follows, the information available is inadequate to
give a clear picture of the gcochemical cycle of mer-
cury oi' even to make accurate estimates of its
abundance in common rock types.
This is in large measure due to the difficulty of
analyzing rocks, soils, waters, and air for the very
small amounts of mercury present, generally in
parts {Kir billion or parts per million.
Many methods have been used for the determina-
tion of these small amounts of mercury. Among
them are the spectrographic method (usually with a
sensitivity of TOO ppb, and extended to 10 ppb in
improved procedures), separation of mercury by
distillation followed by determination by measure-
ment of the collected mercury globule or by a colori-
metrie method (the latter used in most of the analy-
ses in the U.S.S.R.), separation by extraction and
colorimetric determination, neutron activation anal-
ysis, and atomic absorption spectrophotometry.
Comparative data on precision and accuracy are
available only for the last two methods. (See table
l.1) Comparison of the data published by many in-
vestigators indicates that the methods give results
comparable to better than a factor of 5 and, hence,
the averages are within an order of magnitude of the
true values.
An even greater difficulty is that of weighting the
results available. It is now well established that ore
deposits of heavy metals, such as copper, lead, and
zinc, are surrounded by aureoles in which notable
enrichment in mercury has occurred; this is now a
recognized method of prospecting for ore deposits.
(See, fcr example, Friedrich and Hawkes (1966),
James (1962), Ozerova (1962), Saukov (1946),
and Warren and others (1966).) As a result, it is
necessaiy to discriminate between normal samples
and those from mineralized areas.
A further problem is that the data show very
clearly :hat some areas in the world (notably the
Donets Basin, Kereh-Taman area, and Crimea,
U.S.S.R) show extremely high mercury contents in
nearly all the rocks analyzed (100 times normal
contents or more). The reasons for this are not yet
known and it is not known howr many such areas
there may be.
1 Tables fire :n the back of the report.
MERCURY IN IGNEOUS ROCKS
Analyses of basalts, gabbros, diabases, andesites,
dacites, and rhyolitic rocks are given in table 2;
analyses of granitic rocks f.re given in table 3. Most
of these show contents of less than 200 ppb Hg and
the average content, is probably less than 100 ppb.
The two recent analyses of ultramafic rocks in table
4 show less than 10 ppb Hg. The data show no
clear-cut differences between the mafic and the si-
licic igneous rocks, although there is a slight sugges-
tion that the silicic rocks have somewhat higher
contents.
Two types of igneous rocks—deep-seated eclogites
and kimberlites (table 4) and the alkalic rocks
(table 5)—shows markedly higher contents of mer-
cury, with averages of several hundred parts per
billion Hg. Analyses of the individual minerals of
alkalic rocks show fairly uniform distribution of
mercury in the main rock-forming minerals, and
high concentrations in some of the accessory miner-
als of high calcium, strontium, and barium contents
(sphene, aegirine, lamprophyllite), Similar studies
have not been made of the individual minerals of
eclogites or kimberlites.
The foregoing picture is, greatly complicated by
the fact that analyses of all types of rocks from cer-
tain areas (notably in Crimea and the Donets
Basin) show extremely high contents of mercury
(up to 100 times as much as, those of tables 3 and 4).
These analyses have therefore been separated in
table 6. It is possible that these high values repre-
sent analytical error, but this seems unlikely be-
cause one of the laboratories reporting them has
also reported low "normal" values for similar rocks
from other areas (table o). The two areas have
some mercury mineralization; they also are near
areas of mud volcanoes thai: could have been sources
of considerable amounts of mercury. (See "Mercury
in sedimentary rocks and soils.") It should be noted
that basaltic and andesitic lavas from Kamchatka
and the Kurile Islands (table 2) have somewhat
higher than average contents of mercury. These
are, however, far less than many of the contents re-
ported in table 6, even though the volcanic activity
of this area also contributes considerable amounts
of mercury.
mekcuky in metamorphic rocks
The few analyses available of mercury in meta-
morphic rocks (table 7) show the same wide varia-
tion as the analyses of sedimentary rocks. (See
"Mercury in sedimentary rocks and soils.") Two
series of analyses (Ozerova and Aidin'yan, 1966a,
1966b) showed little variation of mercury content
-------
8
MERCURY IN THE ENVIRONMENT
with grade of metamorphism; this was contrary to
the expectation that high-grade metamorphism
would cause mercury to be driven out of the rocks.
MEKCURY IN SEDIMENTARY ROCKS AND SOILS
Analyses are collected of limestones (table 8),
sandstones (table 9), shales and clays (table 10),
miscellaneous sediments (table 11), oceanic and la-
custrine sediments (table 12), and soils (table 13),
Except for the areas that showed high contents in
igneous rocks, nearly all analyses of limestones and
sandstones gave less than 200 ppb Hg, with aver-
ages perhaps of 30 to 50 ppb Hg. The analyses
from the Donets Basin and Crimea show much
higher contents of mercury (up to 100 times).
Considerable variation is shown by the analyses
of shales and clays; again samples from Crimea, the
Donets Basin, and the Kerch Peninsula are anoma-
lously high. It has been suggested that these rocks
might have been enriched in mercury by accumula-
tion of the exhalations of mud volcanoes (tables 10,
11, 13, 15). The data of table 11 and table 12 sug-
gest that mercury is enriched in sedimentary Fe
and Mn ores, perhaps by adsorption or coprecipita-
tion. Bituminous shales are notably richer in mer-
cury than other shales, suggesting the possibility
that mercury may be present as some form of or-
ganic complex.
The analyses of soils in table 13 are similar in
general range to those of shales and clays. High val-
ues in soils above mineralized zones have been re-
ported by many investigators. It has been suggested
that the widespread use of organic mercury com-
pounds as seed fungicides has increased the content
of mercury in cultivated soils, but no data on this
have been found.
MERCURY IN COAL AND FETKOLEUM
The data on coals (table 16) are unrepresenta-
tive. Stock and Cucuel (1934a) found 1.2 to 25 ppb
Hg (average, 12 ppb) in 11 coals. Brandenstein,
Janda, and Schroll (1960) found 1,200 and 2,700
ppb Hg in two anthracites; the remaining 117 sam-
ples contained less than 1,000 ppb Hg. Headlee and
Hunter (19,53) reported <100,000 to 260,000 ppb
Hg (average, 120,000 ppb) in the ashes of coals from
West Virginia (ash content not given). About 1,000
samples from the Donets Basin, U.S.S.R., have been
analyzed (Dvornikov, 1963, 1965, 1967a, 1967b,
1968; Bol'shakov, 1964; Karasik, Yasilev'skaya, Pe-
trov, and Ratekhin, 1962; Ozerova, 1962; and
Tkach, 1966). This is an area with high contents of
mercury in all the igneous and sedimentary rocks
and in which commercial mercury ores occur closely
associated with coals. Background values for coals
not closely associated with mineralization are var-
iously stated by these authors as 200, 400, and 700
ppb Hg, but very much higher values (up to
300,000 ppb) have been reported from coal in lenses
in mercury deposits. Analyses show that the mer-
cury is mostly concentrated in iron sulfides in the
coal deposits; the mercury is generally considered to
be epigenetic and not syngenetic in origin. However,
Shcherbakov, Dvornikov, and Zakrenichnaya (1970)
found that much of the mercury in these coals is
present as organic compounds and suggest that the
mercury is syngenetic.
The only analyses of petroleum for meixury are
those of Bailey, Snavely, and White (1961), who
found 1,900 to 2,900 ppb Hg in petroleum from the
Cymric field, California.
MEBCUBY IN NATURAL WAT1KS
The available data on mercury in natural waters
are given in table 11, Most contain tenths of a part
per billion to a few parts per billion. Insufficient
data are given to permit assessment of the contribu-
tion of contamination. The mercury content of At-
lantic Ocean waters is stated to increase with the
amount of suspended material. The suspended mat-
ter of three samples of river waters contained 0.03
to 0.2 percent Hg, according to Kvashnevskaya and
Shablovskaya (1963), but the proportions of mer-
cury in solution and in suspension are not stated.
The high contents recorded for brines associated
with a petroleum field and in a geothermal well are
noteworthy. Data on some hot springs associated
with volcanism are discussed later.
According to Aidin'yan and Belavskaya (1963),
appreciable amounts of mercury can go into solu-
tion when ground waters react with cinnabar or
other mercury minerals, but this is removed almost
completely when the solution is passed over mud-
stones, This is in accord with data of Dall'Aglio
(1968) and with the experiments of Krauskopf
(1956), who showed that mercury is removed al-
most quantitatively from sea water by adsorption
on Fe(OH)3 or clay; the analyses of oceanic man-
ganese nodules (table 12) and of Mn ores (table
11) suggest that hydrous manganese oxides also act
as collectors of mercury.
It has long been known that some hot springs de-
posit cinnabar and metacinnabar; the conditions of
formation have been discussed by White (1955),
Tunell (1964), and by Ozerova and others (1969).
In addition to the data in table 15, White (1955)
quotes a report of 3,200 ppb Hg in hot spring water
-------
SUMMARY OF THE LITERATURE
9
from New Zealand, and White and Roberson (1962)
report 20 and 200 ppb Hg in hot springs at Sulphur
Bank, Calif.; but most such waters that have been
analyzed did not contain detectable amounts of mer-
cury.
Industrial pollution, notably by alkali-chlorine
plants using the mercury cell method and by the
paper pulp industry, has been referred to exten-
sively in recent newspaper accounts. The mercury is
apparently removed in large part by adsorption on
clayey sediments and on hydrous oxides of iron and
manganese and also by algae and plankton.
MERCURY" IN THE ATMOSPHERE
The available data are given in table 15. The low-
est figures presumably represent unpolluted air,
which apparently contains less than 1 to perhaps 10
ng/m3 Tig. "Natural pollution" caused by the volatil-
ity of .nercury from ore deposits of mercury or
base metals gave values up to 62 ng/m3. It is evi-
dent, however, that much higher concentrations and
very la -ge amounts of mercury reach the atmos-
phere from volcanic emanations, including those
from mud volcanoes.
The effects of industrial pollution probably ac-
count fir the highest figures reported in table 15
for air from California, the Chicago area, and the
Moscow-Tula region. The most probable source is
the burning of coal and perhaps of petroleum. An-
other probable source is from metal smelters. It is
well known that ores of lead, zinc, copper, and other
metals are enriched in mercury and it seems likely
that much of the mercury present escapes from the
stacks during smelting operations. No data are
available, however, either on the amounts of mer-
cury discharged or on its time of residence in the
atmosphere.
ANNOTATED BIBLIOGRAPHY
[The original papers were seen except for those marked
with an asterisk!*) ]
Abuev, I). V., Diyakov, K. S„ and Rad'ko, V. I., 1985, Mer-
cury in some neo-intrusives of the area of Caucasus
mineral springs: Geol. Rudn, Mestorozhd, 7 (6), p.
101-103 (in Russian) ; Chem, Abs. 64, p. 7884, 1966.
Spectrogrsphie analyses gave average contents of SO,
700, 4,000, and 5,000 ppb Hg in four granosyenite por-
phyry intrusives. Argillaceous marls contained 10 to
8,00C ppb Hg.
Afanas'ev, G. D,,and Aidin'yan, N, Kh,, 1961, Preliminary
data on the distribution of mercury in rocks of the
Northern Caucasus; Akad. Nauk SSSR Izvest., Ser.
Geol, 1961 (7), p. 101-104 (in Russian); Chem. Abs. 56,
p. 12586, 1962.
Ar.alyses of 23 igneous rocks are given.
Aidin'yan, N. Kh., 1962, Content of mercury in some natu-
ral waters: Akad. Nauk SSSK, Trudy Inst. Geol. Rudn,
Mestorozhd., Petrog., Mineral,, Geokhim, 70, p. 9-14 (in
Russian); Chem. Abs. 57, p. 16336, 1962,
Colorimetrie analyses gave 0.4 to 2.8 y.g/1 Hg (avg, 1.1
,ug/l) in 24 rivers, European SSSR. Fourteen waters
from seas and oceans gave 0.7 to 2,0 /jg/l Hg (avg, 1.3
1963, The content, of mercury in some waters of the
Armenian SSR: Akad. Nauk Armyan. SSR Izv., Ser.
Geol, i Geog, Nauk 16 (2), p. 73-75 (in Russian); Chem,
Abs. 59, p. 7237, 1963.
Waters from six rivers contained 1-2 /xgf 1 Hg; one
contained 20 jug/1 Hg.
Aidin'yan, N. Kh., and Relavsks.ya, G. A., 1963, The problem
of supergene migration of mercury: Akad, Nauk SSSR,
Trudy Inst, Geol. Rudn. Mestorozhd., Pet rug.. Mineral.,
Geokhim. 99, p, 12-15 (in Russian) ; Chem. Abs. 59,
p, 8471, 1963.
Solutions passed over cinmbar dissolved appreciable
amounts of Hg. This was removed almost completely by
passing the solutions through nnidsTor.es.
Aidin'yan, N. Kh., Mogarovskii, V. V., and Mel'nicheriko,
A, K., 1069, Geochemistry of mercury in the granitic
rocks of the Gissar pluton, central Tadzhikistan :
Geokhimiyaj p. 221-224; translation in Geochemistry In-
termit. 6, p. 154-158, 1969,
Analyses of 64 granites and granodiorites gave 10-75
ppb Ilg (avg, 30 ppb Hg).
'"Aidin'yan, N. Kh., and Ozerova, N. A., 1964, Geochemistry
of mercury during volcanism: Prohlemy Vulkanizma
(Petropavlovsk-Kamchatski! Dal'nevosfc. Kn. Izri.) Sbor-
nik, p. 30-32 (in Russian) ; Chem. Abs, <53, p. 279.5,
1965.
See Ozerova and Unanova (1965).
1966, Some genetic features of the formation of mer-
cury-containing -mineralization from the study of con-
temporary volcanic activity; Akad. Nauk SSSR, Inst.
Geol. Rudn. Mestorozhd., Petrog., Mineral., Geokhim.,
Oelierki Geokhim. Endogenn. i Gipergeiin. Protsessov
1966, p. 87-92 (in Russian),
Analyses are given of many volcanic gases, hot
springs, and solfataric minerals from Kamchatka and
the Kurile Islands.
'Aidin'yan, N. Kh., and Ozerova, N. A., 1968, Geochemis-
try of mercury: Problemy Geokhim. Kosmol. 1968, p.
160-165 (in Russian); Chem. Abs. 70 (7), p. 143, 1969.
A review.
Aidin'yan, N. Kh., Ozerova, N. A., and Gipp, S. K., 1963,
The problem of the distribution of mercury in contempo-
rary sediments: Akad. Nauk SSR, Trudy Inst. Geol.
Rudn. Mestorozhd., Petrog., Mineral., Geokhim. 99, p.
5-11 (in Russian); Chem. Abs, 59, p. 7262, 1963.
Analyses are given of Atlantic Ocean waters, 0.4-1.6
^g/1 Hg (avg, 1.2 /tg/1). The Hg content increases
with increasing amount of suspended matter. Many
analyses of oceanic sediments are given.
-------
10
MERCURY IN THE ENVIRONMENT
Aidin'yan, N. Kh., Shilin, L. L,, and Belavskaya, G, A., 1963,
The distribution of mercury in rocks and minerals of
the Khibiny massif: Akad. Nauk SSSR, Trudy Inst.
Geol. Rudn. Mestorozhd., Petrog., Mineral., Gpokhim. 99,
p. 16-25 (in Russian) ; Chem. Abs. 59, p. 7261, 1963.
Analyses of 179 alkalic rocks gave ,10-4,000 ppb Hg
(avg, 530 ppb Hg). Analyses of many minerals are
given,
Aidin'yan, N. Kb., Shilin, I . L„ and Unanova, O. G., 1986,
Contents of mercury in rocks and minerals of the Lo-
vozero massif: Akad. Nauk SSSR, Inst. Geol. Rudn.
Mestorozhd., Petrog,, Mineral., GeokMm., Ocherki Gco-
khim, Endogenn, i Gipergenn. Protsessov 1966, p. 14-19
(in Russian) ; Chem. Abs. 66, p. 547-5, 1967.
Analyses of 640 alkalic rocks gave an average content
of 273 ppb Hg. Analyses of 35 minerals are given.
Aidin'yan, N. Kh., Troitskii, A. I., and Balavskaya, G, A,,
1964, Distribution of mercury in various soils of the
U.S.S.R. and Vietnam; Geokhimiya, p. 654-659; transla-
tion in Geochemistry Internat. 4, p. 670-675, 1964.
Analyses are given of 130 soils from seven profiles in
European SSSR and 14 profiles of Vietnam,
*Anderssen, Arne, 1967, Mercury in the soil: Grundforbat-
tring, 20, p. 95-105 (in Swedish) ; Chem. Abs. 69, p.
4777, 1968.
Analyses of 273 soils from Sweden average 60 ppb Hg
and 14 soils from Africa average 23 ppb Hg.
Baev, V. G., 1968, Distribution of mercury in natural waters
of the southern slopes of northwestern Caucasus: Akad
Nauk. SSSR Doklady 181, p. 1249-1251 (in Russian);
Chem. Abs. 69, p. 8395, 1968.
Averages of about 7,000 waters in an area of 1,100 sq
km gave for surface waters 0.27-0.68 ugfi Hg and for
subsurface waters 0.25-1.25 /ig,/L
Bailey, E. H., Snavely, P. D,, Jr., and White, D. E., 1961,
Chemical analyses of brines and crude oil, Cymric field.
Kern County, California: U.S. Geol. Survey Prof. Paper
424-D, p. D306-D309,
Six analyses of crude oil showed 1,900-2,900 ppb Hg;
associated brines contained 100-400 ppb Hg,
Bol'shakov, A. P., 1964, The role of coal in ore deposition at
the Nikitovskoye quicksilver deposit: Geokhimiya, p.
477-480; translation in Geochemistry Internat. 3, p. 15!)
462, 1964.
Iligh contents of Hg were found in coals and associ
ated shales and sandstones in a mercury ore deposit.
Analyses are given.
Bostrom, Kurt, arid Fisher, D, E., 1969, Distribution of mer-
cury in east Pacific sediments: Geoehim. et Cosmochim,
Acta 33, p, 743-745,
Oceanic sediments contained 1-400 ppb Hg (carbon-
ate-free basis).
Brandenstein, M,, Janda, I., and Schroll, E., 1960, Rare ele-
ments in German coals and bituminous rocks: Tscher-
maks Mineralog, u. Petrog. Mitt. 7, p. 260-285 (in
German).
Two of 119 samples contained more than 1,000 ppb
Hg (limit of sensitivity of spectrographs method used ).
Rrar, S. S., Nelson, T>. M„ Kanabrocki, E. L,, Moore, C. E,,
Gurnham, C. T)., and Hattori, D. M., 1969, Thermal neu-
tron activation analysis of airborne particulate matter
in Chicago Metropolitan area: Natl. TV.iv. Standards
Spec. Pub. 312, v. 1, p. 43-54.
Analyses for Hg in air were made at 22 stations.
Rulkin, C. A., 1962, The geochemistry of mercury in the Cri-
mean highlands: Geokhimiya, p. 1079-1087; translation
in Geochemistry, p. 1219-1230, 1962.
Analyses are given of 68 igneous rocks and more than
500 sedimentary rocks; they are very high in mercury.
Buturlinov, N. V., and Korchemagin, V. A., 1968, Mercury in
magmatic rocks of the Donets Basin: Geokhimiya, p.
640-644 (in Russian) ; Chem. Abs, 69, p. 1990, 1968.
Analyses of 98 igneous rocks showed 60-4,700 ppb Hg
(avg, 55 ppb Hg).
Dall'Aglio, M., 1968, The abundance of mercury in 300 natu-
ral water samples from Tuscany and Latium (central
Italy), in Origin and distribution of the elements: Inter-
nat. Earth Sci. Ser. Mom, v. 30, p. 1065-1081.
Analyses are given of 300 samples from surface and
spring waters. Most analyses are in the range 0.01-0.05
ppb Hg, but waters draining areas of mercury minerali-
zation contain up to 136 ppb Hg; the mercury contents
decrease rapidly downstream, indicating absorption of
mercury by alluvium.
Donnell, J, R., Tailleur, I, L„ and Tourtelot, H. A., 1967,
Alaskan oil shale: Colo. School of Mines Quart., 62 (3)
p. 39-43.
Two oil shales contained 630-2,800 ppb Hg.
Dvornikov, A. G., 1963, Characteristics of aureole distribu-
tion of mercury in soils and coals of the southeastern
part of the Donets Basin: Akad. Nauk SSSR Doklady
160, p. 894-897 (in Russian); Chem, Abs. 59, p. 7245,
1963.
Analyses of 248 soils showed <50-10,000 ppb Hg
(avg, 300 ppb Hg) ; 206 eoais contained 59-10,000 ppb
Hg (avg, 1,100 ppb Hg). Mercury deposits are known in
the area,
1965, Distribution of mercury, arsenic and antimony
in rocks of the Bokovo-Khrustal'sk ore (Donets Basin) :
Geokhimiya, p. 695-705 (in Rij;:5;an)*, Chem. Abs. 63, p.
5399, 1965.
Graphs show the variation of Hg content (very high)
in sediment associated with Hg ore deposits.
1967a, Some features of mercury-containing coals of
the eastern Donbass (Rostov region) : Akad. Nauk
SSSR Doklady 172, p. 199-202 (in Russian); Chem.
Abs. 66, p. 5450, 1967.
Analyses of 756 coals showed 20 to 20,000 ppb Hg.
1967b, The distribution of mercury in anthracites of
the Bokovo-Khrustalnava basin (Donbass) : Akad. Nauk
-------
SUMMARY OF THE LITERATURE
11
RGR Dopovidi, Ser. B.. 29, p, 298-298 (in Ukrainian) ;
Cham. Abs, 56, p. 5298, 1967.
Analyses showed 100 to 7,000 ppb Hg, which was con-
centrated in the iron sulfides.
1968, Some features of geoehemieal anomalies in coals
in the endogenic aureole of dispersion of the Nikitov
mercury deposits: Akad. Nauk Ukruyin. RSR Dopo-
vMI, Ser, B,, 1968 (8), p 782-785 (in Ukrainian); Chem.
Abs. 70, p. 145, 1969.
Analyses of coals associated with a mercury deposit
shewed 100 to 300,000 ppb Hg (avg, 46,000 ppb Hg).
Dvornikov, A. G., and Klitehenko, M. A., 1964, The distribu-
tio'i of mercury in intrusive rocks of the Nagolnyi
Ridge: Akad, Nauk Ukrayin, RSR Dopovidi, p.
1354-1357 (in Ukrainian); Chem. Abs. 62, p. 3841,
1965.
Camptonite and plagiogranite in ail area of mercury
deposits contained 3,000-7,000 ppb Hg. Shale of the
area averaged 50 ppb Hg; sandstone, 300 ppb Hg.
Dvornikov, A. G., and Petrov, V. Ya,, 1961, Some data on
the mercury content in soils of the Nagolnyi Mt. Range:
Geokhimiya, p. 920-925; translation in Geochemistry p.
10S1-1028, 1961.
Analyses of 131 soils in five profiles over a mercury
deposit (avg, 1,300 ppb Hg).
Ehmann, W. D., and Levering, J. F., 1967, The abundance of
mercury in meteorites and rocks by neutron activation
ant.lysis: Geochim. et Cosmochim, Acta 31, p. 357-376.
Many analyses are given. Noteworthy are the high
contents reported for eclogites and kimberlites,
Friedrieh, G. H., and Hawkes, H. E., 1966, Mercury disper-
sion haloes as ore guides for massive sulfide deposits,
West Shasta district, California: Mineralium Deposita
1, p. 77-88,
Analyses are given of traverses from nonmineralized
ground across the ore body.
Golovnya, S. V., and Volobuev, M. I. 1970, Distribution of
mercury in granitic rocks of the Yenisei Range; Geokhi-
miya, p. 256-261 (in Russian).
Analyses of 70 samples gave ant average of 28 ppb
Hg
"Hamaguchi, Hiroshi, Kuroda, Rokuro, and Hosohara, Kyoi-
chi, 1961, Photometric determination of traces of mer-
cury in sea water: Nippon Kaguku Azsshi 82, p.
347 -349 (in Japanese) ; Chem. Abs. 65, p. 15222, 1961.
Analyses of waters from the Ramapo Deep, Pacific
Ocean, gave 0.08-0.15 fig/l Hg (avg, 0.1 pg/l Hg).
Harriss, R. C., 1988, Mercury content of deep-sea manganese
nodules: Nature, v. 219 (5149), p. 54-55; Chem. Abs.
69, p. 4318, 1968.
Analyses are given of 14 samples from the Pacific,
Atlantic, and Indian Oceans.
Headlee, A, J. W.. and Hunter, R. G., 1953, Elements in coal
ash and their industrial significance: Industrial Engi-
neering Chemistry, v. 45, p, 548-551.
Analyses of 596 samples from 16 seams, West Vir-
ginia, showed <100 to 260 ppb in the coal ash (ash con-
tent not given).
Heide, F,, and Bohm, G., 1957, The geochemistry of
mercury: Chemie Erde, v. IS, p. 198-204 (in German);
Chem. Abs, 52, p. 2685, 1958.
Analyses are given of 14 limestones, three clays,
Saale River water, Elbe River water, and sea water,
Heide, F., Lerz, H., and Bohm, G,, 1957, Content of lead and
mercury in the Saale: Naturwissenschaften, v. 16, p.
441-442 (in German) ; Chem. Abs. 52, p. 9490, 1958.
Analyses are given of eight samples of the Saale
River and one sample of the Elbe River.
"Hosohara, Kyoichi, 1961, Mercury content of deep-sea
water: Nippon Kagaku Zasshi 82, p. 1107-1108 (in Jap-
anese) ; Chem. Abs. 56, p. 4535, 1962.
Analyses of four samples from the Ramapo Deep, Pa-
cific Ocean gave 0.15-0.27 ng/I Hg.
* Hosohara, Kyoichi, Kozuma, Hirotaka, Kawasaki, Kat.su-
hiko, and Tsuruta, Tokumatsu, 1961, Total mercury
content in sea water: Nippon Kagaku Zasshi 82, p.
1479-1480 (in Japanese); Chem. Abs. 56, p. 5766, 1962.
Waters of Minamata Bay, Kyushu, contained 1.6-3.6
ng/1 Hg. Plankton contained 3,500-19,000 ppb Hg.
*Ishikura, Shuriji, and Shibuya, Chieko, 1968, Analysis of
mercury in fish and soils from the Agano River,
Japan: Eisei Kagaku 14, p. 228-230 (in Japanese);
Chem. Abs, 70, p, 234, 1969.
Analyses of soil, waters of the Agano River, and of
fishes are given.
James, C. H., 1962, A review of the geochemistry of mercury
(excluding analytical aspects) and its application to
geoehemieal prospecting: Imperial Coll. Sci. Technol.,
Geoehem. Prospecting Research Centre Teehn, Comm.,
(41), p, 1-42.
A review.
Jovanovic, S,, and Reed, G. W,, 1968, Mercury in meta-
morphic rocks: Geoehem, et Cosmochim. Acta 32, p.
341-346.
Analyses are given of 14 pelitic schists, Vermont, one
gabbro, Quebec, and one amphibolite, Quebec,
Karasik, M. A., and Goncharov, Yu. I., 1963, Mercury in
Lower Permian sediments, of the Donets Basin: Akad.
Nauk SSSR Doklady 150, p. 898-901 (in Russian);
Chem. Abs. 59, p. 7261, 1968.
Analyses are given of 77 sandstones (avg, 870 ppb
Hg), 55 clays and shales (avg, 660 ppb Hg), and 71
evaporites (avg, 700 ppb Hg).
Karasik, M. A,,Goncharov, Yu. I., and Vasilevskaya, A. E.,
1965, Mercury in mineralized waters and brines from the
Permian halogen formations in the Donets Basin: Geok-
himiya, p. 117-121; translation in Geochemistry Internat.
2, p. 82-86, 1965.
Analyses of 26 waters from evaporite beds showed
<1 to 8.5 figfl Hg, except for one sample with 220 pg/1
Hg.
-------
12
MERCURY IN THE ENVIRONMENT
Karasik, M, A,, and Morozov, V. L, 1966, Distribution of
mercury in the products of mud volcanism in the
Kerch-Tainan Province: Geokhimiya, p. 668-878; trans-
lation in Geochemistry Internat. 8, p. 497-507, 1966,
Analyses are given of 156 clay rocks and 223 soils
from an area of mud volcanoes; the rocks are very high
in Kg-,
Karasik, M. A., Vasilev'skaya, A, E., Petrov, V. Ya., and
Ratekhin, E. A., 1962, Distribution of mercury in coals
of the central and Donets-Makeevka regions of the Do-
nets Basin: Akad, Nauk Ukrayin. RSK Geol, Zhurn, 22,
(2), p. 53-61 (in Ukrainian); Chem. Ahs. 57, p. 2513,
1962.
Ranges of Hg content are given for 488 coals; about
half are well above background,
Krainov, S. R., Voikov, G. A,, and Korol'kova, M. Kh,, 1966,
Distribution and mode of migration of the trace ele-
ments Zn, Cu, Hg, Li, Rb, Cs, As, and Ge: Geokhimiya,
p. 180-196; translation in Geochemistry Internat. 3, p.
108-12,3, 1966.
Analyses of waters in the Elbrus volcanic region
showed <0.5 to 80 /tg/l Hg; most samples had 1 fig/l Hg
or less,
Krauskopf, K. B., 1956, Factors controlling the concentra-
tions of thirteen rare metals in sea-water: Geochim. et.
Cosmochim. Acta 9, p. I S2B.
Experiments show that Hg- may be removed from sea
water by adsorption on Fe (OH)j or clay, or by take-up
by plankton.
"Kurmanaliev, K. K.. 1967, Presence of mercury in Cambrian
formations of Madygen village, so'itbern Feighana:
Rasseyan, Elim. Osad. Form, Tyan-Shanya 1967, p.
122—124 (in Russian) ; Chem. Abs., v. 68, p. 502, 1968.
Average Hg- contents are given for sandstones and
schists.
Kvashnevskaya, N. V., and Shablovskaya, E, I., 1963, Study
of the contents of ore elements in the suspended matter
of river systems: Akad. Nauk SSSR Doklady 151, p.
426-429 (in Russian) ; Chem. Abs. 59, p. 12506, 1963.
Hg was detected and determined in the suspended
matter of three of the 48 samples tested from Armenia,
Georgia, Kazakhstan, Tadzhikistan, and Uzbekistan.
Landstrom, O., Samsahl, K., and Wenner, C, G., 1969, An in-
vestigation of trace elements in marine and lacustrine
deposits by means of a neutron activation method: Natl.
Bur. Standards Spec. Pub. 312, v, 1, 353-366.
Analyses are given of two lake sediments and two sea
sediments.
McCarthy, J, H., Jr., Vaughn, W. W., Learned, R. E., and
Meuschke, J. L., 1969, Mercury in soil gas and air—a
potential tool in mineral exploration: U.S. Geol. Survey
Circ, 609, 16 p.
Analyses of air showed four to six times normal back-
ground content in the air over two porphyry copper de-
posits; seven to 13 times normal background content in
air over two mercury deposits.
Morozov, V. I., 1965, Mercury in Cenozoic Deposits of the
Kerch Peninsula: Akad. Nauk SSSR Doklady 163, p.
209-211 {in Russian) ; Chem. Abs. 63, p. 11187, 1965,
Analyses are given of 194 clay rocks and of 264 soils
in an area of mud volcanoes. Contents of Hg are high.
Nekrasov, I. Ya., and Timofeeva, M. A., 1963, Mercury in
rocks and minerals of northeastern Yakutia: Akad.
Nauk SSSR, Trudy Yakutsk Filial Sibirsk Otdei, Ser.
Geol, 16, p. 23-38 (in Russian) ; Chem. Abs. 59, p,
15069, 1963.
Analyses are given of 41 limestones, sandstones, and
shales; 21 effusive rocks, 150 intrusive rocks, arid many
minerals.
Nikiforov, N. A., Aidin'yan, N. Kh., and Kusevich, V. I.,
1966, The content of mercury in Paleozoic sedimentary
rocks of southern Ferglana: Akad. Nauk SSSR, Inst,
Geol. Rudn. Mestorozhd., Petrog., Mineral., Geokhlm.,
Ocherki Geokhim. Endogenn. i Gipergenn. Protsessov
1966, p. 294-296 (in Russian) ; Chem. Abs, 66, p. 5475,
1967.
Average contents of Hg were determined for shales,
sandstones, and limestones in unaltered rocks, in rocks
near large fractures, and in areas of mercury minerali-
zation,
Ozerova, N. A. 1962, Primary aureoles of dispersion of mer-
cury: Akad. Nauk SSSR, Trudy Inst, Geol. Rudn. Mos-
torozhd., Petrog,, Mineral., Geokhim, 72, p. 1-135 (in
Russian).
A review, with many new analyses of minerals, ig-
neous rocks, and shales from ore bearing areas.
Ozerova, N. A., and Aidin'yan, N. Kh., 1966a, Distribution
of mercury in sedimentary rocks: Litol i Polezn. Iskop.
1966, (3), p. 49-57; translation in Lithology and Min-
eral Resources, p. 312-318, 1966,
Analyses of 500 sedimentary rocks are given.
1966b, Mercury ir. sedimentary processes: Akad. Nauk
SSSR, Inst. Geol. Rudn. Mestorozhd., Petrog., Mineral.,
Geokhim., Ocherki Geokhim. Endogenr,. i Gipergenn.
Protsessov 1966, p. 211-237 (in Russian) ; Chem. Abs.
66, p. 5475, 1967.
A review.
Ozerova, N. A., Aidin'yan, N. Kh., Dobrovol'skaya, M. G,,
Shpetalenko, M. A., Martynova, A. F., Zubov, V. I., and
Laputina, I. P., 1969, Contemporary mercury ore forma-
tion in the Mendeleev Volcano, Kurile Islands: Geol.
Rudn. Mestorozhd. 11 (5), p. 17-33 (in Russian).
Analyses are given of lavas, opalite, and iron sulfides
from cinnabar-containing altered dacites in a solfatara
area.
Ozerova, N. A., and Unanova, O. G., 1965, The distribution
of mercury in lavas of active volcanoes in Kamchatka
and the Kurile Islands: Geol. Rudn. Mestorozhd. 7, (1),
p. 58-74 (in Russian); Chem. Abs. 62, p. 12932, 1965.
-------
SUMMARY OF THE LITERATURE
IS
Analyses are given of 63 basalts, 209 andesites, and
two (Sacites.
*Panov, 15. S., 1959, Mercury in volcanic rocks of the south-
western district of the Donets Basin: Donets Ind. Inst,
Trudy 37, p. 149-152 (in Russian): Chem. Abs. 55, p.
9192, 1961.
Analyses of five effusive rocks show very high con-
tents of Hg.
Preuss, F1940, Spectrographic methods. II. Determination
of Zn, Cd, Hg, In, TI, Ge, Sn, Pb, Sb, and Hi by frac-
tional distillation: Zeitschr, Angew. Mineralogie 3, p.
8-20 (in German).
Analyses are given of composite samples of gabbros,
granites, shales, and sandstones.
Saukov, A. A., 194C, Geochemistry of mercury: Akad. Nank
SSSIt, Trudy Inst. Geol. Nauk 78, p. 1-129 (in Rus-
sian.
A :*eview.
*Shabalir, V. V., and Solov'eva, V. V., 1967, Distribution of
mercury in Cambrian formations of the Dzetym-Too
Ridge: Rasseyan, Elem, Osad. Form. Tyan-Shanya 19C7,
p. 103-108 (in Russian) ; Chem. Abs. 68, p. 502, 1968.
Analyses of Ave series of sedimentary rocks.
Shcherbakov, V. P., Dvornifcov, A. G., and Zakrenichnaya, G.
L,, 1970, New data on the forms in which mercury oc-
curs in coals of the Donets Basin: Akad. Nauk Ukrayin
RSR Dopovldi, Ser. B, 32 (2), p. 126-180 (in Ukrain-
ian) ; Chem. Abs. 73 (4), p. 180, 1970.
A considerable part of the Hg present in these coals
is present as organic compounds, in part humie acids.
Skinner, B. J., White, D. E., Rose, H. J., Jr., and May, R.
E., 1967, Sulfides associated with the Saltan Sea geo-
thermal brine: Econ. Geology, v. 62. p. 316-330.
A brine contained 6 ppb Hg.
Stock, AL'red, and Cucuel, Friedrieh, 1934a, The distribution
of mercury: Naturwissenschaften, v. 22, p. 390-393 (in
German); Chem. Abs. 28, p. 7086, 1934.
Analyses are given of igneous rocks, sedimentary
rocks, soils, coals, waters, and air.
Stock, Al fred, and Cueuel, Friedrieh, 1934b, The determina-
tion of the mercury content of air: Deut. Chem, Ges.,
Ber., S7B, p. 122-127 (in German).
Analyses showed 8' ng/m3 Hg in two samples of uncon-
tamii ated air.
"Tkach, I!. L, 1966, Geochemical characteristics of the distri-
bution of mercury in coal beds of the Lisichansk area,
Donets Basin: Geokhimiya p. 610-616 (in Russian);
Chem. Abs. 65, p. 5257, 1966.
Analyses of coals indicate that the Hg was introduced
and not syngenetic.
Twiell, George, 1964, Chemical processes in the formation of
mercury ores and ores of mercury and antimony: Geo-
chem. et Cosmochim. Acta 28, p. 1019-1037.
A discussion, including tl:e deposition of mercury sul-
fides from hot springs.
1968, The geochemistry of mercury, in Handbook of
chemistry: Berlin, Springer Verlag, 65 p. (In press).
A review.
Warren, H, V., Delavault, R. EI., and Barakso, John, 1966,
Some observations on the geochemistry of mercury as
applied to prospecting: Econ. Geology, v. 61, p.
1018-1028.
Analyses are given of soils and vegetation in trav-
erses from unmineralized to mineralized areas.
White, D. E., 1955, Thermal springs and epithermal ore de-
posits: Econ. Geology, 50th anniversary volume, p.
99-154.
A review.
White, D. E., and Roberson, C. E., 1962, Sulphur Bank,
Calif., a major hot spring quicksilver deposit: Geol, Soc.
Am., Budding-ton volume, p. 397—428.
Description, with analyses of hot springs depositing
mercury sulfides.
*Wikander, Lambert, 1968, Mercury in ground and river
water: Gruridf orbaettring 21, p. 151-155 (in Swedish);
Chem. Abs. 70, (7), p. 208, "..969.
Analyses are given of 36 waters drained from culti-
vated soils and of four rive:: waters; 38 samples showed
0.02-0.07 /ig/1 Hg (avg, 0,05 pg/l Hg), two showed 0.2
MKA
Williston, S. IT., 1968, Mercury in the atmosphere: Jour.
Geophys. Research, v. 73, p. 7051-7055.
Analyses of air from California, Most soils have
20-40 ppb Hg, but some have 100-200 ppb, even in ap-
parently unmineralized areas.
Zautashvili, B. Z., 1966, The problem of mercury hydro-
geochemistry, as illustrated by the mercury deposits of
Abkhazia: Geokhimiya, p. 357-362 (in Russian) *, Chem.
Abs. 64, p. 17267, 1966.
Ground waters of the region and mine waters were
low in Hg (<0.5-5 pg/I).
-------
MERCURY CONTENT OF ROCKS, SOTLS, AND STREAM SEDIMENTS
By A. P. Pierce, J. M. Botbol, and R. E, Learned
Mercury is routinely determined in U.S. Geologi-
cal Survey laboratories with atomic absorption
equipment developed by Vaughn (1967). An hide-
J, H. MnTnrthy r'in !
Ehrnann and Lover in
With the possible exception of standard rock
AGV-1, the analyses with two entirely independent
methods compare remarkably well, especially con-
sidering the rather low mercury content of the
rocks.
We have tabulated statistics on mercury content
of rocks, soils, and sediments as determined by the
atomic absorption method, from three readily avail-
able sources: analytical data that are computer
stored and that are immediately available for proc-
essing; data that have already been published, and
data that are in the process of publication attd have
limited computer availability. All three sources of
information contributed to the compilation of table
17 (in the back of this report) in which statistics
for about 25,000 samples from 32 areas are listed.
Areas represented in table 17 are located in the cen-
tral and western conterminous United States, in
Alaska, and in Puerto Rico. The bulk of the samples
were collected in order to test for the presence of
anomalous concentrations of metals in surface ma-
terials.
A wide range from <10 to 6,000 ppb mercury, is
seen in the modal mercury values listed in table 17.
This variability indicates that levels of natural mer-
cury concentrations, or abundance, are relatively
complex functions of geologic conditions and that
criteria for either mercury mineralization or abnor-
mal mercury contamination should be evaluated sep-
arately in any single area of interest.
The modal mercury values canvassed in table 17
also indicate that mercury tends to occur most fre-
pendent check by J. H. McCarthy, Jr., of this
method against the method of neutron activation is
summarized below:
DTs-i nric i
quenlly at certain concentrations. For example,
modes at about 50 ppb and at about 200 ppb are es-
pecially common. The tendency may be identified
both with sample type and with the effects of spe-
cific geologic processes, occurring at or hear the
surface in the area sampled. The common occur-
rence of mercury ores in concentrations of about 0.1
to 0.8 percent mercury (1,000 to 8,000 ppm) (Level-
ing, 1069, p. I 15) may be another instance of this
tendency, although 11 represents the effects of geo-
logic processes operating" under rare geothermal
conditions.
The percentile ranges of mercury distributions
for the first, I." areas listed in table 17 (see also fig.
1) indicate that far less than 20 percent of the rock
samples and stream-sediment samples have concen-
trations greater than 1,000 ppb mercury. For rocks
and stream sediments the upper limit of the ranges
of 90th percentiles indicate that any mercury values
greater than 1,000 ppb are considered worthy of
further investigation as possible results of (1) mer-
cury mineralization processes or (2) surface con-
tamination by mercury-bearing wastes.
Statistics for only four sets of soil samples are
available, and these suggest a background value of
500 ppb mercury for soils in Western United States.
These critical values are generalized estimates
based on the data in table 17. As mentioned pre-
viously, firm criteria for determination of anoma-
lous mercury values should be evaluated individu-
ally for each area of interest.
Determination of mercury in parts per hilliov in U.S. Geokt/'i rl S'lt 11
-------
ROCKS, SOILS, AND STREAM SEDIMENTS
15
?04r
10-
ct:
\jj
a.
to
i-
ct
<
Qu
o: io2
Z>
a
or
io L
~r
ROCK
Jvcnnoe
Ivanhoe
i I
25
50
I i
I I
I I
I I
I—-I
I I
f i
I t
R
I I
I I
25
SOIL
Ivanhoe
,Ivanhoe
ivcmhce <
I
50
75
PERCENTILES
"T"
STREAM SEDIMENTS
i I
i i
i i
Gulf
sedinentsc
90
J
75
Figure 1.—Percentile ranges of mercury distribution in rock, soil, and sediments.
As a frequency distribution approaches normality
tlie arithmetic mean approaches the median. Many
of the mercury distributions we have seen approach
normality. Therefore, where median values were
not available, arithmetic means (table 17) were
used as approximations of the median. Where nei-
ther arithmetic means nor medians were available,
geometric means were used as measures of central
tendency. These statistics are listed in the 50th per-
centile column of table 17 and in the graphical
summary shown in figure 1.
We acknowledge the assistance of Lamont T.
Wilch, Theodore M. Billings,, and Raoul V. Mendes
for their aid in the computer processing for this re-
port.
REFERENCES CITED
Clark, A. L., Condon, W. H„ Hoare, J. M., Sorg., D. H.,
197(i, Analyses of rock and stream-sediment samples
from the Taylor Mountains C-S quadrangle, Alaska:
U.S. Geol. Survey open-file rept., 110 p.
Ehmann, W. D., and Lovering, J. F., 1967, The abundance of
meriury in meteorites and rocks by neutron activation
analysis: Geoehim. et Cosmochim. Acta, v. 31, no 3, p.
857-376.
Fischer. K. P., Luedke, R. G., Sheridan, M. J., and Raabe, R.
G., 1968, Mineral resources of the Unconnpahgre primi-
tive area, Colorado: U.S. Geol. Survey Bull. 1261-C, 01
p. [1969J.
Flanapan, F, J., 1969, L". S. Geological Survey standards; 2,
First compilation of data for the new U.S.G.S. rocks:
Geoehim. ot Cosmochim. Acta, v. S3, No. 1, p. 81—120.
Gott, G. 1!., riothol, .1. M., Hillings, T. M., and Pierce, A. P.,
1969, Gc-ochemical abundance and distribution of nine
metals in rocks and soils of the C-oeur d'Alene district,
Shoshone County, Idaho; U.S. Geol, Survey open-file
rept., 3 p.
Gower, H. D., Vedder, J. G., Clifton, H. E,, and Post, E. V.,
1966, -Mineral resources of the San Rafael primitive
area, California: U.S. Geol. Survey Bull. 1280-A, 28 p.
Harrison, J. E., Reynolds, M. W., Kleinkopf, M. D., and
Patee, E, C., 1969, Mineral resources of the Mission
Mountains Primitive Area, Missoula and Lake Counties,
Montana: U.S. Geol. Survey Bull. 1261-Dj 48 p.
Lovering, T. S., 1969, Mineral resources from the land, in
Resources and man: San Francisco, W. H. Freeman and
Co., p. 109-134.
Pearson, R. C., Hayes, P. T., and Fillo, P. V., 1967, Mineral
resources of the Ventana primitive area, Monterey
County, California: U.S. Geol. Survey Bull. 1261-B, 42
P-
-------
16
MERCURY IN THE ENVIRONMENT
Ratte, W. Landis, E. JR., Gaskill, D. I.., and Raabe, R, G..
196!), Mineral resources of the Blue Range primitive
area, Greenlee County, Arizona, and Catron County,
New Mexico, with a section on Aeromagnetic interpreta-
tion, by G. P. Eaton: U. S. Geol, Survey Bull. 1261-E,
91 p.
Tveto, Ogden, Bryant, Bruce, and Williams, F. E.. 15)70,
Mineral resources of the Gore Range-Eagle Nest Primi-
tive Area and vicinity, Summit and Eagle Counties, Col-
orado: U.S. Geol. Survey Bull. 1319-C, 127 p.
Vaughn, W, W., 1967, A simple mercury vapor detector for
geochemieal prospecting: U.S. Geol. Survey Cire. 540, 8
P-
-------
MERCURY IN SEDIMENTARY ROCKS OF THE COLORADO
PLATEAU REGION
By R. A. Cadigan
Mercury content of sedimentary rocks in the Col-
orado Plateau region ranges from < 10 ppb to
>10,000 ppb. Sedimentary rocks compose or imme-
diately underlie more than 90 percent of the surface
of the region.
Samples have been collected by the author and
other Geological Survey employees engaged in var-
ious geologic investigations in the Colorado Plateau
region over the past 20 years. The major projects
involved were the stratigraphic studies program
conducted on behalf of the Atomic Energy Commis-
sion, 1948-56, and the Geological Survey's continu-
ing Heavy Metals program which began in 1967.
Samples collected for studies of mineral deposits or
to confirm geochemical anomalies were omitted
from this summary.
The data presented here were obtained from
3,012 samples collected from surface outcrops at ap-
proximately 150 localities in the Colorado Plateau
region (fig. 2). The samples were analyzed in the
laboratories of the U.S. Geological Survey by means
of an atomic absorption technique.
Data, on mercury content of most of the major
sedimentary stratigraphic units are summarized in
UTAH
COLORADO
NEW MEXICO
ARIZONA
Figure 2,—Location of Colorado Plateau
region (stippled)
table 18, in the back of this report. Statistics are
listed under the following headings: "Number of
samples," the number of analyses on which the com-
puted statistics are based; "Median," the middle
value of each distribution (half of the values are
larger and half are smaller) ; "Highest," the maxi-
mum value determined; "Lowest," the minimum
value; and "Middle 68 percent of samples," the
range of values grouped around the median, ap-
proximately 31 percent (one standard deviation) on
each side. "Dominant rock types" refers to the tex-
tural rock type listed below in order of importance
and which makes up 90 percent or more of the for-
mation or the group. "Approximate average thick-
ness" is given to provide an idea of the order of
magnitude of the amount of rock involved. The sta-
tistical distributions of mercury values are approxi-
mately log normal.
The stratigraphic units are listed in table 18 in
order of youngest to oldest; not all units are present
in all parts of the region. Their absence is clue to
erosion or nondeposition. The Duchesne River For-
mation is present and was deposited only along the
north edge of the region. The Dolores and arkosic
facies of the Cutler are present and were deposited
only in the eastern part of the region.
As depicted in a series of outcrop maps of many
formations in the Colorado Plateau region (New-
man, 1962), outcrops of the Tertiary and Upper
Cretaceous sedimentary rocks in the region are dis-
continuous because of erosion, but they occupy ap-
proximately 20 and 30 percent, respectively, of the
surface area of outcropping sedimentary rocks. Ju-
rassic and Triassic rocks crop out in approximately
40 percent of the sedimentary rock surface area and
Paleozoic rock outcrops (Permian, Pennsylvanian,
and others) occupy the remaining 10 percent.
The average distribution of mercury in the sedi-
mentary rocks which form the surface or which im-
mediately underlie soil-covered surfaces of the Colo-
rado Plateau region is shown in figure 3. The figure
17
-------
18
MERCURY IN THE ENVIRONMENT
MERCURY, JN PARTS PER BILLION
Fk ::tire 3.-—Frequency histogram of percent of samples
plotted over mercury content—a composite of the forma-
tion and the group sample data summarized in table 18,
weighted for area of outcrop and unit thickness. Basal
scale is logarithmic. The statistics for mercury content of
Colorado Plateau sedimentary rocks are as follows: Me-
dian, 160 ppb; maximum >10,000 ppb; minimum <10
ppb; range of middle 68 percent of samples, 66-370 ppb.
is a composite of values of the samples used for
table 18, weighted in terms of the proportions of
the rocks by geologic period composing the surface
outcrops and in terms of thickness of individual
units. It is thus a rough generalization, but it is
based on the best information available at the mo-
ment. The Tertiary contribution to the average is
computed using the three units listed in table 18.
The Duchesne River unit is given a weight of 2 for
the proportion of Tertiary rocks and a thickness
weight of 0.13 (thickness of the Duchesne River di-
vided by total thickness of the Tertiary units). The
Uinta and Green River unit is given a weight of 2
for the Tertiary and a thickness weight of 0.7; and
the Wasatch and Colton unit is given a weight of 2
and a thickness weight of 0.17. The units in the
other periods are treated similarly with the Creta-
ceous receiving a weight of 3, the combined Jurassic
and Triassic receiving a weight of 4, and the com-
bined Permian and Pennsylvanian units receiving a
weight of 1.
Samples containing the highest mercury content
(>10,000 ppb) were collected in mineralized areas
near uranium deposits in the Morrison, Entrada,
Chinle, and Moenkopi Formations. The maximum
mercury content has not been determined in these
areas, nor has the three-dimensional pattern of oc-
currence. Most of the samples from the Morrison
and Chinle which contain more than 1,000 ppb mer-
cury were collected from localities near known ura-
nium deposits. Stream-sediment samples collected
from streams adjacent to and draining the mineral-
ized areas have been found to contain as much as
1,100 ppb mercury. Samples from the Green River
oil shale strata also contain higher amounts of mer-
cury (4,000 ppb).
No significant correlation appears to exist be-
tween mercury content and rock texture per se in
Colorado Plateau sedimentary rocks. For example,
mercury is present in the Navajo Sandstone in
lower quantities than in any of the other forma-
tions. Regional distribution of mercury in the Na-
vajo was previously studied (Cadigan, 1969). The
Wingate Sandstone, similar in structure to the Na-
vajo and only slightly finer grained and slightly less
well sorted, contains substantially higher amounts
of mercury than the Navajo. This example suggests
that factors other than texture may exert a higher
level of control of the abundance of mercury in for-
mations. There is certainly a strong suggestion that
rocks that are predominantly composed of altered
volcanic detritus, such as the mudstone strata of the
Wasatch, Colton, Maneos, Morrison, and Chinle
Formations, contain higher amounts of mercury
than do the rocks that contain little volcanic detri-
tus.
Limestones in the ITermosa and Rico Formations
contain more mercury than the values given in the
literature (Turekian and Wedepohl, 1961).
Studies of the distribution of mercury and other
metallic elements in Colorado Plateau sedimentary
rocks are continuing and may yield additional infor-
mation to modify or supplement data and conclu-
sions presented in this report.
REFERENCES CITED
Cadigan, R. A., 1969, Distribution of mercury in the Navajo
Sandstone, Colorado Plateau region, in Geological Survey
research 1969: U.S. Geol. Survey Prof. Paper 650-B, p.
B94-B100.
Newman, W. L., 1962, Distribution of elements in sedimen-
tary rocks of the Colorado Plateau—A preliminary re-
port: U.S. Geol. Survey Bull. 1107-F, p. 337-445.
Turekian, K. K., and Wedepohl, K, H., 1961, Distribution of
the elements in some major units of the Earth's crust:
Geol. Soc. America Bull., v. 72, no. 2, p. 175-191.
-------
CHEMICAL BEHAVIOR OF MERCURY IN AQUEOUS MEDIA
By John D. Hem
The chemical behavior of the element mercury in
water is highly interesting, although rather compli-
cated and still not entirely explainable. Its behavior
is "mercurial" in more than one sense of the word.
A general statement of what is known and can rea-
sonably be inferred about the aqueous chemistry of
mercury is given here. This review should aid in the
interpretation of analyses for mercury in surface
and ground water and may help predict what will
happen when mercury is added to river or lake
water in waste-disposal processes.
OXIDATION AND REDUCTION BEHAVIOR
Under the usual conditions of temperature and
pressure that occur in river and lake water and wa-
ter-saturated sediment, mercury can be present in
one or more of three different oxidation states. The
most reduced, in a chemical sense, of these forms is
the metal, which is a liquid at ordinary tempera-
tures arid which has a distinct tendency to vaporize.
The other two forms are ionic; the more reduced of
the two ions is the mercurous ion Kg', where the
average valence of mercury is I 1. In oxidizing con-
ditions, especially at low pH, the stable form is the
mercuric ion, Hg!".
Although chemical oxidation does not necessarily
require the presence of oxygen, this element is the
most common oxidizing agent and systems in con-
tact with air tend to be relatively oxidized. In the
absence of oxygen relatively reducing conditions
may become established, permitting the conversion
of elements such as sulfur to the sulfide form. The
intensity of oxidizing or reducing conditions in a
chemical system is usually expressed as an electrical
potential, in volts. The more intensely oxidizing sys-
tems have positive potentials and reducing systems
have, negative potentials. By theoretical chemical
equations, applicable at equilibrium, the potentials
to be expected in water solutions under various
chemical conditions can be calculated. The theoreti-
cal solubility and stability of many elements can be
usefully calculated in a similar way, by considering
the interrelationships of oxidation-reduction equi-
libria and the effects of common anions in forming
various compounds.
CHEMICAL THERMODYNAMIC DATA
Chemical research has provided basic data such
as equilibrium constants, standard electrochemical
potentials, and free energies of formation, for many
of the most significant species of mercury that can
be present in water. Table 191 is a compilation of
chemical equilibrium constants and standard poten-
tials that were taken from published literature. Po-
tentials are given only for redox reactions. Data on
additional species can be obtained from the compila-
tion of Si lien and Martell (1964). These kinds of
data are useful in calculating mercury behavior and
solubilities. Table 20 contains standard free ener-
gies of formation of the mercury species that are
reported in the literature. These permit calculation
of the relative stability of different forms of mer-
cury in aqueous media under a wide range of condi-
tions.
STABILITY AND SOLUBILITY CALCULATIONS
As the data in tables 19 and 20 imply, mercury
forms many solute species. Some of these are com-
plex ions with a high degree of stability. A calcula-
tion of solubility for mercury must take into ac-
count a large number of possible forms. This
situation is further complicated because of the pos-
sible existence of different oxidation states. Mer-
cury in the form of liquid metal is somewhat vola-
tile and can escape from systems open to the
atmosphere, and many mercury compounds are
somewhat volatile also. Mercury forms many strong
organic complexes and is generally much more solu-
ble in organic liquids than in water.
Data from tables 19 and 20 were used to con-
struct the stability-field diagram, figure 4, which
shows the solid and liquid forms of mercury that
will be stable in the conditions of pH and redox po-
1 Tal>Ies are in the buck of the repor".
19
-------
MERCURY IN THE ENVIRONMENT
1.20
Water oxidized
.00
HgCI2 c
.80
.60
HgO c
.40
LU
.00
HgS c
-.20
-40
Water reduced
-.60
-.80
PH
Figuke 4.—Fields of stability for solid (c) and liquid (1) mercury species at 2o°C and 1 atmosphere pres-
sure. System includes water containing 36 ppm C1-, total sulfur 96 ppm as S04"-.
-------
CHEMICAL BEHAVIOR IN AQUEOUS MEDIA
21
tentia'. under which water itself is chemically stable.
The existence of mercuric chloride, calomel, and cin-
nabar depend on the presence of chlorine and sulfur
species in the system. Values arbitrarily selected
are 10~3 moles per liter of each. This concentration
is equivalent to 36 ppm CI" and 96 ppm SOr'-'. No
single value for mercury concentration need be
specified for locating the boundaries. Calculation
techniques used in preparing Eh-pII diagrams have
been described extensively in the literature. Solid
specie;, are identified by the abbreviation "c", gases
"g", liquids by "1", and dissolved species by super-
script plus or minus signs or by the abbreviation
"aq " The calculations are for the standard temper-
ature of 25°C. Effects of temperatures 10 to 15 de-
grees above or below this value are probably small
enough to be ignored for this type of approximate
treatment. Temperature effects may be important in
some systems, however.
At the conditions of pH and Eh likely to occur in
aerated or anaerobic water (pH 5 to 9 and Eh less
than 0.5 volts) the species Hg° liquid and HgS (cin-
nabar) are the principal ones likely to enter into
equilibria affecting the solubility of mercury. The
organcmetallic compound dimethyl mercury for
which a standard free energy value is given in table
20 was considered in preparing the stability field
diagram. Dimethyl mercury is not thermodynami-
cally stable in the system as specified.
The data in tables 19 and 20 can also be used to
calculate the solubility of mercury at equilibrium in
the system of figure 4 and to identify the predomi-
nant solute species at any area of interest in the
diagram. Figure 5 represents the areas of domi-
nance of the solute species that will be stable in the
presence of the same levels of chloride and sulfur
species as specified for figure 4.
Calculations of solubility of the dominant species
also were made in preparing figure 5, and results
are given in a general way on the diagram.
The main features of the aqueous inorganic
chemistry of mercury under equilibrium conditions
are clearly indicated by the two diagrams. Over
much of the area of moderately oxidizing conditions
above j: IT 5 the predominant mercury species in so-
lution is undissociated mercury. The solubility of
this material is nearly constant over the whole area
where the liquid metal is stable, and is relatively
low, absut 25 ppb, as Hg. This represents the likely
upper equilibrium limit of mercury in surface
streams; and lakes that are low in chloride. Studies
of this form of aqueous mercury were made by Par-
iaud and Archinard (1952 ).
Mildly reducing conditions, as are likely to occur
in many lake and streambed sediments, can cause
the mercury to be precipitated as the sulfide, cinna-
bar. This compound has a:n extremely low solubility.
In the fields of Mg< IIS)-: aq and HgS,"3 near neutral
pi I, the equilibrium solubility of mercury may be
lower than .002 ppb. Very strongly reducing condi-
tions, however, may increase the solubility somewhat
by converting the mercuric ion to free metal.
In solutions that are high in chloride the solubility
of mercury in oxygenated water may be greatly in-
creased by the formation of the uncharged HgCl2
complex, or anionic complexes such as IlgClr". The
area of dominance shown for chloride complexes
would be enlarged if chloride had been increased
above 10 molar. Inorganic mercury complexes in
waters in Sweden were reported by Anfalt and
others (1968) to include HgCl.0, IlgOHCP, and
Hg(OH)with predominant forms depending on
chloride concentration and pll. Stability data for the
HgOHCP species were net given by Wagman and
others (1969).
It would appear that mercury concentrations in
stream water could be as high as 25 ppb without
loss by chemical precipitation. It does not seem that
such levels are likely to be common, however, for
various reasons, two of which are;
1. Mercury tends to be volatile and will be lost as
vapor from the water surface exposed to the
air.
2. Most mercury species are much more soluble in
organic solvents than in water. Moser and
Voigt (1957) found, for example, that dis-
solved free mercury was taken up strongly by
organic solvents. When cyclohexane was added
to water that contained metallic mercury, the
ratio of mercury retained in the water to that
in the cyclohexane was only 0.03. This implies
a mechanism for removal of mercury from
water by aquatic organisms and the effect of
organisms is known to be very important.
Mercury that enters reduced sediments can become
relatively immobile, so long as a reasonable degree
of reduction continues to prevail. At high pH, if
much reduced sulfur is present, however, mercuric
sulfide anions can become very soluble.
Complexes of mercuric ions with ammonia are de-
scribed in the literature and some data on one such
complex are given in table 19. This complex is not a
predominant form of mercury unless the solution
-------
MERCURY IN THE ENVIRONMENT
.20
.00
Water oxidized
.80
.60
SOLUBILITY
HIGH
.40
§ .20
LlI
.00
-20
[Hg]=25ppb
-40
-.60
Water reduced
-80
pH
Figure 5.—Fields of stability for aqueous mercury species at 25°C and 1 atmosphere pressure. System includes
water containing 36 ppm Ch, total sulfur 96 ppm as sulfate. Dashed line indicates approximate solubility
of mercury in this system.
-------
CHEMICAL BEHAVIOR IN AQUEOUS MEDIA
23
contains more than 100 ppm of NH4\ a level sel-
dom attained in natural water,
ORGANIC COMPLEXING EFFECTS
The relative importance of organic solute com-
plexes of mercury in the aqueous chemistry of the
element cannot be fully decided at present. The in-
formation on such complex species is incomplete
and some of it is conflicting'. Mercury does form
some very strong organic complexes. Some of these
are relatively soluble in water. Most forms for
which data are readily available, however, might be
expected to be altered to other, more stable and gen-
erally ess soluble, forms in natural water systems.
Nevertheless, the fact that a given organic complex
is not thermodynamically stable should not be used
as a basis for dismissing or ignoring it. Species that
are not at equilibrium are commonly found in natu-
ral wa :er and can be very important factors in the
composition of the solution. Nonequilibrium species
are especially likely to be important in surfrce
streams that are used for disposal of wastes, and
organic, complexes of mercury could be important in
these streams.
A particularly significant question arises in
connection with the organic complex methyl mer-
cury. The liquid dimethyl mercury is reported in
table 20 to have a standard free energy formation
of 33,5 kcal (kilocalories) per mode. This value was
used in the calculations for preparing figure 4. No
region exists in the diagram where Hg{CH::). would
be the most stable phase.
Methyl mercuric ion, HgCH/, is cited in publi-
cations by various authors as the most important
form in fish and various other food products of ani-
mal origin (Westoo, 1967). It has been identified in
cultures of methane-generating bacteria to which
mercuric ions had been added (Wood and others,
1968). Although the literature has been examined
carefully no free-energy value for HgC'II ' could
be found, and no firm basis for calculating or esti-
mating such a value seems to be available. This spe-
cies could not be considered in constructing figure 5.
In the absence of positive information it seems
logical to allow for the possibility of finding methyl
mercury or other organic complexes in natural
water, and these complexes may offer problems to
the analytical chemist,
LIMITATIONS OF THEORETICAL EVALUATION
The summary of aqueous mercury chemistry that
is obtainable from the Eh-pH diagram and related
calculations seems to fit reasonably with what can
be observed in the field. However, there are impor-
tant areas where available information is inade-
quate to permit full acceptance of the theoretical
model without further testing. The frequent depar-
ture of natural systems from equilibrium is well
known, and must be kept in mind when using equi-
librium calculations. There are two aspects of mer-
cury chemistry that are particularly important
sources of departure from what can be predicted
theoretically. One of these, the formation of organic
complexes and participation of mercury in biochem-
ical processes has been mentioned already. How-
ever, it has not been proved conclusively that
methyl mercury is produced in abundance in sedi-
ment by bacterial activity; the energy that the orga-
nisms would have to expend is large, which is con-
trary to most metabolic processes.
A second property of importance is the tend-
ency for mercury to participate in dismutation
reactions—that is, in reactions of the type
H«v" tig'* : Hg*". This and similar reactions are
well known, and provide a means whereby mer-
cury could be converted to the liquid form and es-
cape as vapor. The oxidation and reduction reac-
tions of mercury seem to be less inhibited by energy
barriers than those for many other elements, and
the course of such reactions may be difficult to pre-
dict at times. The combination of oxidized mercuric
ion with the reduced sulfide ligand to form cinna-
bar, for example, is an unusual feature and seems
to give a high degree of immobility to mercuric
mercury in a reduced environment where it would
not normally be expected to occur at all.
Thus, although a good beginning toward under-
standing of the aqueous chemistry of mercury has
been made, a considerable amount of basic research
is still needed, especially on rates and mechanisms
of reaction and on the behavior of organic mercury
complexes.
REFERENCES CITED
Anfatt, Torbjorn, Dyrssen, David, Ivanova, Elena, and Jag-
ner, Daniel, 1968, State of divalent mercury in natural
waters; Svensk Kem. Tidsskr., v. 80, no. 10, p. 340-342.
Helgeson, H. C., 1969, Thermodynamics of hydrotherrnal sys-
tems at elevated temperatures and pressure: Am. Jour.
Sci., v. 267, p. 729-804.
Latimer, W. M., 1052, Oxidation potentials: Englewood
Cliffs, N. J., Prentice-Hall, Inc., 852 p.
Moser, H. C., and Voigt, A. P., 1957, Dismutation of the
mercurous dimer in dilute solutions: Am, Chem. Soc.
Jour., v. 79, p. 1837.
Pariaud, J, C,, and Archinard, p., 1952, Sur la solubilite des
metaux dans 1'cau: Soc. Chim, France Mem. 99, p.
454-456.
-------
24
MERCURY IN THE ENVIRONMENT
Silien, L. G,, and Martell, A. B,, 1964, Stability constants of
metal-ion complexes [2d ed,]: Chcm. Soc. [London]
Spec, Pub. 17, 754 p.
Wag-man, D, D„ Evans, W. H„ Parker, V. B., Harlow, I.,
Bailey, S. M., and Schumm, R. H,, 1968, Selected values
of chemical thermodynamic properties: Natl. Bur,
Standards Tech. Note 270-3, 264 p.
1969, Selected values of chemical thermodynamic
properties: Natl. Bur. Standards Tech. Note 270-4, 141
p.
Waiig-h. T. D,, Walton, H. F., and Laswick, J. A., 1955, Ioni-
zation constants of some organomereuric hydroxides and
halides: Jour, Phys. Chemistry, v. 59, no. 5, p. 393-399.
Westoci, Gunnel, 1967, Determination of methylmercury com-
pounds in foodstuffs; 2, Determination of methylmer-
cury in fish, egg, meat, and liver: Acta Chem.
Scandinavica, v, 21, no. 7, p. 1790-1800.
Wood, J. M., Kennedy, F. S,, and Rosen, C. G., 1968, Syn-
thesis of methylmercury compounds by extracts of a
methanogenic bacterium: Nature, v. 220, no, 5163, p.
173-174.
-------
MERCURY CONTENTS OF NATURAL THERMAL AND MINERAL FLUIDS
Bv D. E. White, M. E. Hinkle arid Ivan Barnes1
VOLCANIC FUMAROLES
Data on mercury contents of fumaroles are lack-
ing because of the rarity of volcanic eruptions and
high-temperature fumaroles and, until recently, the
lack of adequate methods of analysis. Hawaiian and
Alaskan fumaroles should be studied.
GASES
Water condensed from volcanic fumaroles was
analyzed by Aidin'yan and Ozerova (1966) and was
found to contain 0.3-6 ppb mercury. Fumaroles of
the lowest temperature (~100°C) contain the least
mercury (?s0.3 ppb) ; at 220°C, the mercury con-
tent is about 1.5 ppb, and at 270°C, it is about 6
ppb. Residual gases (not condensed in water) con-
tain 3xl0"7 to 4 x 10~B g/m3 (grams per cubic
meter) of gas.
SUBLIMATES FROM FUMEROI.F.S
Sublimates are commonly more enriched in mer-
cury than is vapor; reported contents range from
about 10 to >10,000 ppb (Aidin'yan and Ozerova,
1966). Native sulfur, sulfates, and ammonium
chloride have the highest reported mercury con-
tents.
HOT SPRINGS
The relationships of hot springs to mercury de-
posits have been studied by Brannock (1948),
White (1955, 1967), White and Roberson (1962),
and Dickson and Tunell (1968). Some springs of
special interest are also discussed by Barnes
(1970). Efforts to determine the mercury contents
of the fluids of these springs were not notably suc-
cessful until 1966, when effective analytical methods
were developed by the U.S. Geological Survey
(Vaughn, 1967; Hinkle and Learned, 1969).
We have recently analyzed thermal and mineral
waters by amalgamating mercury on silver in acid
solution. The silver-mcrcury amalgam was heated in
an induction furnace and the mercury vapor deter-
mined in a mercury vapor detector by photo absorp-
1 Incoi pora-tes data from W. W. Vaughn, Howard McCarthy, F. N.
Ward, and R. O. Fournier and background data from the literature, mainly
Russian.
tion. The detection limit is 0.01 ppb. The results are
given in table 21.2
CASKS
The hot spring gases at Coso Hot Springs, Calif.,
have been shown to be enriched in mercury (f)upuy,
1948; White, 1955; Dickson and Tunell, 1968), but
concentrations were not determined precisely. Su-
perheated steam from steam wells at The Geysers,
Calif., contains a measurable amount of mercury.
An early analysis of condensed steam showed a con-
tent of 130 ppb Hg (White, 1967, p. 590), but this
value is almost certainly too high. Condensed steam
from the McKinley steam field at Castle Rock
Spring, Lake County, Calif., contains 1 to 3 ppb
mercury (table 21). The mercury content of hot-
spring gases is not adequately known and needs de-
tailed study.
WATERS
R. L. Wershaw, in this report, summarizes data
that suggest that the natural mercury content of
unpolluted rivers in areas where the rocks have a
normal mercury content is less than 0.1 ppb. The
mercury contents of water closely associated with
mercury deposits, reported prior to 1966, are sum-
marized by White (1967). Although various analyti-
cal procedures were used, these values are probably
much too high—they range from <20 ppb (stated
detection limit) to 400 ppb. In contrast, recent anal-
yses of the same type of water range from <0.05 to
20 ppb mercury.
Tentative generalizations on mercury contents re-
ported from the thermal and mineral waters of the
northern California Coast Range are: (1) Waters
that are low to moderate in salinity (<5,000 ppm
total solids) and in temperature (<40°C) are
nearly always low in mercury (<0.05 ppb) ; (2)
cool waters of high salinity tend to have higher
mercury concentrations (table 21) such as 0.1 ppb
(Salt Spring north of Wilbur Springs) and 1.5 ppb
2 Tables are in the back of the report.
25
-------
26
MERCURY IN THE ENVIRONMENT
(Complexion Spring") ; (3) hot, dilute waters (table
21) are low in mercury; (4) the hot, moderately sa-
line waters (table 21) of Sulphur Bank and the
warm saline Wilbur Springs contain about 1.5 ppb
mercury; (5) the mercury content of most of these
waters exceeds the contents obtained by the U.S.
Geological Survey for relatively unpolluted river
waters. (See R. L. Wershaw, "Sources and behavior of
mercury in surface waters," this report.) Solid
materials (table 21) depositing from the fluids seem
to retain mercury.
Aqua de Ney Spring of Siskiyou County, Calif., is
remarkable for its high salinity, pH, and sulfide
content (Feth and others, 1961); its mercury con-
tent is 20 ppb (J. H. McCarthy, written comm.,
1966) but no mercury minerals have been identified.
The silica-magnesia gel deposited from Aqua de
Ney contains 500 ppb mercury. In contrast, the cin-
nibar-depositing Amedee Springs of Lassen County,
Calif., contain only 2 ppb mercury (J. H. McCarthy,
written comm., 1966).
Mercury contents are reported in table 22 for 17
thermal waters in Yellowstone National Park,
Wyo., which is an area that has been affected by ex-
treme volcanic activity of Pleistocene age, with
present total heat flow of at least 80 times the
world average. The thermal waters have relatively
low disolved solids content but are high in tempera-
ture. Mercury contents of water of the major gey-
ser basins are all close to 0.1 ppb; Cinder Pool in
Norris Basin has the highest content, 0.28 ppb. The
Sylvan Springs area in Gibbon Basin, Yellowstone
National Park, has higher mercury contents than
most other Yellowstone National Park waters; four
analyses range from 0.2 to 0.3 ppb,
PRECIPITATES FROM THERMAL FLUIDS
Cinnabar and metacinnabar are precipitating
from the thermal waters of Sulphur Bank and Ame-
dee Springs, Calif., Steamboat Springs, Nev., and
Boiling Springs, Idaho (White, 1967; Dickson and
Tunell, 1968). Sulphur Bank is the most remarkable
of the four, having produced more than 5,000 tons of
mercury before mining operations ceased, which is
the highest yield in the world from a deposit clearly
formed from hot springs (White and Roberson,
1962). According to White (1967) only a little cin-
nabar is precipitating from vapor escaping from
natural vent areas of The Geysers geothermal steam
system of California. No mercury minerals have
been recognized in Yellowstone National Park
thermal spring precipitates.
Precipitates and bottom sediments in many hot
springs, even where no mercury mineral is evident,
contain quantities of mercury much above the aver-
age content for crustal rocks, (Michael Fleischer,
this report), which provides evidence for mercury
transportation and concentration from the associated
fluids. Reported contents of mercury-enriched sedi-
ments in addition to those in table 21 include:
Steamboat Springs, 12,000, 150,000, 200,000 and
500,000 ppb; elemental sulfur "cinders" of Cinder
Pool, Norris Basin, Yellowstone National Park,
50,000 ppb; and silica from Primrose Spring of Syl-
van Springs, Gibbon Basin, Yellowstone, 5,000 ppb;
and elemental sulfur precipitated from condensed
steam of P.G.
-------
NATURAL THERMAL AND MINERAL FLUIDS
27
combines with II S from "sour" gases of other oil
fields and is precipitated in the pipelines. Native
mercury separates from the crude oil at the local
pumping station. Total mercury yield from all the
fluids is unrecorded from the field but may be in the
order of hundreds of tons.
Petroleum and tarry residues containing mercury
(table 23) are associated with the mercury deposits
of the Wilbur Springs district. Light petroleum of
the "froth veins" of the Abbott mine (White, 1967)
contained 100,000 ppb mercury. Tarry petroleum,
probably residual from loss of the lighter hydrocar-
bons, contained 500,000 ppb. Hydrocarbons ex-
tracted from fault gouge from the Abbott mine by
organic solvents contained 1,000 to 5,000 ppb, but a
sampU of petroleum that had flowed from a new
underground working and was stored for several
years prior to analysis contained only 300 ppb. Tar
from "iie nearby Wilbur oil test well (table 23) con-
tained 1,000 ppb mercury.
Some additional evidence for enrichment of mer-
cury in fluid hydrocarbon deposits is indicated by the
mud volcanoes of the Kerch-Taman territory of the
U.S.S.R. (Karasik and Morozov, 1966). Mud and
other debris that were extruded with hydrocarbon
gases and waters of the oil-field type are enriched
in mercury by about 100 times the mercury con-
tents of Tertiary argillaceous rocks.
SUMMARY
Dilute thermal springs contain readily detectable
mercury. The springs include high-temperature wa-
ters of Yellowstone National Park, which are
closely associated with extensive Pleistocene volcan-
ism. Some California thermal waters, and nonther-
mal waters of appreciable salinity (>5,000 ppm
total diselved solids) but not closely associated with
volcanism, contain mercury in the range of 1 to 3
ppb, concentrations notably higher than Yellow-
stone National Park waters. Sediments associated
with some of these springs are rich in mercury,
containing about 50 to 5,000 times the mercury con-
tent of ordinary rocks (Fleischer, this report), and
the mercury contained is presumed to have been
transported by the spring water.
Of the natural fluids examined, petroleum and es-
pecial'y the tarry residues of petroleum contain the
highest determined mercury contents; available
analyses show a range from 300 to 500,000 ppb or
from about four to six orders of magnitude above
most thermal waters. In the formation of some mer-
cury deposits, petroleum and hydrocarbon gases ap-
parently played a role, but the origin and nature of
the fluids that have formed most large mercury de-
posits are not yet clearly understood. Our data are
incomplete for hot spring- and volcanic gases, espe-
cially in view of anomalous contents of mercury in
associated solid phases which indicates vapor trans-
port.
REFERENCES CITED
Aidin'yan, N. Kh.. and Ozerova, N. A., 1966, Behavior of
mercury in recent volcanism: Sovrem. Vulkanizm, v. 1,
p. 249-253.
Bailey, E. H.. Suavely, P. D,, Jr., and White, D. E., 1961,
Chemical analyses of brines and crude oil, Cymric field,
Kern County, California, in Short papers in the geologic
and hydrologie sciences: U.S. Geol. Survey Prof. Paper
424-D, p. D306-B3Q9.
Barnes, Ivan, 1970, Metamorphie waters from the Pacific
tectonic belt of the west coast of the United States: Sci-
ence, v. 168, no. 3934, p. 973-975.
Brannock, W. W,, 1948, Preliminary geochemieal results at
Steamboat Springs, Nevada: Am, Geophys. Union
Trans., v, 29, no. 2, p. 211-226.
Dall'Aglio, Mario, Roit, R. da, Orlandi, C., and Tonani,
Franco, 1966, Prospeziono geochimica del rr.emirio; dis-
tribuzione del mereurio rtelle alluvium del la T oscana:
Industria Mineraria, v. 17, no. 9, p. 391-398.
Dickson, F, W., and Tunell, George 1968, Mercury and anti-
mony deposits associated with active hot springs in the
Western United States, in Ridge, J, D., ed., Ore deposits
of the United States, 1933-1967 (Graton-Sales volume),
volume 2: Am. Inst, Mining, Metall., and Petroleum En-
gineers, p. 1673-1701.
Dupuy, L. W., 1948, Bucket-drilling the Coso mercury de-
posit, Inyo County, California: U. S. Bur. Mines Rept.
Inv. 4201, 45 p.
Feth, J. H., Rogers, S. M., and Roberson, C. E., 1961, Aqua
de Ney, California, a spring of unique chemical charac-
ter: Geochim. et Cosmochim. Acta, v. 22, nos. 2—4, p.
75-86.
Hinkle, M. E., and Learned, R. E., 1969, Determination of
mercury in natural waters by collection on silver
screens, iv Geological Survey research 1969: U.S. Geol.
Survey Prof. Paper 650-D, p. "D251-D254 [1970],
Karasik, M. A., and Morozov, V. I,, 1966, Distribution of
mercury in the products of mud volcanoes of the
Kereh-Tamin' province; Geokhimiya, no. 6, p. 668-678.
Spencer, J. N., and Voight, A. P., 1968, Thermal dynamics
of the solution of mercury metal, 1. Tracer determina-
tions of the solubility in various liquids: Jour. Phys.
Chemistry, v. 72, no. 2, p. 464-474.
Vaughn, W. W., 1967, A simple mercury vapor detector for
geochemieal prospecting: U.S. Geol. Survey Circ, 540, 8 p.
White, D. E., 1955, Thermal springs and epithermal ore de-
-------
MEECUEY IN THE ENVIRONMENT
posits, in Part 1 of Bateman, A, M., ed., Economic geol-
ogy, 50th anniversary volume, 1905-1955: Econ. Geology
Publishing Co., p. 99-154.
—1967, Mercury and base-metal deposits with associated
thermal and mineral waters, t'n Barries, H. L., ed., Geo-
chemistry of hydrothermal ore deposits: New York,
Holt, Binehart, and Winston, Inc., p. 575-631.
White, D. E,, Muffler, L. J. P., and Truesdell, A, H., 1970,
Vapor-dominated hydrothermal systems compared with
hot-water systems; Econ. Geology (in press).
White, D, E.. and Tloberson, C. E., 1962, Sulphur Bank, Cali-
fornia, a major hot-spring quicksilver deposit, in Petro-
logic studies—A volume to honor A. F. Buddington:
Geol. Soc. America, p. 397-428.
-------
J
SOURCES AND BEHAVIOR OF MERCURY IN SURFACE WATERS
By R. L. WEKSHAW
NATURAL LEVELS OF MERCURY IN
SURFACE WATERS
Befcre one declares a water body polluted with
waste mercury from man's activities, it is necessary
to knotv the natural background level of the metal.
The drta in table 24: were obtained on water sam-
ples collected for this purpose by district offices of
the U.S. Geological Survey, in cooperation with the
Federal Water Quality Administration, during May,
June, and July 1970. These samples were analyzed
for dissolved mercury using a silver wire atomic ab-
sorpticn method discussed by F. N. Ward (this re-
port) . The 73 samples, representing surface waters
in 31 states, range in concentration from less than
0.1 to 17 ppb. Of the total, 34 contained less than
the de:ectable concentration (0.1 ppb). Of the re-
mainder, 27 samples ranged from 0.1 to 1.0 ppb and
10 samples ranged from 1.0 to 5.0 ppb. Only two
samples contained more than 5.0 ppb, the Public
Health Service limit for potable water supplies. The
fact that many of the samples were taken in areas
of suspected mercury contamination would appear
to indicate that mercury concentrations in surface
waters generally do not exceed tolerable limits ex-
cept in the immediate vicinity of waste outfalls.
Table 25 shows that the mercury levels measured
in surface waters in other parts of the world gener-
ally fall in the same low range of values as found in
the United States. For example, studies of
Dall'Aglio (1968), Heide, Lere, and Bohm (1957),
and of Stock and Cucuel (19S4) show that natural
mercury contents of unpolluted rivers in areas
where mercury deposits are not known, are less
than 0.1 ppb; this is in general agreement with data
presented in table 24 for U.S. rivers.
Samples- from rivers draining mercury deposits
are known to have natural mercury contents exceed-
ing 5 ppb. Kvashnevskaya and Shablovskaya (1963)
found mercury minerals in the suspended particu-
late matter of the Yagnob-Dar'ya River 15 to 35
1 Tables are in the back of the report.
kilometers downstream from mercury ore deposits.
Dall'Aglio (1968) measured mercury concentrations
as high as 136 ppb in Italian rivers which drained
basins having worked and unworked mercury de-
posits (table 25). Mercury concentrations in these
waters were found to decrease as a function of dis-
tance downstream from the mercury deposit. Oil
field brines as well as thermal and mineral fluids in
general (D. E. White and others, this report) and
Karasik, Gomeharov, and Vosilevskaya (1965) may
contain high mercury concentrations which can be a
source of pollution to surface and ground waters.
The fact that the oceans contain an estimated 50
million metric tons of mercury suggests that small
amounts of the element always have been present in
surface water's.
INDUSTRIAL PRODUCTION
The potential for waste mercury contamination of
surface waters can be judged in part from a study
of the use pattern of mercury by industry. The
world production of mercury in 1968 was 8,000
metric tons, of which the United States produced
only 1,000 metric tons from mines located princi-
pally in California, Nevada, Idaho, and Oregon. The
United States imported 860 metric tons of mercury
in 1968 so that together with imports and seven hun-
dred tons of reclaimed mercury domestic use
amounted to about 2,500 metric tons during that
year. During the period 1930-70, the total mercury
mined in the United States was 31,800 metric tons
and 39,600 metric tons were imported. It is estimat-
ed that as much as 25 percent of this total may have
been leaked to the environment.
INDUSTRIAL USES
Table 26 gives data for mercury consumption by
various users in the United States during the calen-
dar year 1969. The largest commercial consumption
occurred in the manufacture of chlorine and caustic
soda, a process thought to introduce appreciable
amounts of waste mercury in to the environment.
For example, Lofroth and Duffy (1969) estimated
29
-------
30
MERCURY IN THE ENVIRONMENT
that eight chlorine factories in Sweden lose from 25
to 35 metric tons of mercury per year. Mercury
losses from such operations have been reported in
the United States (Chemical and Engineering News,
1970a) although considerable effort now is being
made to reduce their losses of mercury (Chemical
and Engineering News, 1970b).
The second largest consumptive use of mercury is
in the manufacturing of electrical apparatus. Mer-
cury also finds very widespread use as a fungicide,
bacteriacide, and slimicide. For example, the paint
industry uses phenyl mercuric compounds for mil-
dew-proofing and mercury organic compounds are
used as seed dressings in agriculture. Mercury com-
pounds are also used in the paper industry to pre-
vent fungal growth in stored pulps and to prevent
the growth of slimes in machinery. Because of this,
some papers are not used in food packaging (Lutz
and others, 1967). Mercury compounds also are em-
ployed to a limited extent as catalysts in the pro-
duction of many organic materials in pharmaeuti-
cal and dental preparations, and, because of its
conductive properties in the liquid state, in a vari-
ety of industrial control instruments.
INDUSTRIAL POLLUTION
The wide variety of uses of mercury by man has
resulted in significant mercury pollution of natural
water bodies in many parts of the world. If in-
dustrial outfalls are not properly scavenged for
mercury, or if mercury-bearing materials are im-
properly disposed of, some of the waste inevitably
finds its way into surface waters. For example, An-
derssen (1967b) measured mercury concentrations
of 6 to 29 ppb (dryweight) in sludge from Swedish
sewage-treatment plants. Obviously, care must be
exercised in the disposal of such sludge to avoid
contaminating water resources.
During the summer of 1970, the U.S. Geological
Survey analyzed more than 500 water samples rep-
resentative of industrial effluents and outfalls where
mercury contamination was suspected. This work
was done in cooperation with the Federal Water
Quality Administration. Of the more than 500 sam-
ples, 28 percent had Jess than detectable (0.1 ppb)
mercury concentrations; an additional 55 percent
contained between 0.1 and 5 ppb. In other words, 83
percent of all the samples analyzed had concentra-
tions which were within the range of Public Health
Service mercury content allowable for drinking
water supplies despite the fact they represented in-
dustrial areas. An additional 12 percent of the sam-
ples had mercury contents ranging between 5 and
100 ppb. Less than 5 percent had concentrations
greater than 100 ppb and only two samples of the
total had concentrations greater than 10,000 ppb.
Sediment samples from the Missouri River basin
were also analyzed for mercury content. Of the 15
samples studied, 11 had mercury contents ranging
between 40 and 170 ppb. The remaining four had
concentrations of 900, 1,800, 3,000, and 32,000 ppb.
CONCLUSIONS
Natural surface waters contain tolerably small
concentrations of mercury except in areas draining
mercury deposits. Industrial, agricultural, scientific,
and medical uses of mercury and mercury com-
pounds introduce additional mercury into surface
waters. Whatever its source, the concentration of
mercury compounds, dissolved or suspended, is re-
duced rapidly by sorption and by complexing reac-
tions with clays, plankton, colloidal proteins, humic
materials, and other organic and inorganic colloids
(J. D. Hem, E. A. Jenne, this report.) These reac-
tions tend to keep the concentration of dissolved
mercury at levels near the normal background ex-
cept at points of actual mercury discharge.
SELECTED REFERENCES
Aidin'yan, N. Kh,, 1982, Content of mercury in some natural
waters: Trudy Inst. Geol. Rudii. Mestorozhd., Petrog,,
Mineraiog. i Geokhim., no. 70, p. 9-14; Chem. Abs., v.
57, no. 16.3."!6e,
1963, The mercury contents of some water in the Ar-
menian S.S.R,: Izv. Akad. Nauk Arm, SSR, Geol. i
Geogr. Nauki, v. 16, no. 2, p. 73-75; Chem. Abs., v. 59
no. 7237b.
Aidin'yan, N. Kh., and Relavskaya, G. A., 1963, Supergene
transfer of mercury: Trudy Inst. Geol. Rutin. Mesto-
rozhd., Petrog-., Mineraiog. i Geokhim,, no. 99, p. 12-15;
Chem. Abs., v. 59, no. 8471e.
Aiiderssen, Arne, 1967a, Mercury in the soil: Grundforbat-
tring, v. 20, nos, 3-4, p. 95-105; Chem. Abs., v. 69, no,
5X226j.
1967b, Mercury in decayed sludge: Gruridforbattring',
v. 20, nos. 3-4, p. 149-150; Chem. Abs., v. C9, no.
45867d.
Chemical and Engineering News, 1970a, Mercury stirs more
pollution concern: v, 48, no. 26, p. 36-37.
—1970b, Mercury—Widespread spillage: v. 48, no. 29, p.
15.
Dall'Aglio, M., 1968, The abundance of mercury in 300 natu-
ral water samples from Tuscany and Latium (central
Italy), in Ahrens, L. H., eel., Origin and distribution of
the elements—A symposium, Paris, 1967: New York,
Pergamon Press, p. 1065-1081.
Hamaguchi, Hiroshi, Kuroda, Rokuro, and Kyoiclii, Hoso-
hara, 1961, Photometric determination of traces of mer-
cury in sea water: Nippon Ka.sniku Zasshi, v, 82, p.
347-349: Chem, Abs., v. 55, no, 15222c.
-------
SOURCES AND BEHAVIOR IN SURFACE WATERS
31
Heide, Fritz, Lerz, H., and Bohm, G., 1957, Gehalt des
Saale-wassers an Blei und Quecksilber [Lead and mer-
cury content of water from the Saale River] : Naturwis-
sensehaften, v, 44, no. 16, p. 441-442.
Hosolu.ra, Kyoichi, 1961, Mercury content of deep-sea water:
Nippon Kagaku Zasshi, v. 82, p. 1107-1108; Chem,
Abs., v. 56, no. 4535d.
Hosohara, Kyoichi, Kozuma, Hirotaka, Kawasaki, Katauhiko,
and Tsuruta, Tokumatsu, 1961, Total mercury content
in sea water: Nippon Kagaku Zasshi, v. 82, p.
1479-1480; Chcm, Abs., v. 56, no. 5766h.
Jensen, S,, and Jernelov, A., 1969, Biological methylation of
mercury in aquatic organisms: Nature, v. 223, no. 5207,
p. 753-754.
Karas'k, M. A., Goncharov, Yu. I., and Vasilevskaya, A. Ye,,
1965, Mercury in waters and brines of the Permian salt
deposits of Donbas: Geokhimiya, no. 1, p. 117-121.
Kvashnevakaya, N. V.. and Shablovskaya, Ye. I., 1963, An
investigation of metal content in the suspended load of
streams: Akad. Nauk SSSR Doklady, v. 151, no. 2, p.
426-429.
Lofroth, Goran, and Duffy, M. E,, 1969, Birds give warning:
Environment, v. 11, p. 10-17.
Lutz, G. A., Gross, S. B,, Boatman, J. E,, Moore, P. J.,
Darby, R. L„ Veazie, W. H,, and Butrico, F. A., 1967,
Design of an overview system for evaluating the pub-
lic-health hazards of chemicals in the environment: Co-
lumbus, Ohio, Battelle Memoiral Inst. Test-case studies,
v. 1, p. A1-A38.
National Materials Advisory Board, 1969, Trends in usage
of mercury—Report of the panel on mercury, Committee
on technical aspects of critical and strategic materials:
Washington, Natl. Research Council-Natl. Acad. Sci.-
Natl. Eng. Pub. NMAB-258, 37 p. [For sale by Clear-
inghouse for Federal Sci, and Tech. Inf.]
Reutov, O. A., and Beletskaya, I. P., 1968, Reaction mecha-
nisms of organometallic compounds: Amsterdam,
North-Holland Publishing Co., 466 p.
Stock, Alfred, and Cucuel, Friedrich, 1934, Die Verbreitung
des Quecksilbers [The occurrence of mercury]: Natur-
wissenschaften, v. 22, no. 22/24, p. 390-393; Chem. Abs.,
v. 28, no. 7086,
Wood, J, M., Kennedy, F. S , and Rosen, C. G., 1968, Syn-
thesis of methyl-mercury compounds by extracts of a
methanogeme bacterium: Nature, v. 220, no. 516S, p.
173-174.
Zautashvili, B. Z., 1966, Problem of mercury hydrogeochem-
istry (as illustrated by the mercury deposits of Ab-
khasia) [in Russian]: Geokhimiya, no. 3, p. 357-362;
Chem. Abs., v. 64, no. 17267.
-------
BIOLOGICAL FACTORS IN THE CHEMISTRY OF MERCURY
By Phillip E. Greeson
FLOW OF MERCURY THROUGH AQUATIC
FOOD CHAINS
The living organisms in an aquatic, community
represent an assemblage of groups, called trophic-
levels, that are classified according to food utiliza-
tion. The size of an aquatic community is dependent
upon the availability of food materials and its
transport through the various groups.
The ultimate basic food substances are the inor-
ganic materials dissolved in the water or the insolu-
ble materials that can be readily converted to bodily
needs. The chlorophyll-bearing phytoplankton and
higher plants are the principal organisms for con-
version of these ultimate basic materials to living
matter. They, therefore, are called the primary
producers of the system and all other organisms de-
pend upon their existence.
Those organisms that feed upon the plants, such
as zoopiankton, insects, snails, and small fish, are
known as primary consumers. Secondary consumers
feed upon the primary consumers and are repre-
sented by the larger fish, such as trout, pike, bass,
and salmon. Every organism in an aquatic commu-
nity may, by death and decomposition, contribute di-
rectly to the dissolved materials, or may be con-
sumed as food by other organisms. Micro-organisms
are responsible for the breakdown of organic
materials and the releasing of dissolved substances
for reuse. Figure G is a simplified representation of
the flow of materials through, an aquatic food chain.
Although mercury is not considered to be an es-
sential food material for organisms, it is incorpo-
, Bacteria.
^Phytoplankton \
//
Dissolved ---'
substances\
.•Zooplcmkton'
Small fish^
¦ Insects
Large fish
'Higher plants » Herbivores'
Figure 6. -Simplified representation of the flow of materials
through an aquatic food chain.
rated into the body of the organism by virtue of its
presence in the water. Mercury in living tissues is
believed to be largely organic and primarily methyl
mercury (Westoo, 1967). -Jenson and Jernelov
(1969) indicated that much of the inorganic and or-
ganic mercurial wastes from industrial eilluents are
converted by anaerobes into methyl mercury,
CH.Hg4", or dimethyl mercury, i''!I ) I!>•:. This find-
ing was confirmed by Wood, Kennedy, and Rosen
(1968), who stated that the methvlation of mercury
is due to bacterial activity. The latter authors con-
cluded that, dimethyl mercury is the ultimate prod-
uct but that in situations where an excess, of mer-
curic ion Hg^-) exists, methyl mercury is also
produced.
Dimethyl mercury, although stable in alkaline so-
lutions, dissoc.ia1.es to ionic methyl mercury at low
pll values. Such low pll conditions may sometimes
exist in the anaerobic bottom muds of streams and
lakes. Methyl mercury, being soluble in water, is
available for incorporation into the body tissues of
organisms in the aquatic environment and secondar-
ily into terrestrial predators, such as man. Methyl
mercury tends to concentrate in living tissue and at
critical concentration can be extremely toxic.
The concentration of mercury by living things
may come by way of the food chain or by direct as-
similation from the surrounding medium (Rucker
ancl Amend, 1969). In either event, when mercury
is introduced into a food chain, it becomes available
to fill organisms of the chain.
TOXICITY
Mercury compounds inhibit the growth of bacte-
ria, thus their longstanding use as antiseptics and
disinfectants. It is to be expected, therefore, that at
some concentration mercury compounds added to a
natural water system will have a deleterious effect
on the bacteria of the system. Mercuric chloride at
a concentration of 610 ppb was reported by Her-
mann (1959) to cause a 50-percent decrease in the
5-dav utilization of oxygen by sewage. Ingols
32
-------
BIOLOGICAL FACTORS
(1954) reported that a concentration of 2,000 ppb
results in complete baeteriostasis. The toxicity of
mercury to various aquatic organisms is shown in
table 27 (in the back of the report).
Mercury in the aquatic environment also is
known to have acute effects on the primary produ-
cers, but there is not complete agreement on toxic
levels. Studies by North and Clendenning (1958)
and Clendenning and North (1960) indicated that
100 ppb of mercuric chloride caused a 50-percent
inactivation of photosynthesis in the giant kelp Ma-
crocysiis pyrifera during a 4-day exposure. A con-
centration of 500 ppb caused a 15-percent decrease
in photosynthesis in 1 day and complete inactiva-
tion in 4 days.
UMes (1962) reported 0.6 ppb of ethyl mercury
phosphate as the threshold concentration for inhib-
iting the growth of marine phytoplankton and that
60 ppb was found to be lethal to all marine spe-
cies. Burrows and Combs (1958) concluded that
ethyl mercury phosphate was an effective algicide at
1,000 ppb. In contrast, Ilueper (1960) reported that
the threshold of lethal concentrations of mercury
salts for phytoplankton ranged from 900 to 60,000
ppb.
Cler denning and North (1960) reported that
mercury was found to be more toxic to aquatic or-
ganisms than copper, hexavalent chromium, zinc,
nickel, or lead. Corner and Sparrow (1956) empha-
sized that the toxic effects of mercury salts are in-
creased appreciably by the presence of copper.
Glooschenko (1969) showed that the accumula-
tion o:f mercury by the marine diatom Chaetoceros
costatum, was largely by passive surface adsorption
with limited uptake by metabolic processes. He
stated that it is not important whether the primary
producers concentrate mercury by active uptake or
by passive surface adsorption in the transfer to
higher trophic levels.
Glooschenko's studies of mercury accumulation il-
lustrate an important ecological principle. Aquatic
organisms, as well as man, will concentrate mercury
withir. their bodies when the intake rate exceeds the
elimination rates. The result, under these condi-
tions, is a buildup with time to the extent that the
accumulated mercury can become toxic and, eventu-
ally, lethal.
Bueker and Amend (1969) studied the accumula-
tion of mercury in fish. They exposed rainbow
trout, Salm.o gairdneri, for an hour a day to nonle-
thal concentrations of ethyl mercury phosphate.
After 10 days, several fish were sacrificed, and their
38
tissues were analyzed fcr mercury. The results
showed the following concentrations in the tissues:
Ti.-wue Mercury (ppb)
Blood 22,800
Kidney 17,300
Liver 16,700
Brain 10,100
Gonad 4,100
Muscle 4,000
The remaining fish were maintained in mercury-
free water. The authors found that after 45 weeks,
mercury had been eliminated from all tissues except
the liver and kidney, where concentrations had sta-
bilized at 1,800 and 12,300 ppb respectively.
MERCURY POISONING IN MAN
The toxic effects of waterborne mercury to man
were emphasized during the early 1950's when
about 50 persons out of more than 100 affected in
Japan died of the strange "Minamata Disease." Ex-
tensive investigations revealed that the deaths were
caused by the consumption of mercury-contami-
nated fish and shellfish obtained from Minamata
Bay. The bay had received large amounts of methyl
mercury compounds in the waste effluents from a
plastics factory (Kurland and others, 1960). Simi-
lar mercury contamination of fish has been reported
in Sweden and recently in several places in North
America, particularly Lake St. Claire.
As a result of these findings a tentative upper
limit of 5.0 ppb of mercury in drinking water has
been proposed by the U.S. Public Health Service
and the same upper limit set in the U.S.S.R. The
maximum is thought to be safe for human health
when the total probable mercury intake rates of
physiological processes, and excretion rates are
taken into account. The U.S. Food and Drug Ad-
ministration has declared that fish and other foods
which contain more than. 500 ppb of mercury are
unsafe for human consumption,
REFERENCES CITED
Burrows, Ii, E., and Combs, B. 1)., 1958, Lignasan as bacte-
ricide and alg-aeririe: Prog. Fish Culturist, v. 20, p.
143—115,
Clendenning, K. A., and North, W, J., 1960, Effects of
wastes on the giant kelp, Macroeystix pyrifera, in Pear-
son, E. A., ed,, International conference on waste dis-
posal in the marine environment, 1st, Berkeley, Calif.,
1959, Proceeding's: Pergamon Press, v. 1, p. 82-91.
Corner, E. D. S., and Sparrow, B. W„ 1956, The modes of
action of toxic agents; Poisoning of certain crusta-
ceans by copper and mercury; Marine Biol. Assoc.
United Kingdom Jour., v, 35, p. 531-548.
Glooschenko, W. A., 1969, Accumulation of mereury-203 by
-------
34
MERCURY IN THE ENVIRONMENT
the marine diatom Chaetoceros costatum: Jour. Phycol-
ogy, v. 5, no. S, p. 224-226.
Hermann, E. R., 1959, A toxicity index for industrial
wastes: Indus, and Eng. Chemistry, v. 51, no. 4, p.
84A-87A.
Hueper, W. C., 1960, Cancer hazards from natural and arti-
ficial water pollutants, in Conference on physiological
aspects of water quality, Proceedings: Washington,
U.S. Public Health Service, p. 181—193.
Ingols, R. S., 1854, Toxicity of mercuric chloride, chromium
sulfate, and sodium chromale in the dilution B.O.D.
test: Sewage and Indus. Wastes, v, 26, p. 536.
Jenson, S. R., and Jernelov, A., 16G9, Biological methylation
of mercury in aquatic organisms: Nature, v. 223, no.
5207, p. 753-75-1.
Kuriand, L. T., Faro, S. N., and Siedler, H. S., 1960, Mina-
mata disease: World Neurologist, v. 1, p. 320-325.
North, W. J., and Clendenning, K. A., 1958, The effects
waste discharges on kelp—Annual progress report: La
Jolla, California Univ. Inst. Marine Resources, IMR
Ref, 58-11.
Rucker, R, R,, and Amend, D. F,, 1969, Absorption and re-
tention of organic mercurials by rainbow trout and Chi-
nook and sockeye salmon: Prog, Fish Culturist, v. 31, p.
197-201.
Ukelea, Ravenna, 1962, Growth of pure cultures of marine
phytoplankton in the presence of toxicants: Appl. Mi-
crobiology, v. 10, no. 6, p. 5.32-537.
Westoo, Gunnel, 1967, Determination of methylmercury com-
pounds in foodstuffs; 2, Determination of methylmer-
eury in fish, egg, meat, and liver; Acta Chem,
Scandinaviea, v. 21, no. 7, p. 1790-1800.
Wood, J. M., Kennedy, P. S„ and Rosen, C. G„ 1968, Syn-
thesis of methyl-mercury compounds by extracts of a
methanogenic "bacterium: Nature, v. 220, no. 5163, p.
163-174.
-------
MERCURY CONTENT OF PLANTS
By Hansford T. Shacklette
There are but few data available upon which to
base an estimate of the amounts of mercury that
are absorbed by plant roots and translocated to the
upper parts of the plants. Apparently, most plants
growr in soils that typically are low in amounts of
this element contain very little mercury in their tis-
sues. The difficulties of detecting these small
amounts by chemical methods has made routine
mercury analyses of plant samples impractical for
most laboratories. Under certain environmental con-
ditions, however, plant samples may contain larger
amounts of mercury that can be readily defected by
less rigorous analytical methods. The discussion
that follows distinguishes typical chemical environ-
ments for plants from those that, because of natu-
rally occurring mercury minerals or contamination
by industrial or agricultural practices, contain
anomalous amounts of mercury.
PLANTS GROWN IN A TYPICAL ENVIRONMENT
Typical soils that support vegetation contain
very small amounts of mercury; Hawkes and Webb
(1962, p. 369) reported 30-300 ppb, and Warren
and Delavault (1969, p. 537), 10—60 ppb. The few
available reports of mercury analysis of plants sug-
gest that this metal is not concentrated to a great
extent, if at all, in the tissues of most plants that
grow in these soils. Malyuga (1964, p. 15) stated
that the amount of mercury in plants is 1 ppb; this
figure is presumed to be an arithmetic mean, but
the data upon which this value is based were not
given and no other statement was found in the lit-
erature of the "average" mercury content of plants.
In a recent U. S. Geological Survey biogeochemi-
cal study conducted in Missouri, 196 native trees
and shrubs were sampled for chemical analysis. The
species studied were post oak (Quercus stellata
Wang.), over-up oak (Q. lyrata Walt.), white oak
(Q. alba L.), smooth sumac {Rhus glabra L.), winged
sumac (R. copallina L.), and red cedar (Jimiperus
virgimana L.). Terminal parts of stems (branches,
without leaves) of deciduous trees and shrubs, and
terminal branches including scalelike leaves of red
cedar, were selected for sampling. These plants
grew in an apparently "normal" mercury environ-
ment, All samples were reported by T. F. Harms,
analyst, to contain less than 500 ppb mercury in the
dry material. In an associated study of roadside
contamination of vegetation and soils in Missouri,
33 red cedar samples were found to contain less
than 500 ppb mercury (T. F. Harms, analyst),
whereas the mercury content of dry samples of the
soils in which these trees were rooted ranged from
40 to 650 ppb (E. P. Welsch, analyst).
PLANTS GROWN IN AN ENVIRONMENT
CONTAINING ABNORMAL AMOUNTS OF MERCURY
Soils overlying cinnabar deposits may contain as
much as 40,000 ppb mercury in their AL. and B hori-
zons ( Shacklette, 1965, p. C10). In a study of mer-
cury and other elements in plants that grew over
cinnabar veins at Red Devil on the Kuskokwim
River, Lower Yukon River district, Alaska, mercury
analyses performed by L E.
Patton yielded the fol-
lowing results:
Plant Number
FJmit species;
i-ar< of
(Pph of chs-
EllUil} v-ot; samjilt
i'S plant l
Ald^r (Altms erispa subsp.
crixfta Hult.)
Stems 1
1,000
Black spruce (Pixea mnriaim
(Mill.) Rritt., Sterns & Pog?.) .
Stems 4
1,000-1,500
and
leaves
Dwarf birch (Betula minti L.) . .
Stems 6
500-1,000
Labrador tea {Ledum jmlustrc
subsp. decumbent; (Ait.) Hult.) .
Stem? 7
1,000-3,500
Spiraea (Spiraea bemtverdiova
Sclmeld.)
Stems 1
3,000
and
leaves
White birch (Betula papyrifira
subsp. humilif (Regel) Hult.) . Stems 4 500-2,000
Mercury, if present, in other samples of these
plant species collected in the same area occurred in
amounts below the lower detection limit of 500 ppb
35
-------
36
MERCURY IN THE ENVIRONMENT
of the analytical method that was used. It is note-
worthy that trees whose roots extended through the
loess mantle and came in contact with a cinnabar
vein (as observed in prospect trenches that were
dug) invariably contained measurable amounts of
mercury in their branches; the branches of adjacent
trees whose roots did not contact these veins con-
tained no detectable amounts of mercury.
Rankama and Sahama (1950, p. 334) stated,
"Droplets of metallic mercury have been found in
the seed capsules of Holosteum umbellatum [jagged
chickweed; family Caryophyllaceae] growing on
some mercury-rich soils," and further, "Marine
algae may concentrate mercury, and some species
are found which contain more than a hundred times
as much mercury as sea water does. In exceptional
cases mercury is concentrated as native mercury in
some land plants. Vegetable fats are relatively rich
in mercury."
Goldschmidt (1954, p, 278) reported the
occurence of drops of metallic mercury under the
moss cover of the forest floor near hydrothermal
mercury deposits In the Rhine Palatinate. A U.S.
Geological Survey search for evidence of mercury
contamination of plants growing adjacent to a mer-
cury smelter at Red Devil, Alaska, by examination
of the soil surface under moss mats and by chemical
analysis of leaves from trees, revealed none.
Malyuga (1964, p. 25) stated that the possibility
of using the biogeochemical method of prospecting
for mercury was quite realistic, but that the slow
adoption of this method was due to difficulties in de-
termining the presence of mercury in soils and
plants.
The toxicity of mercury to plants apparently de-
pends on the chemical state of the element. Very
small amounts of volatilized elemental mercury are
believed by some floriculturists to be toxic to cer-
tain crops, particularly roses, and they do not use
mercury thermometers in their greenhouses because
of the danger of accidental breakage. Compounds of
mercury, in contrast, are widely used in crop pro-
duction for the control of certain fungus diseases
and, if properly used, produce no apparent toxic
symptoms in the plants. Shacklette (1965, p.
C9-C10) reported on examination of plants in the
Red Devil area for evidence of mercury poisoning
as follows:
* * * Presumably, the soil in the vicinity of the mine, mill,
and smelter has been contaminated as a result of several
years' operation of these installations; however, both bry-
ophytes [mosses and liverworts] and vascular plants ap-
peared to be remarkably unaffected. Mosses common to the
region grow in a cinnabar mill and smelter drainage stream
in which metallic mercury could be seen, and plants on a
mountain tundra slope immediately adjacent to and on a
level with the mercury-smelter exhaust stacks appeared un-
damaged, No undisturbed outcrops of cinnabar that bry-
ophytes could have colonized were found; but cinnabar was
found in placer deposits and in rock used to surface a road,
as well as around the mine shafts, and it did not appear to
have had any effect on the mosses growing1 near it. We ex-
posed some cinnabar outcrops by digging and found tree and
shrub roots that were in contact with the mineral. Branches
of the plants having root contact contained anomalous
amounts of mercury 4 * * yet the plants showed no toxicity
symptoms.
The amounts of mercury found in some samples
of plants or plant parts that have been treated with
mercury compounds may be large, but the analyses
alone do not demonstrate whether the element was
absorbed into and translocated throughout the plant
tissues or occurred only as a surficial residue, Nov-
ick (1968, p. 4) stated that mercury compounds arc
easily absorbed by plants and can be translocated
from one part of the plant to another, that mercury
fungicide applied to leaves of apple trees may be
translocated to the fruits, and that mercury may be
moved from potato leaves to the tubers.
SUMMARY
Plants growing in environments that have the
normal small amounts of mercury probably seldom
exceed 500 ppb mercury in their tissues. In environ-
ments that have significantly larger amounts of
mercury because of the natural occurrence of mer-
cury-bearing deposits, the plants may contain be-
tween 500 and 3,500 ppb mercury in their dried tis-
sues. Much larger amounts of mercury may be
found in plant samples as surficial residues or as
deposits in the tissues as a result of intentional ap-
plication of mercury compounds or from contamina-
tion.
REFERENCES CITED
Goldschmidt, V. M., 1954, Geochemistry: Oxford Univ. Press,
780 p.
Hawkes, II. E,, and Webb, J. S,, 1962, Geochemistry in min-
eral exploration: New York, Harper & Row, Publishers,
415 p.
Malyuga, D, P., 1964, Biogeochemical methods of prospect-
ing: New York, Consultants Bur., 205 p,
Noviek, Sheldon, 1369, A new pollution problem: Environ-
ment, v. 11, no.*4, p. 2-9.
Rankama, Kalervo, and Sahama, T. G., 1950, Geochemistry:
Chicago Univ. Press, 912 p.
Shacklette, H. T., 1965, Bryopliytes associated with mineral
deposits and solutions in Alaska: U.S. Geol, Survey
Bull. 1198-C, 18 p.
Warren, H. V., and Delavault, R. E., 1969, Mercury content
of some British soils: Oikos, v. 20, no. 2, p. 537-539.
-------
MERCURY IN THE ATMOSPHERE
By J. H. McCarthy, Jr., .J, L, Meuschke, W, H. Ficklin, and R, E. Learned
INTRODUCTION
Little is known about the abundance and distribu-
tion of mercury in the atmosphere. The mercury
content of air over scattered mineralized and non-
mineralized areas of the Western United States has
been measured in a study of the application of such
measurements in geochemical exploration for ore
deposits. Some of the data have been reported pre-
viously (McCarthy and others, 1969) ; additional
data are reported here. Several factors that influ-
ence the mercury content of air are discussed.
DATA
The mercury content of air over 15 ore deposits
and above four nonmineralized areas is shown in
table 28 (in the back of the report). For several lo-
cations data are given for mercury in air at ground
level and at 400 feet above the ground. In general,
the maximum concentration of mercury is found in
air over mercury mines, lower concentrations over
base aid precious metal mines, and still lower con-
centrations over porphyry copper mines. The con-
centration of mercury in air over nonmineralized
areas ranged from 3 to 9 ng/m3 in the areas investi-
gated.
Neville (1967) reported that in the mercury mine
at I dr. a, Yugoslavia, the mercury vapor concentra-
tion is 1-20 X105 ng/m3, and that the concentration
of mercury vapor in air of the mercury processing
plant s 0.6-9.7 X10'1 ng/m3. Sergeev (1961) found
that mercury vapor in soil air collected from bore-
holes 1-2 meters deep contained 0-100 ng/m3
whereas air collected 1 meter above the surface con-
tained 10-20 ng/m3.
The concentration of mercury in air as a function
of altitude is shown graphically in figure 7. The
data were collected at Blythe, Calif. The curve for
January indicates that above 300 feet the mercury
concentration dropped markedly whereas data col-
lected at the same site in late April show no appar-,
ent trend. Figure 7 also illustrates that lower values
for mercury are obtained in January than in April.
Williston (1968) found similar mercury contents in
air in the San Francisco Bay area. This seasonal
variation in the mercury content of air is ascribed
to seasonal temperature differences.
In addition to seasonal variations in the mercury
content of air, there are daily variations, as shown
in figure 8. A record of temperature, barometric
pressure, and mercury in air at ground level
(dashed line) is shown for 2 days. The data were
collected at the Silver Cloud mine near Battle
Mountain, Nev. The maximum amount of mercury
in air is found at about midday; much smaller
amounts are found in the morning and in the eve-
ning. The barometric pressure curve is typical and
reveals a consistent diurnal variation. The pressure
begins to fall at 8:00-9:00 a.m. and falls steadily
until about 6:00-7:00 p.m.; then it rises steadily
through the night. Thus if no atmospheric disturb-
ances exist, the pressure record transcribes an ap-
1000
900
800
700
uj 600
uj
11.
z 500 -
°
p 400
< 300 -
200 -
100
Jan. I, 1968
o
T
April 27, 1968
-7—0-
/
\
\
/
\
/
I 23456789 10
MERCURY IN AIR, IN NANOGRAMS PER CUBIC METER
Figure 7.—Mercury in air as a function of altitude, Blythe,
Calif.
37
-------
38
MERCURY IN THE ENVIRONMENT
FRIDAY
SATURDAY
w
NOON
'TEMPERATURE
o
50
24.2
o
60'
"^BAROMETRIC
PRESSURE
Ll)
24.0 O
50'
Figure 8.—Daily variation of mercury in air at the ground
surface, temperature, and barometric pressure, Silver
Cloud mine near Battle Mountain, Nev.
proximate sine wave with maximum rate of fall
about midday. When the barometric pressure begins
to fall, mercury is released to the atmosphere and
reaches a maximum when the rate of fall of baro-
metric pressure is greatest.
The mercury content of air was measured at 2-
hour intervals for a period of 36 hours at the Ord
mine in Arizona, Daytime patterns similar to those
at Silver Cloud were observed with a maximum of
600 ng/rn3 of mercury found near midday and a
minimum of 20 ng/m3 found at 2:00 a.m. The mini-
mum mercury concentration occurred during the
time when the rate of increase in barometric pres-
sure was greatest. Thus the daily content of mer-
cury in air is a function of the diurnal change in
barometric pressure resulting in the exhalation of
mercury through the earth's "breathing process."
The effect of temperature is less obvious; the maxi-
mum daily temperature commonly occurs 2-4 hours
later than the time when maximum mercury is
found in air.
Most of the data reported here have been col-
lected on clear days with no precipitation. However,
at one sample site near the Ord mine 20 ng/m3 of
mercury was found in the air the day before a rain-
storm. On the following morning, several hours
after the rain, no mercury was detected in the air.
Rankama and Sahama (19fi0) also reported that
mercury in the atmosphere is removed by precipita-
tion. Stock and Cucuel (1934) reported an average
content of 0.2 ppb of mercury in rain water com-
pared with oceanic abundance of 0.03 ppb mercury.
SUMMARY
The abundance of mercury in the earth's crust is
estimated to be 60 ppb (Green, 1959), and the
abundance of mercury in soils is estimated to be
about 100 ppb (A. P. Pierce and others, this re-
port) . Mercury in the atmosphere is derived from
surface rocks and soils and from continuing hypo-
gene and supergene processes.
Elemental mercury results from either process,
and owing to its relatively high vapor pressure, it is
released to the atmosphere. More mercury is found
in air over mercury deposits than elsewhere, and
the rate of release of mercury over the deposits is
determined by barometric pressure and tempera-
ture. The data shown in table 28 indicate that
anomalous concentrations of mercury are found in
air over mineral deposits but that small amounts
are found in air over nonmineralized areas. The
data of figure 7 indicate a seasonal variation in the
mercury content of air which may be the result of
seasonal temperature variation. The data shown in
figure 8 indicate that daily variations result from
changes in barometric pressure. Lesser concentra-
tions of mercury are found in air over the ocean;
Williston (1968) found 0.6 to 0.7 ng/m3 of mercury
20 miles offshore over the Pacific Ocean, suggesting
that the land surface is the principal source of mer-
cury in the atmosphere.
CONCLUSIONS
Several tentative conclusions about mercury in
the atmosphere can be drawn:
1. Mercury vapor is released to the atmosphere by
evaporation from and by degassing of surface
material.
2. Mercury content of air is highest over areas
where the rocks are richest in mercury (2,000
to 20,000 ng/m3 at the surface and 24 to .108
ng/m:1 at 400 ft).
3. The maximum content of mercury in air was
found near midday; lesser amounts were found
in the morning and evening; and minimum
amounts were found near midnight.
4. The mercury content of ground surface air is
considerably higher than that of air above the
ground (108 to 20,000 ng/m3 at the Ord mine).
5. Background concentrations of mercury in air at
400 feet above ground in the Southwestern
United States range from 3 to 9 ng/m3.
REFERENCES CITED
Green, Jack, 1959, Geoehemical table of the elements for
1959: Geol, Soc. America Bull., v. 70, no. 9, p.
1127-1183.
McCarthy, J. H., Jr., Vaughn, W. W., Learned, R. E., and
Meuschke, J. L., 1969, Mercury in soil gas and air—A
-------
ATMOSPHERE
39
potential tool in mineral exploration: U.S. Geol, Survey
Circ. 609, 16 p.
Neville; G. A., 1967, Toxicity of mercury vapor: Canadian
Chem, Education, v. 3, no. 1, p. 4-7.
Rankana, Kalervo, and Sahama, T. G., 1950, Geochemistry:
Chicago Univ. Press, 912 p.
Sergeev, Y. A., 1961, Methods of mercurornetric investiga-
tions: Internat. Geology Rev., v. 3, no. 2, p. 93-99.
Stock, Alfred, and Cueuel, Fricdrich, 1934, Die Verbreitung
des Quecksilbers: Naturwissenschaften, v. 22, p. 390-893.
Williston, S. 11., 1968, Mercury in the atmosphere: Jour,
Geophys. Research, v. 73, no. 22, p. 7051-7055.
-------
ATMOSPHERIC AND FLUVIAL TRANSPORT OF MERCURY
By E. A. Jenne
Mercury is supplied to the environment from many
sources. Near-surface mercury-bearing mineral de-
posits, industrial wastes and exhausts, and applica-
tions of agricultural chemicals serve locally to in-
crease the mercury level of streams, lakes, and
impoundments. Natural laws govern the rate and
manner of movement of mercury.
ATMOSPHERIC TRANSPORT OF MERCURY
Mercury enters the atmosphere in both gaseous
and particulate forms. The mobility of mercury is
greatly enhanced by a property which is unique
among the metals, namely the relatively high vapor
pressure of the metallic state and, to a lesser extent,
certain of its compounds. The vapor pressure is suf-
ficiently high that air drying at 20"0 for 2 days in
a sealed box through which previously dried air was
passed resulted in losses of 15, 24, 42, and 42 per-
cent of the mercury originally present in minus 200
mesh fractions of four soils (Koksoy and others,
1967). These authors also note "the detectable mer-
cury content of a sample originally containing 220
ppb (5 determinations) was increased by 25 percent
when stored for 30 days at room temperature in the
same box as a sample containing 8,000 ppb mer-
cury."
The rate of vaporization of mercury and certain
of its inorganic compounds decreases in the sequence
Hg>Hg2CL>HgCl2>HgS>HgO according to the
data of Koksoy and Bradshaw (1969). Vapor pres-
sure of mercurial fungicides is much greater for the
methyl and ethyl forms (0.8 to 23 times 10~3mm
(millimeter) mercury at 35°C) than phenyl forms
(0.8 to 17 times 10~6mm mercury at 35°C) (Phillips
and others, 1959). Methymercury choride is the
most volatile of the compounds tested1 (23xl0-3mm
1 Methylmereury chloride, mercury (gray powder with talc), ethnxyethyl
mercury silieate (tech.), methoxyethyl mercury silicate (tech.), ethylmer-
cury chloride, ethylmercury isothiourea hydrochloride, methoxyethyl
mercury chloride (tech,), ethoxyethyl mercury chloride (tech.), mercuric
chloride, ethylmercury dicyandiamide (tech.), methylmereury dicyandiamide,
bis-ethylmercury phosphate, tolylmercury acetate (mixed isomers?), phenyl-
mercury acetate, phenylmereury oxinate, phenylmereury iso-nrea, phenyl-
mercury salicylanilide (tech.), phenylmereury fluoroacetate, phenylmereury
chloride, his-phenylmercury methanodinaphthodisulphnate (tech.), phenyl-
mereury nitrate, phenylmereury salicylate, NN-dimethyldlthlocarbamate.
mercury at 35°C). The methyl and ethyl forms
tested, other than methylmereury chloride, have a
volatility similar to metallic mercury (1.2 to 3.4
times 10 'mm mercury (Phillips and others, 1959).
Gaseous and particulate mercury are commonly
contained in the exhaust fumes from various in-
dustrial and smelting processes. Dust from sulfide-
bearing mineral deposits may occasionally be a sig-
nificant local source of mercury, inasmuch as "dust
obtained during the treatment of tin ores" has been
used for the industrial recovery of mercury (V. E.
Poiarkov, cited by Sergeev, 1961). Mercury may be
vaporized directly from the land surface, particu-
larly from mineralized areas, by radiant energy.
The saturation level of mercury in air in equilib-
rium with metallic mercury, increases logarithmi-
cally with increasing temperature (Vaughn, 1967).
Sergeev (1961) found the mercury content of soil
air over a mercury ore deposit to be 100 ng/m3,
whereas the atmospheric air immediately over the
deposit contained 10 to 20 ng/ma. By comparison of
these values with the value of 10G ng/m3 for air sat-
urated with metallic mercury vapor at 17°C
(Vaughn, 1967), the soil air sampled by Sergeev
would appear to have been undersaturated by a fac-
tor of about 104. The high degree of undersatura-
tion of the soil air directly over a mercury deposit
probably represents the faster rate of exchange of
soil air with atmospheric air as compared to the
rate of evaporation of mercury and its volatile com-
pounds. McCarthy and others (1969) concluded that
mercury in soil air samples was unrelated to the
mercury content of the soil from which it was sam-
pled, hence, most of the mercury in the soil air was
assumed to come from greater depth. According to
Williston (1964), the presence of a water table
above mercury deposits does not greatly reduce the
rate of mercury loss by vaporization.
Presumably, the microbial methylation of mer-
cury (P. E. Greeson, this report) will increase the
vapor phase loss of mercury. Although monomethyl
mercury is the principal product of biological meth-
40
-------
ATMOSPHERIC AND FLUVIAL TRANSPORT
41
ylatiori (Jensen and Jernelov, 1969), to the extent
that the uncharged dimethyl mercury complexion is
also formed, a net increase in volatility will result.
Little is known concerning the extent or nature
of the reactions of gaseous mercury with earth ma-
terials although gaseous mercury readily forms
amalgams with the noble metals platinum, gold, and
silver. Ginzburg (1960, p. 104) and Koksoy and
Bradshaw (1969) assumed that gaseous mercury is
sorbed by organic matter and clays. If it is, then
the amount of gaseous mercury that escapes from
the land surface into the atmosphere is appreciably
less than it would otherwise be. To the extent that
this process occurs, the amount of mercury vapor in
the atmosphere is being continually decreased by re-
action with air-borne particulate matter and with
the land surface. Mercury that enters the atmos-
phere is returned to the earth's surface. Some of
the particulate atmospheric mercury returns to the
earth in dry fallout, but most of the atmospheric
mercury, both gaseous and particulate, returns to
the earth in rainfall. Stock and Cueuel (1934) re-
ported five rainwater samples whose mercury con-
tents were only a few tenths of a part per billion
above the background value of approximately 0.01
ppb. They also reported that the average of 12 sam-
ples, whose mercury content was significantly
greater than the background value, was 0.2 ppb;2
the maximum value found was 0.48 ppb. The atmos-
pheric mercury yield by rainfall was estimated by
Anderssen and Wiklander (1965), who reported 1.2
gram,3 per hectare per year (0.48 gram per acre per
year) in Sweden and noted that this amount is
about the same as that used for seed dressing I fun-
gicide ). Near industrial areas, more mercury may
possibly be deposited by dry fallout than by rainfall
during dry seasons. Thus, Dams and others (1970)
found. 21/2 times as much particulate mercury in the
atmosphere in an industrial area of Chicago as in a
rural area; that is, 4.8 versus 1.9 ng/m3.
PLUVIAL TRANSPORT OF MERCURY
The oxidation of mercury-bearing sulfide ores pre-
sumably results in the formation of both mercuric
and mercurous ions. Mercurous chloride (Hg7Cl,)
is only slightly soluble (0.002 g/1 (gram per liter)
or 2,000 ppb). It has a strong tendency to dismutate
according to the reaction Hga+'-'-frHgo + Hg*4 under
aqueous conditions (Sidgwiek, 1950, p. 294). This
reaction may be promoted by ultraviolet radiation
(Sidgwiek, 1950, p. 295). James (1962) sug-
9 Incorrectly cited by R&nk&ma and Sahama, (1950, p, ?18) as 2 ppb.
gested that the rather insoluble basic sulfate salt
Hg:SO<-IIgO-H;,0 is also likely to form as the result
of oxidation of mercury-bearing sulfide ores. Mer-
curic chloride, HgCL, being highly soluble (69 g/1 at
25°C), will be readily leached by rainfall and carried
to streams by runoff, underflow, or ground water
discharge. Rainfall-induced erosion and leaching also
convey a part of the atmospheric mercury, previ-
ously returned to the land surface, to streams and
other waters. Of course, a part of the atmospheric
mercury is returned directly to water bodies by dry
fallout and rainfall. According to Warren, Delavault,
and Barakso (1966) the mercury contfent of soils
varies appreciably in the areas studied by them.
Soils completely unaffected by mineralization or
local industrial contamination varied from 10 to 50
ppb of mercury. In contrast, soil within some hun-
dreds of feet of mercury associated major base metal
deposits ran from 250 to 2,500 ppb of mercury. In
the immediate area of mercury mineralization, soils
commonly contained from 10,000 to 20,000 ppb but
ranged from 1,000 to 50,000 ppb of mercury. They
suggest that where the soil B or C horizons contain
more mercury than the A horizon, which is com-
monly enriched by vegetative litter, it is probable
that there is mineralization in the immediate vicinity.
However, they note that anomalous clay or organic
matter contents of the various horizons may alter
this general rule.
Where streams have ipcised mercury-bearing de-
posits, both solute and particulate mercury are re-
leased directly to the fluvial environment. In places,
thermal springs, nonthermal springs, and mine
drainage contribute significant amounts of mercury
to streams.
Quantitative data on the sorption and desorption
of ionic mercury by earth materials were not found
in the literature in the course of the preparation of
this report. However, in common with other metals
such as zinc and cadmium (Rankama and Sahama,
1950, p. 715; Goldschmidt, 1954, p. 275) or anti-
mony (Koksoy and Bradshaw, 1969), mercury ap-
pears to be strongly sorbed by soils and sediments.
Mercury must be fixed, that is, be desorbed very
slowly, by soils and fluvial sediments. Otherwise,
the high vapor pressure of free mercury and certain
of its compounds as well as the solubility of the
chlorides of mercury would preclude the notable en-
richment of some soil horizons over mercury depos-
its and the very considerable increase in mercury
concentration in fluvial sediments immediately
below industrial outfalls that contain mercury
-------
42
MERCURY TN THE ENVIRONMENT
wastes. Likewise, the affinity of certain soils for
mercury is indicated by the failure of mercury ap-
plied as orchard sprays (phenyl-mercury acetate)
over a period of several years to migrate below the
surface 2 inches; the soil contained 500 or 1,100 ppb
of mercury depending on the number of sprays ap-
plied (Ross and Stewart, 1962), A further indica-
tion of the tendency of mercury to be sorbed by sol-
ids is the marked loss of mercury from solution
when unacidified water samples are stored in either
polyethylene or glass containers. From 50 percent
to 175 percent of the mercury lost from solution
was recovered by acid washing the glass containers
in which water samples were stored for only 2
weeks (Hinkle and Learned, 1969). It has been ob-
served that the amount of mercury present in the
surface horizon of five Swedish soils varied directly
with the organic matter content (Anderssen and
Wiklander, 1965) and that both plankton and peat
moss sorbed significant amounts of mercury from
solution (Krauskopf, 1956). Mercury forms stable
complexes with a number of different types of or-
ganic compounds found in natural waters, such as
sulfur-containing proteins and humic materials.
Some species of marine algae concentrate mercury
from sea water to more than 100 times the sea
water value of 0.03 ppb (Stock and Cucuel, 1934).
Mercury is also concentrated to some degree in coal
(Goldschmidt, 1954; and Michael Fleischer, this re-
port) and notably in petroleum fluids (D. E. White
and others, this report). Inasmuch as mercury
forms many stable organo-metallic compounds in-
cluding sulfur-containing proteins, probably a very
significant part of the cationic mercury that has re-
sided in natural fresh waters for times on the order
of hours to days will be in some organic form. Fur-
thermore, one may in some cases find a greater
amount of mercury in the particulate fraction than
in the solute fraction where the amount of sus-
pended solids is relatively high and especially where
the relative quantity of particulate organic matter
is high relative to the soluble organic matter. Hin-
kle and Learned (1969) found from five to 25 times
as much mercury in a 1 N hydrochloric acid extrac-
tion of the suspended sediment separated from some
samples as was found in the filtrate.
The single analysis found of marine manganese
nodules for mercury (J. P. Riley and P. Sinhasong,
cited by Mero, 1965, p. 181) yielded a value of 2,000
ppb, a concentration factor of 10' over the 0,03 ppb
level in sea water. Likewise, manganese ores and
"brown" iron ore are reported to contain as much
as 1,000 ppb (A. A. Saukov, 1946, cited by Sergeev,
1961). In support of these observations are the find-
ing of Krauskopf (1956) that initially divalent mer-
cury was effectively sorbed by microcrystalline iron
oxides. In solutions containing 30,000 ppb of
Fe,03 ¦ nILO and initial mercury concentrations of
200 ppb, 90 to greater than 95 percent of the mer-
cury was sorbed by the iron oxide within a few days.
Montmorillonite was less effective as a sorbent (~10
times more solids required to obtain similar sorption
efficiency). A number of limonite samples from
chalcopyrite deposits in the Southern Ural Moun-
tains had an average mercury content of 16,000 ppb
(Ginzburg, 1960, p. 104). The sorption efficiency
ascribed to clays (Koksoy and Bradshaw, 1969) is
very likely due to the nearly ubiquitous microcrys-
talline iron and, to a lesser extent, manganese oxide
coatings present on the clays (Jenne, 1968; Ander-
son and Jenne, 1970). James (1962) has postulated
the sorption of mercuric chloride anion complexes
(HgCLr, IlgClr'2) by clays; sorption of molecular
salts (HgeCl.j, HgCL) is also a possibility. The hy-
drous oxides of iron and manganese provide the
most likely sites for both anionic and molecular salt
sorption by earth materials.
Less rapid reactions that may remove mercury
(Hg"J radius—1,10 angstroms) from waters and
soils solutions are the possible isomorphous substitu-
tion for barium (Ba+2 radius—1.34 angstroms) and,
to a lesser extent, for calcium (Ca+2 radius=0.99
angstrom). However, the much greater electronega-
tivity of mercury (1.9) than of calcium (1,10) and
the fact that the ionic radius of divalent mercury is
more than 15 percent smaller than the ionic radius
of barium will certainly limit its solid solution for
calcium and barium (Ringwood, 1955). Nonetheless,
in districts that contain metallic mercury, barium
sulfate (barite) may contain from 20,000 to 190,000
ppb mercury (A. A. Saukov, 1946, cited by Sergeev,
1961). Similar results were obtained by Vershkov-
skzia (1956, cited by Ginzburg, I960, p. 19).
Little information is available on the cation ex-
change properties of mercury. Ginzburg (1960, p.
155) stated that "Divalent ions form the following
series, in reference to their uptake by montmoril-
lonite from aqueous solutions Pb>Cu>Ca>Ba>
Mg>Hg, and in reference to the facility of the re-
placement, Mg>Ba>Ca>Cu>Pb. The energy of ad-
sorption series of heavy metals by kaolinite are as
follows: Hg>Cu>Pb; the calcium replacement
series Pb>Cu>Hg." Thus, it appears that the sorp-
tion capacity of this kaolinite for mercury is low,
but that mercury which is sorbed is held strongly.
-------
ATMOSPHERIC AND FLUVIAL TRANSPORT
43
A regular decrease in mercury down the Paglia
River ; Italy) below a mercury anomaly was ob-
served by Dall'Aglio (1968). The mercury concen-
tration in the stream water decreased from a high
of 136 ppb to a low of 0.04 ppb 50 to 60 kilometers
downstream. (It is not clear from the paper
whether these analyses are on filtered or unfiltered
sample:;; presumably they were filtered). Wisconsin
River sediment contained 560,000 ppb at a chemical
compary outfall but only 50,000 ppb 4 miles down-
stream (Chemical and Engineering News, 1970).
The mercury concentration in the sediment had de-
creased to 400 ppb 21.4 miles downstream (Francis
II. Schraufnagel, oral commun., July 20, 1970). The
downstream decrease in the amount of mercury in
the sediment is indicative of the rapid downstream
decrease in mercury concentration. Concerning pos-
sible seasonal variations, Heide, Lerz, and Bohm
(1957) concluded that such variations did not occur
in the mercury content of the Saale River (Ger-
many) although they reported a minimum value of
0.066 ppb and a maximum value of 0.141 ppb of
mercury at one sampling station in the course of a
year, a progressive increase in downstream mer-
cury concentration in the Saale River due presuma-
bly to industrial pollution is indicated by their data.
EXPERIMENTAL DATA
Recent experimental data indicate that the sorp-
tion of mercury by membrane filters is minimal
and that mercury sorption by peat moss, micro-
crystal line oxides, and soils is rapid (V. C. Ken-
nedy, unpub. data, 1970). Solutions containing 1
and 1C ppb of mercury (originally divalent) were
made up in tap water prefiltered through a 0.1 mi-
cron membrane filter. From 1 to 7 percent of the
mercury in 50 ml (milliliters) of these solutions
was retained by 0.45-micron 2-inch cellulose acetate
membrane filters in a single pass. This was true for
both pEI 6 and 8 solutions. Sorption of mercury by
three soils, by a microcrystalline manganese oxide,
and by peat moss was rapid. From half to nearly all
the mercury In 50 ml of a 10 ppb solution of pH 6
was sorbed within 1 hour by Vi-gram samples.
After 24 hours, all the samples had sorbed more
than three-fourth's of the added mercury.
The amount of mercury desorbed in 1 hour from
the manganese oxide, from the 24-hour set of sam-
ples, by filtered tap water and subsequently by one-
half normal sodium chloride (to approximate es-
tuary salinity) was between 10 and 20 percent and
30 to 40 percent, respectively. The remainder of the
24-hour set of samples desorbed from less than 1 to
5 percent of the mercury originally sorbed, using fil-
tered tap water. Subsequent desorption in one-half
normal sodium chloride in general removed slightly
less mercury than was desorbed by tap water. A
similar amount of mercury was desorbed from the
manganese oxide from botk the 1-hour and the 24-
hour sorption sets. However, a slightly lesser per-
centage of the mercury originally sorbed was de-
sorbed from the other samples which were exposed
to mercury containing solutions for 24 hours. From
2 to 7 percent was desorbed in tap water and 1 to 2
percent in one-half normal sodium chloride.
Thus, mercury at trace concentrations is rapidly
taken up by microcrystalline oxides, peat moss, and
soils. Most of the mercury was held irreversibly
against filtered tap water and one-half normal so-
dium chloride. However, it is not known to what ex-
tent the uptake by these earth-material samples is
due to sorption of cationic mercury and to what ex-
tent the uptake may be due to a reduction to metal-
lic mercury. The Eh-pH diagrams of Symons
(1962) and the discussion of J. D. Hem (this re-
port) indicate that metallic mercury is the stable
form in most natural fresh waters. In very well ox-
ygenated acid to neutral waters the mercurous ion
may be the stable ion whereas under alkaline condi-
tions the mercuric oxide, montroydite, may be the
stable phase.
FATE OF MERCURY INTRODUCED INTO
ENVIRONMENT
Mercury is being continuously removed from the
atmosphere and deposited on the earth's surface by
dry fallout and by rainfall. Solute mercury intro-
duced into streams is quickly transformed to the
particulate form by reduction to metallic mercury,
by sorption on to inorganic sorbates, by eomplexa-
tion with nonviable particulate organics, and by
sorption and ingestion by viable biota. The avail-
able evidence (Heide and others, 1957; Dall'Aglio,
1968; V. C. Kennedy, unpub. data, 1970) is that
stream sediments and related fine-grained materials
remove a high percentage of any slugs of mercury,
introduced into streams, within a distance of a few
to several miles, depending on the existing redox
potentials, the amount of suspended sediment,
stream discharge, and the mineralogieal-chemical
nature of the sediment.
When a mercury pollution source is eliminated,
mercury will be slowly released from bed sediment
to the stream water over a period of time (possibly
months) until a steady state condition is reached.
The complexing of mercury by soluble organics
-------
44
MERCURY IN THE ENVIRONMENT
will greatly increase its mobility as will the forma-
tion of strong inorganic complex ions. Considering
the known ability of natural soluble organics to ex-
tract trace metals from soils and sediments, it is
likely that to a first approximation the mobility of
mercury in natural waters will be dependent upon
the amount and chemical nature of the soluble or-
ganics present. Thus, mercury may have greater
mobility in waters containing large amounts of dis-
solved org-anics. In the case of ground waters, the
mercury concentration has been found to be directly-
related to their bicarbonate content (Karasik and
others, 1965).
The quantity of sediment in transport is the sec-
ond most important factor in determining the
downstream movement of mercury. For example,
Hinkle and Learned (1969) found from five to 25
times as much mercury in the suspended sediment
as in the filtered water.
Organic pollution of natural waters, whether
from natural or manmade sources, frequently
causes reducing conditions to develop on the
streambed. The occurrence of reducing conditions
will cause the partial release of sorbed mercury due
to dissolution of manganese and iron oxides present
in the sediment. On the one hand, this will have the
effect of enhancing mercury mobility by increasing
the amount of mercury available for eomplexing by
organics at the expense of mercury sorbed by the
inorganic sediments. On the other hand, it is likely
that under such reducing conditions a significant
part of the mercury present will be reduced to the
metallic state. This will decrease its mobility to the
extent that the metallic mercury amalgamates with
iron oxides or falls to the bed as droplets. (How-
ever, Fedorchuk (1961) notes that mercury is not
concentrated in the heavy mineral fraction of
shales.) The solubility of metallic mercury, in the
presence of 5 to 10 ppb of chloride and under condi-
tions where the mereurous ion is stable, is generally
less than 2 ppb (J. D, Ilem, this report). However,
the total solubility of both dissociated and undisso-
ciated species is from 20 to 30 ppb {Sidgwiek, 1950,
p. 287; Pariaud and Archinard, 1952). Thus, mer-
cury can be expected to be released to the stream
water rather slowly. The apparent ease of microbial
transformation of inorganic mercury in bed sedi-
ments to the highly soluble methylmercury form (P.
E. Greeson, this report) will noticeably increase
mercury mobility. This transformation can be rather
rapid, near steady state conditions being reached in
a few days in batch tests (Jensen and Jernelov,
1969). The release of sulfides to or production of
sulfide in the stream, as a result of reducing condi-
tions, may markedly affect the mobility of mercury.
The precipitation of the rather insoluble mercuric
sulfide, HgS (1.25XKH4 gy'l, Sidgwiek, 1950, p.
293), will tend to concentrate mercury in the sedi-
ment. In those unusual instances wherein alkaline
reducing conditions exist, and hence greater sulfide
concentrations occur, the formation of the rather
soluble HgS;"- ion may facilitate mercury transport.
Although mercuric mercury is generally unstable
with respect to metallic mercury in stream waters
(Symons, 1962), mercuric sulfide is formed by the
reaction Hg,S^Hg° + HgS (Sidgwiek, 1950, p. 293).
ACKNOWLEDGMENTS
The author is much indebted to V. C. Kennedy for
permission to use unpublished data, to both V. C.
Kennedy and T. T. Chao for helpful discussions and
literature references, and to R. L. Malcolm and Paul
T. Voegeli for rapid but helpful technical reviews.
It is indeed a pleasure to acknowledge the excellent
library assistance of William Sanders and Ann H.
Schwabecher.
REFERENCES CITED
Anderson, R, ,J., and Jenne, E, A., 1970, Free-iron and -man-
ganese oxide content of reference clays: Soil Sci., v. 109,
no. 3, p. 163-169.
Anderssen, Arae, and Wiklander, I., 1965, Something about
mercury in nature: Grundforbattring, v. 18, p. 171-177.
Chemical and Engineering News, 1970, Mercury stirs more
pollution concern; v. 48, no, 26, p. 24,
Dail'Aglio, M., 1968, The abundance of mercury in 300 natu-
ral water samples from Tuscany and Latium (central
Italy), in Ahrens, L, H,, ed.. Origin and distribution of
the elements*. New York, Pergamon Press, p. 1065-1081,
Dams, R,, Robbing, J, A., Rahn, K. A., and Winchester, J.
W., 1970, Nondestructive neutron activation analysis of
air pollution particulates: Anal, Chemistry, v, 42, no. 8,
p. 861-867.
Fedorchuk, V. P., 1961, Formation of aureoles of direct ore
indicators around mercury deposits: Geochemistry, no,
10, p. 1010-1020.
Ginzburg, I, I., 1960, Principles of geochemical prospecting;
techniques of prospecting for non-ferrous ores and rare
metals: New York Perg&mon Press, 311 p.
Goldschmidt, V, M., 1954, Geochemistry: Oxford, Clarendon
Press, 730 p.
Heide, Fritz, Lerz, H., and Rohm, 1957, Lead and mer-
cury content of water from the Saale River: Naturvvis-
senshaften, v. 44, no. 16, p. 441-442.
Hinkle, M. E„ and Learned, R. E., 1969, Determination of
mercury in natural waters by collection on silver
screens: U.S. Geol. Survey Prof. Paper 650-D, p.
D261-254,
-------
ATMOSPHERIC AND PLUVIAL TRANSPORT
45
James, 0. IT., 1962, A review of the geochemistry of mercury
(excluding analytical aspects) and its application to
geoshemical prospecting: London, Imp, Coll, Sci, and
Technology, Tech, Commun. 41, 42 p.
Jenne, 13. A., 1968, Controls on Mn, Fe, Co, Ni, Cu, and Zn
consentrations in soils and water—The significant role
of hydrous Mn and Fe oxides, in Trace inorganics in
water: Advances in Chemistry Ser,, no. 73, p. 337-387.
Jensen, S., and Jernelov, A., 1969, Biological methylation of
mercury in aquatic organisms: Nature, v. 223, p.
753-754.
Karasik, M. A., Goncharov, Yu. I., and Vasilevskaya, A.
Ye., 1965, Mercury in waters and brines of the permian
salt deposits of Donbas: Geochemistry Internat., v. 2,
no. 1, p. 82-87,
Koksoy, M., arid Bradshaw, P. M. D., 1969, Secondary dis-
persion of mercury from cinnabar and stibnite deposits,
West Turkey: Colorado School Mines Quart., v. 64, no.
1. p. 383-356.
Koksoy M, Bradshaw, P. M. D„ and Tooms, J. S., 1967,
Notes on the determination of mercury in geological
samples: Inst. Mining Metall. Ball, v. 726, p. B121-124,
Krauskopf, K. B., 1956, Factors controlling the concentra-
tions of thirteen rare metals in sea-water: Geochim. et
Cosmochim. Acta, v. 9, nos. 1-2, p. 1-32B.
McCarthy, J. EL, Jr., Vaughn, W. W„ Learned, II. E., and
Meuschke, J. L., 1969, Mercury in soil gas and air—a
potential tool in mineral exploration: U.S. Geol. Survey
Che, 609, p. 1-16.
Mero, J. L., 1965, The mineral resources of the sea: Amster-
dam, Elsevier Publishing Co., 312 p.
Pariau i, J. C., and Archinard, P., 1952, Sur la solubilite des
metaux dans l'eau: Soc, Chim. France Bull., v. 1952, p
454-456.
Phillips, G. P., Dixon, B. E., and Lidzey, R. 6., 1959, The
volatility of organo-mereirry compounds: Sci. Food Ag-
riculture Jour., v. 10, p. 601-610.
Rankaina, Kalervo, and Sahama, Th. G., 1950, Geochemistry:
Chicago, Chicago Univ. Press, 912 p.
Eingwood, A. E,, 1955, The principles governing trace ele-
ment distribution during raagmatie crystallization; Part
1, The influence of electronegativity: Geochim. et Cos-
niochim. Acta, v. 7, nos. 3/4, p. 189-202.
Ross, R. G., and Stewart, D. K. R., 1962, Movement and
accumulation of mercury in apple trees and soil: Cana-
dian Jour. Plant Sci., v. 42, p, 280-285.
Sergeev, E. A., 1961, Methods of mercurometric investiga-
tions: Internat. Geology Rev., v. 3, no. 2, p. 93-99.
Sidgwick, N, V., 1950, The chemical elements and their com-
pounds: Oxford, Clarendon Press, 1,700 p.
Stock, Alfred, and Cucuel, Fred rich, 1934, Die Verbreitung
des Quecksilbers: Naturw:ssensehaften, v. 22, no. 22/24,
p. 390-393.
Symons, I)., 1962, Stability relations of mercury compounds,
in Schmitt, H. H„ ed,, Equilibrium diagrams for miner-
als at low temperature and pressure; Cambridge, Geo-
logical Club of Harvard, p. 164-175.
Vaughn, W. W., 1967, A simple mercury vapor detector for
geodiemieal prospecting: U.S. Geol. Survey Cire. 540, 8
P-
Warren, H. V., Delavault, R. E,, and Barakso, John, 1966,
Some observations on the geochemistry of mercury as
applied to prospecting: Econ. Geol. v. 61, p. 1010-1028.
Williston, S, II., 1964, The mercury halo method of explora-
tion: Eng. and Mining Jour,, v. 165, no. 5, p. 98-101,
-------
ANALYTICAL METHODS FOR DETERMINATION OF MERCURY IN
ROCKS AND SOILS
By F. N. Ward
The mercury content of most uncontaminated
solid earth materials is between 10 ppb and 500
ppb, and for water resources, generally is less than
0.1 ppb, as is shown by data elsewhere in this re-
port. Hence, to be useful, any analytical method
must be at least sensitive enough to detect as little
as 10~s gram and in some analyses one or two or-
ders of magnitude less. With the exceptions of the
techniques described by Ward and Bailey (1960) and
by L, L. Thatcher (written commun,, 1970), both dis-
cussed below, all methods mentioned in this article
measure only inorganically-bound mercury. Using
the best applicable methods, analytical limitations
of the methods are 10 ppb for rock and soils and 0.1
ppb for aqueous solutions if 100 ml (milliliters) of
sample is used. An exception to this statement is
the neutron activation method which may reach
0.05 ppb for water and sediment samples.
The requirements of sensitivity limit the number
of techniques that appear useful for determining
trace amounts of mercury in soils and rocks. (Al-
though not rigorously defined, trace amounts may
be considered as those occurring at 0.01 percent
(100,000 ppb) or less.) Among the applicable tech-
niques, including kinds of separations as well as
final measurements, are those based on molecular
and atomic absorption, molecular and atomic emis-
sion, catalysis, nephelornetry, polarography, and ac-
tivation to produce measurable decay products. Sev-
eral analytical methods for determining trace
amounts of mercury in geologic materials based on
some of these techniques are discussed below. Gra-
vimetric and volumetric methods are not generally
applicable, but under certain conditions large sam-
ples can be taken and the separated mercury meas-
ured by weighing or titrating with thiocyanate in
the presence of iron alum to a persistent pink color
(Hillebrand and Lundell, 1953). An old gravimetric
method (Eschka, 1872, quoted in Hillebrand and
Lundell, 1953) is discussed below.
The literature on analytical methods for deter-
mining' mercury in soils and rocks is voluminous,
especially when one considers that most of this lit-
erature covers less than a half century. Interests of
agricultural chemists in the effects of trace elements
in agriculture and of a few scientists like Gold-
schmidt and the Noddacks in trying out a new tech-
nique—the spectrograph utilizing emission phenom-
ena'—account in part for the literature becoming so
large in such a short time. Fischer's (1925) re-
search on the newly discovered large molecular com-
pounds, such as dithizone, that were capable of re-
acting with 10 6 gram and less of certain metals
(especially mercury ) to produce highly colored
products triggered the development of trace analyti-
cal methods.
Because of the vast literature available no claim
is made of complete coverage herein, and the men-
tion of a particular method to the exclusion of oth-
ers is only for illustration and with no intended
bias. Emphasis here is on procedures used by the
U.S. Geological Survey because of the author's
greater experience with them.
Molecular absorption—absorptiometric, spectro-
photometries, colorimetric—methods depend on the
reaction of mercury under special conditions such
as pH, etc., with high molecular weight compounds
—usually organic—to form a species that uniquely
absorbs certain light frequencies in the visible or
ultraviolet range. The amount of absorption can be
measured instrumentally or visually and then re-
lated to the initial concentration of mercury in a
homogeneous, isotropic medium; most often it is an
organic solvent. Immiscible organic solvents are es-
pecially useful for enriching the species to a thresh-
old level and for removing it from other compounds
so as to inhibit or prevent interfering side reac-
tions.
Dithizone is one of the most common organic
reagents that forms a highly colored and extracta-
ble species with Hg*2. The molar absorptivity of
Hg"2 dithizonate is about 70,000; that is, as little
46
-------
ANALYTICAL METHODS
47
as 0.012 microgram Hg per square centimeter gives
a measurable absorbance of 0.004 to 0.005 (unit dif-
ference in percent transmission as usually measured
insfcrumentally). Differences of such magnitude are
easily measured, and the dithizone procedure there-
fore is applicable to mercury concentrations found
in soils and rocks. The dithizone reaction was the
basis of the first practicable field method for de-
termining traces of mercury in such materials
(Ward and Bailey, 1960). Briefly, the procedure in-
volved treatment of a finely powdered sample with
sulfuric and hydrobromic acid and bromine in a test
tube. The acidity of the sample solution was ad-
justed ;o pH 4 and treated with dithizone in n-hex-
ane. Separation of the organic from the aqueous so-
lution and subsequent removal of un reacted
dithizone left an amber-colored solution of mercuric
dithizonate whose intensity was measured visually
against that of standard solutions.
The phenomenal growth of atomic absorption
methods following the classic paper by Walsh
(1955) tends to hide the fact that atomic absorption
determinations of mercury were made by noritechni-
cally oriented prospectors in the latter part of the
19th century. Mercury is unique with respect to its
high volatility and resulting large number of
ground state atoms in the vapor. Such atoms absorb
resonant frequencies of incident energy, and the
amount of absorbed energy is proportional to the
concentration of mercury.
Instrumentation useful for determining many ele-
ments beeame commercially available in the early
1960's and since then even more chemical elements
can be determined by atomic absorption. Sample in-
troduction is done in two different ways. In one
technique the sample is prepared in a solution,
which is nebulized in the acetylene-air flame that is
positioned in the path of incident energy. In a sec-
ond technique, which is unique to mercury, the sam-
ple is volatilized from a soil or rock sample by heat
or from a solution prepared from the sample, and
the resulting vapor is introduced into the path of
incident energy. The first technique is used by Tin-
dall (1967) and variants of the second are used by
Brandtnberger and Bader (1967) and Hatch and
Ott (1968). Sensitivities of the second technique are
of the order of 0.1 to 0.2 nanogram of mercury; if
the starting solution contains all the mercury ex-
tracted from a 1-gram sample, an analyst could
measure as little as 10~10 gram mercury in geologic
materials. This is equivalent to 0.1 ppb.
In the U.S. Geological Survey laboratories, mer-
cury in soils and rocks is measured by an instru-
mental atomic absorption method described by
Vaughn and McCarthy (1964) and Vaughn (1967).
The sample is heated to about 500°C in an rf (ra-
dio frequency) field to drive oft* mercury and parti-
culate and vapor oxidation products of any organic
material. The mercury is trapped on gold or silver
leaf, and the other evolved products are shunted
through a bypass and out of the system (diagramed
by Vaughn, 1967). Then the rf field is changed so
as to heat the gold or silver leaf, and the two-way
stopcock is rotated in order to direct the mercury
into the long measuring chamber, which has an ul-
traviolet lamp near one end and a photocell detector
at the other. The ground state atoms in the mercury
vapor attenuate the light from the ultraviolet lamp,
thereby decreasing the current output of the photo-
cell. The decrease is amplified in a differential am-
plifier causing' a meter deflection that is propor-
tional to the concentration of mercury. Under
routine conditions the sensitivity achieved is about
1 ppb, which is quite adequate for signaling anom-
alous concentrations in soils and rocks.
Mercury in aqueous solutions is determined by
amalgamation on a silver screen and subsequently
heating the dried screen in a rf heating coil. The re-
leased mercury vapor is measured in a mercury-
vapor absorption detector. The technique is describ-
ed by Hinkle and Learned (1969).
A similar method for sediment free water sam-
ples (Fishman, 1970) follows. The water samples
are filtered through 0.45 micron membrane filters
immediately after collection and acidified with 1,5
ml of concentrated nitric acid per liter of sample to
stabilize the mercury and to minimize loss by sorp-
tion on container walls. Mercury is collected from
the acidified water sample by amalgamation on a
silver wire. The silver wire is electrically heated in
an absorption cell placed in the light beam of an
atomic absorption spectrophotometer. The mercury
vapors are drawn through the cell with a water as-
pirator and the absorption is plotted on a recorder.
Samples containing between 0.1 and 1.5 ppb of mer-
cury can be analyzed directly; samples containing
more than 1.5 ppb must first be diluted.
Much of the data given in this report, and espe-
cially those used to produce the statistics shown in
A. P. Pierce and others (this report) were obtained
on atomic absorption units similar to those just de-
scribed.
Analytical methods based on optical emission
spectrography are seldom used in the U.S. Geologi-
cal Survey when many geologic samples must be an-
-------
48
MERCURY IN THE ENVIRONMENT
alyzed and time is short. Without specialized tech-
niques to enrich the mercury content of the sample
or to maintain the excited mercury atoms in an arc
column for several seconds, the overall sensitivity of
spectrographic methods is inadequate. Several Rus-
sian workers have exercised the patience and skill
needed to utilize the potential of optical emission
spectrograph}7 in measuring trace amounts of mer-
cury in soils and rocks; hence the method should not
be underestimated. For the most part, however, the
availability of other procedures that achieve greater
sensitivity with less effort precludes any large-scale
and in-depth investigations of optical emission spec-
trograph;*7 to determine mercury in ordinary mate-
rials such as soils, rocks, and vegetation.
Analytical methods based on catalysis are poten-
tially applicable to the determination of trace
amounts of mercury in soils and rocks. One such
method used by the Geological Survey is described
by Hinkle, Leong, and Ward (1966). This procedure
is based on the catalytic effect of mercury on the re-
action of potassium ferroeyanide with nitrosoben-
zene to give a violet-colored compound, whose inten-
sity is proportional to the mercury concentration.
The color can be measured instrumentally or vis-
ually. As little as 3X10~8 gram (10° ppb) of mer-
cury is readily measured, and starting with a 1-
gram sample, the analyst can measure concentra-
tions as little as 30 ppb.
Until recently, gravimetric methods of chemical
analysis have not been useful in determining con-
stituents occurring in amounts of 0.01 percent
(100.000 ppb) or less. Owing to recent improve-
ments in the sensitivity of analytical balances and
especially the improvements that permit accurate
weighing to a microgram or less, gravimetric meth-
ods should be evaluated, and the Eschka gravimet-
ric method for assaying mercury in soils and rocks
shows new promise.
The Eschka method consists of heating a sample
in the presence of copper (€utS) oxide and lime in a
closed system and amalgamating the - volatilized
mercury onto gold foil. With the improved analyti-
cal balances the amalgamated mercury can be meas-
ured by weight, and the increase resulting from
amalgamation is proportional to the mercury con-
tent of the sample.
Mass spectrometry has quite recently been used
for determining trace amounts of mercury in geo-
logic materials. The method is sensitive and fast, es-
pecially when directly linked to computer facilities,
but the large initial costs as well as the need of
skilled operators limit its application.
Activation methods for determining trace
amounts of mercury have been described by several
authors including Brune (1966) and Dams and oth-
ers (1970). The sensitivities achieved by these au-
thors range from 0.1 nanograms to 30 nanograms
depending on type of sample, irradiation time, and
chemical treatment. Measurement of the gamma (y)
radiation of Hgu'7 (65-hour half life) after irradia-
tion for 70 hours with a flux of 1012 nanograms per
square centimeter per second yields an absolute sen-
sitivity of about 5 nanograms in a nondestructive
procedure devised by L. G. Erwall and T. Wester-
mark (written commun., 1965). A sensitivity one
order of magnitude less was achieved by Sjostrand
(1964) in a destructive technique.
According to L. L, Thatcher (written commun.,
1970) neutron activation analysis is now being used
to determine mercury concentrations in water and
sediments down to 0,05 ppb. Two methods have
been developed; (1) A reference method which is
very specific for mercury and is capable of extract-
ing mercury from the stable complexes with which
it may be associated in water, and (2) a more gen-
eral method for toxic heavy metals including mer-
cury. In the reference method, 20 milliliters of
water sample are irradiated in a sealed quartz vial
at 1 megawatt for 4 hours. The mercury isotopes
HglllTm (24-hour half life) and Hg,s? (65-hour half
life) are generated. After irradiation the mercury
isotopes are isolated by performing a carrier pre-
cipitation with added mercury salt followed by stan-
nous chloride. The latter reduces the mercury and
radio-mercury compounds to the free metal includ-
ing any radio-mercurv that may be tied up as a sta-
ble complex. The activity of Hg1UT is counted in a
coaxial GeLi detector at 77 kilo electron volts. The
combination of chemical isolation of radio-mercury
and photon spectrum characterization provides very
specific identification of mercury. Sensitivity of the
method may be extended down beyond 0.05 ppb by
taking a larger water sample for the irradiation
and (or) by increasing the irradiation time.
The more general toxic heavy metal determina-
tion is carried out by stripping the heavy metals
from a 40 ml water sample by sulfide precipitation
using lead sulfide as carrier. The mixed sulfide pre-
cipitate is activated (lead does not activate) in poly-
ethylene or quartz as above. The lead sulfide pro-
tects the mercury from significant volitalization
during irradiation and also minimizes sorption loss
to the polyethylene. After irradiation, the photon
spectrum of the sulfides is scanned to identify the
characteristic photo peaks of mercury, copper, chro-
-------
ANALYTICAL METHODS
49
mium, cadnium, cobalt, and arsenic and to quantify
these heavy metals. The success of the method de-
pends on the ability to make a lead sulfide precipi-
tate of sufficiently high purity. This has not proved
to be a significant problem but reagent blanks are
always run as a precaution.
The reference method can be applied to the deter-
mination of mercury in waterborne materials, such
as sediment and biota, by dissolving the irradiated
materia] in hydrofluoric or oxidizing acids and fol-
lowing through with the carrier precipitation.
REFERENCES CITED
Brandcnbsrger, H., and Bader, H., 1967, The determination
of nanogram levels of mercury in solution by a flame-
less atomic absorption technique: Atomic Absorption
Newsletter, v. 6, no. 5, p. 101-108.
Brune, Dag, 1966, Low temperature irradiation applied to
neutron activation analysis of mercury in human whole
blood: Stockholm, Aktiebolaget Atomenergi AE-213, 7
p.
Dams, R., Robbins, J. A., Rahn, X. A., and Winchester, J.
W., " 970, Nondestructive neutron activation analysis of
air pollution particulates: Anal. Chemistry, v. 42, no. 8,
p. 861-867.
Fischer, H., 1925, Compounds of diphenythioearbazone with
metals and their use in analysis: Wiss. VeroelT. Sie-
mens-Konzern, v. 4, p. 158—170.
Fisliman, M. J., 1970, Determination of mercury in water:
Anal. Chemistry, v. 42, p. 1462-1463.
Hatch, W. II., and Ott, W. L,, 1968, Determination of sub-
microgram quantities of mercury by atomic absorption
spectrophotometry: Anal. Chemistry, v. 40, no. 14, p.
2085-2087.
Hillebrand, W. F,, and Lundell, G. E. F., 1953, Applied inor-
ganic analysis, with special reference to the analysis of
metals, minerals, and rocks [2d ed.]: New York, John
Wiley and Sons, Inc., 1034 p.
Hinkle, Ma, Leong, K. \V„ and Ward, F. N., 1966,
Field determination of nanogram quantities of mercury
in soils and rocks, in Geological Survey research 1966:
U.S. Geol. Survey Prof. Paper 550-B, p. B135-B137.
Hinkle, M. E., and Learned, R. E.f 1969, Determination of
mercury in natural waters by collection on silver screens:
U.S. Geo], Survey Prof. Paper 650-D, p. D251-D254.
Sjostrand, Rernt, 1964, Simultaneous determination of mer-
cury and arsenic in biological and organic materials by
activation analysis: Anal. Chemistry, v. 36, no. 4, p.
814-819.
Tindall, F. M., 1967, Mercury analysis by atomic absorption
spectrophotometry: Atomic Absorption Newsletter, v. 6,
no. 5, p. 104-106.
Vaughn, W. W,, 1967, A simple mercury vapor detector for
geocheniical prospecting: U.S. Geol, Survey Circ. 540, 8
P.
Vaughn, W. W.. and McCarthy, J. H., Jr., 1964, An instru-
mental technique for the determination of submicrogram
concentrations of mercury in soils, rocks, and gas, in
Geological Survey research 1964: U.S. Geol. Survey
Prof. Paper fiOl-D, p. D123-1)127 [1965],
Walsh, A., 1955, Application of atomic absorption spectra to
chemical analysis: Speetrochim, Acta, v. 7, p. 108-117.
Ward, F. N., and Bailey, E. H., 1960, Camp and sample-site
determination of traces of mercury in soils and rocks:
Am. Inst. Mining, Metal!., and Petroleum Engineers
Trans., v. 217, p. 343-350.
-------
receding page oimin _
TARLKS 1-28
-------
Preceding page blank
TABLES
53
Table 1.—Determinations of mercury in U.S.G.S, standard rocks by different laboratories
[Method: NA, neutron activation; AA, atomic absorption]
Sample
Granite G-l, Rhode Island 1 _ ...
Diabase W-l, Virginia
Granite G-2, Rhode Island-
Granodiorite GSP-1, Colorado.
Andesite AGV-1, Oregon.
Basalt BCR 1, Washington.
Peridotite PCC-l, California.
Dunite DTS-1, Washington.
Mercury
content
(ppb>
Year
Metho
310
1964
NA
130
1965
AA
245
1967
NA
120
1968
NA
70
1969
NA
97
1970
AA
80
1970
A A
170
1964
NA
340
1965
A A
110
1967
NA
330
1968
NA
94
1969
NA
280
1970
AA
290
1970
A A
39
1967
NA
29
1969
NA
50
1970
AA
50
1970
AA
10
1970
AA
120
1970
NA
21
1967
NA
41
1969
NA
15
1970
A A
17
.970
AA
15
1970
AA
4
1967
NA
16
1969
NA
25
1970
AA
2G
1970
A A
15
1970
AA
rr
1
1967
NA
4
1969
NA
18
1970
AA
10
1970
AA
5
1970
AA
4
1967
NA
4
1969
NA
5
1970
AA
11
1970
AA
10
1970
AA
4
1967
MA
6
1969
NA
12
1970
AA
10
1970
A A
8
1970
A A
: It has been suggested that some of the samples anaivzed ha
in the laboratory.
I become contaminated by mercury durirg tang storage
Table 2.—Analyses for mercury, in parts per billion, of basalts, yabbros, diabases, ondeailes, daeiles, and It pa riles
[Compare with table 6]
Sample
Number of
Basalt BCR-1, Washington
Diabase W-l, Virginia.
Three basalts, two dolerites, Iceland, Hawaii,
and Tasmania.
Basalts, cceanic sediments near Iceland
Gabbro, Quebec
Composite 11 gabbros, Germany
Composite 11 gabbros, Germany
Gabbros, Yakutia ...
Gabbros, northern Caucasus
Gabbros
Basalt, Germany
Range
samples
Average
analyzed
Min
Max
l
4
18
9
i
94
340
231
5
5
21
13
180
300
i
1
l
100
l
80
n
0
50
26
13
20
250
100
6
<1,100
500
240
1
190
Reference
Five labs.
Eight labs.
Ehmann and Lovering (1967).
Aidin'yan> Ozerova, and Gipp (1963).
Jovanovie and Reed (1968).
Preuss (1940).
Stock and Cucuel (1934a).
Nekrasov and Timofeeva (1963).
Afanas'ev and Aidin'yan (1961).
Ozerova (1962).
Stock and Cucuel (1934a).
-------
54 MERCURY IN THE ENVIRONMENT
Table 2.—Analyses for mercury, in parts per billion, of basalts, ga.bhros, diabases, andesites, daeites, and liparties—Continued
Number of Rangn
Sample samples Average Reference
analyzed
Min
Max
Basalt, Yakutia
3
(i
40
20
Nekrasov and Timofeeva (1963).
Basalt, Kamchatka and Kuriles. ..
63
20
100
47
Ozerova and Unanova (1965).
Basalts, Andesites, Mendeleev Volcano,
100
120
Ozerova and others (1969).
Kuriles.
Lavas, central Kamchatka
460
Aidin'yan and Ozerova (1964).
Lavas, eastern Kamchatka. .. _
640
Do.
Granophyre, associated with dolerite, Tas-
1
26
Ehmann and Lovering (1967).
mania.
Andesite, AGV-1, Oregon . . ..
1
4
26
17
Five labs.
Andesites, Kamchatka and Kuriles.
209
20
400
75
Ozerova and Unanova (1965).
Trachytes, northern Caucasus.
5
60
200
130
Afanas'ev and Aidin'van (1961).
Trachytic tuffs, northern Caucasus
19
70
500
160
Do.
Eruptive breccia, northern Caucasus
1
500
Do.
Keratophyres, northern Caucasus
7
20
300
100
Do.
Daeites, Kamchatka.
37
20
150
83
Ozerova and Unanova (1965).
Daeites, Yakutia . . ...... . .
6
9
30
10
Nekrasov and Timofeeva (1963).
Liparites, Yakutia
4
15
200
70
Do.
Liparites, northern Caucasus.. ...
3
40
80
60
Afanas'ev and Aidin'van (1961).
Ignimbrites, northern Caucasus
4
40
80
65
Do.
Sample
Table 3.—Determinations of mercury, in parts per billion, m granitic ¦
[N.f., not found. Compare with tablo 6]
Range
Number of
samples —
analyzed
Max
Average
Reference
Granite G-l, Rhode Island . _ .
Granite G-2, Rhode Island
Granodiorite GSP-1, Colorado
Composite 14 German granites
Composite 14 German granites
Granite, Karelia
Granites, diorites, granodioritcs,
Tadzhikistan.
Granitic rocks, Yenisei Range
Granites, Yakutia ..
Diorites, granodiorites, Yakutia
Diorites porphyrites, Yakutia
Granites and diorites
Granites, northern Caucasus. _
Extrusive granitoids, northern Caucasus.
Quartz porphyry, northern Caucasus
Porphyry, northern Caucasus
1
70
340
155
Seven labs.
1
29
120
55
Six labs.
1
15
41
22
Five labs.
1
58
Stock and Cucuel (1934a}.
1
100
Preuss (1940).
1
... .....
160
Aidin'yan, Troitskii, and Balavskava
Aidin'van, Mogarovskii, and Mcl'tii
(1969).
64
75
30
68
5
180
28
Golovnya and Volobuev (1970).
45
N.f.
80
20
Nekrasov and Timofeeva (1963 ).
26
N.f.
40
13
Do.
8
2
20
5
Do.
18
<100
400
190
Ozerova (1962).
2
130
200
165
Afanas'ev and Aidin'yan (1961'].
4
100
200
150
Do.
4
60
50
110
Do.
5
60
200
130
Do.
Table 4. —Determinations of mercury, in parts per billion, in ultramafic and deep-seated igneous rocks
Sample
Number of
samples
analyzed
Peridotite PCC-1, California
Dunite DTS-1, Washington
Serpentinites
Kimberlite, South Africa
Eclogite inclusion in kimberlite, South Africa.
Garnet peridotite in kimberlite, South Africa.
Eclogite inclusion in pipe, Australia
Granulite inclusion in pipe, Australia
Range
11
12
500
Reference
7 Five labs,
8 Do.
140 Ozerova (1962).
200 Ehraann and Lovering (1967).
640 Do.
780 Do.
1,480 Do.
1,230 Do.
-------
TABLES
55
Table 5. -Determinations of mercury, in parts per billion, in alkalic rocks
[Compare with table 6]
Sample
Number of
samples —
analyzed
Range
Average tor four granosyenite porphyries,
Caucasus, 90, 700, 4000, 5000.
Nepheline syenites, etc., Lovozero massif, Kola
Peninsula, U.S.S.K.
Nepheline syenites, etc., Khibiny massif, Kola
Peninsula, U.S.S.K.
Nepheline syenites
Min
Max
—
50
80
,000
90-5,000
640
140
580
273
179
30
4
,000
530
72
60
200
200
Average
Reference
Abuev, Divakov, and Rad'ko (1965).
Aidin'yan, Shilin, and Unanova (1966).
Aidin'yan, Sliilin, and Belavskaya (1%3).
Ozeryva (1962).
Tablk 6.
-Determinations of mercury, in parts per billion, in igneous rocks of areas of very high content, mainly from the Crimea and
Donets Bavin, U.S.S.R.
[Trt> trace]
Sample
Nurnbnr of
samples —
analyzed
Rangr*
Min
Max
Average
Diabases, Crimea
Spilites, Crimea_ _
Basalts, Donets Basin
Traehydolerit.es, Donets Basin
Andesite-basalts, Donets Basin
Camptonit.es, Donets Basin . .
Do
Basaltic andesite, Viet Nam.
Andesites, Donets Basin
Tuffs, Crimea_ _ . _
Keratophyres, Crimea
Granodiorit.es, Crimea _.
Porphyry, Crimea
Plagiogra lite, Donets Basin
Plagioporphyry, Dor.ets Basin
Granite, Donets Basin
Monzonites, Donets Basin
Pyroxenites, Donets Basin
Shonkinitss, Donets Basin
Nepheline syenites, Donets Basin_
33
3
8
4
4
18
13
~~fi
1
3
4
12
11
Tr.
500
200
200
300
60
3,000
10~200
Tr.
Tr.
Tr.
Tr.
3,400
200
<100
100
200
400
500,000
5,600
1.500
540
490
550
7,000
30,600
24,000
5,000
1,000
5,000
7.000
900
610
300
720
2,000
17,600
1,700
625
350
400
300
"9 ,"000
8.100
2,100
700
350
200
520
250
.320
1,200
Bulkin (1962).
Do.
Buturlinov and Korchemagin ("1968).
Do.
Do.
Do.
Dvornikov and Klitchenko (1964).
Aidin'yan, Troitskii, and Balavskaya (1964).
Panov (1959|.
Bulkin (1962).
Do.
Do.
Do.
Dvornikov and Klitchenko (1964).
Buturlinov and Korchemagin (1968).
Do.
Do.
Do.
Do.
Do.
Table 7.—Delerminaiiom of mercury, in parts per billion, in metamorpMc rocks
Sample
Nurabor of
samples —
analyzed
Quartzites, Valdai Series, Prussian platforrn___
Parapneisses, Valdai Series, Russian platform_
Granitic, Valdai Series, .Russian platform
OrthoamphiboHtes, Valdai Series, Russian
platform.
Phyllit.es ind schists, Trtysh 7,one
Amphibolite, Quebec
Pelitic schists, Vermont
Pelitic schists, Vermont (omitting highest)
Schists and hornfels, Khibina massif, Kola
Peninsula (country rocks of alkalic massif).
Schist, northern Caucasus
100
1
14
13
10
Min
55
25
30
30
2.5
2.5
70
Max
60
100
65
90
28
2.
942
600
Average Reference
57 Ozerova and Aidin'van (1966a, 1966b).
51 Do.
47 Do.
51 Do.
Do.
18 Jovanovic and Ileed (1968).
360 Do.
193 Do.
407 Aidin'yan, Shilin, and Belavskaya (1963).
60 Afanas'ev and Aidin'yan (1961).
-------
56
MEIICURY IN THE ENVIRONMENT
Table 8.—Analyses for mercury, in parts per billion, in limestones
Number of
Rantje
Sainplt;
saniplt-s
.
Average
Reference
analyzed
Mill
Max
1
33
Stock and Cueucl (1934a).
Germanv
14
28
220
66
Ileide and Bfthm ¦'19 57).
Nineteen Composites, Russian platform
19
10
90
31
Ozerova and Aidin'vau (1966a).
Argillaceous marls, Cauascus,
10
8,000
Abuov, Divakov, and Rad'ko (1965).
background = 50.
Limestones, Crimean highlands
8
100
6,400
2,300
Bulkin (1962).
Marls, Crimean highlands. . ..
5
500
5,000
1,500
Do.
Donets "Basin
314
<100
10,000
900
Karasik and Goneharov (196.1),
Kerch-Taman area, near mud volcanoes
2,000
5,000
Karasik and Morozov (1966).
Limestones and dolomites, southern Ferghana.
oo
20
150
75
Nikiforov. Aidin'van. and Kusevich (11J6G i
Northeast Yakutia
26
rj
70
18
Nekrasov and Timofeeva (1963 i.
Kazakhstan .
nOO
<20
Fursov, as quoted by Ozerova artel Aidin'yan
(1 966b'i.
Marble, Viet Nam
1
500
Aidin'yan, Troitskii, and Ba'.avskaya (1964),
Table 9.—
-Analyses for mercury.
in parts per billion, in-
sandstones-
Number of
Range
Sample
samples —
—
Average
Reference
analyzed
Min
Max
2
26
40
33
Stock and Cueuel (1931a).
Composite of 23
1
100
Preuss (1940).
Sandstones, mudstones, Russian platform
45
0
95
39
Ozerova and Aidin'van (1966b).
Effusive-sedimentarv, Kamchatka. ..
!>
97
Do.
Kazakhstan ... ... . .
nOO
20
Fursov, quoted by Ozerova and Aidm'ya:
(1966b i.
Northeast Yakutia
6
<2
30
12
Nekrasov and Timofeeva (1963V
Sandstones, Crimean highlands
83
100
11,000
5,700
Bulkin (1962).
Conglomerates, Crimean highlands
10
100
7,000
2,300
Do.
Donets Basin _ . .
< 50
1,000
300
Dvornikov and Klitchenko (1964).
Donets Basin. ...
77
<100
7,000
870
Karasik and Goneharov (1963).
Donets Basin, contact with dike
1
600
Buturlinov and Korchemagin (1968).
Donets Basin, from mercury deposit
3.000
10.000
6,000
Bol'shakov (1964).
Sandstones with limestones, southern Fer-
3,000
10,000
Kurmanaliev (1967).
ghana.
Aidin'yan, Troitskii, and Balavskaya ''1964)
Viet Nam..
4
280
1,000
620
Table 10.—Analyses fur mercury, in parts per billion, in shales and clays
Sample
Number of
samples —
analyzed
Range
Composite ,36 German shales
Composite 26 Gorman shales _.
Shales
Marly clays
Clays, Russian platform-
Shales, northeast Yakutia
Shales, sandstones, southern Ferghana
Shales, Komi A.S.S.R.
Argillites, sedimentary-volcanic, Kamchatka.
Bituminous shale, Alaska. _
Oil shales, Baltic region
Oil shales, Povolzlie region,
Oil shales, Tula region
Silurian shales outside ore region .
Silurian.shales within ore region
Shales, Crimean highlands
Shales, Donets Basin _
Shales, Donets Basin, contact with dikes
Shales, Donets Basin
Shales, Donets Basin, from mercury deposit.
Clays, Kerch Peninsula
Clays, Viet Nam
Min
Max
Average
Reference
1
300
1
510
4
130
250
182
.3
100
320
188
58
0
130
35
6
15
80
50
36
20
150
70
26
42
230
11
85
2
630
2,800
10
170
1,500
11
200
1,600
440
2
50
100
75
<100
200
nO
nOOO
48
<100
19,000
2,300
0
<50
80
50
8
<200
500
350
55
<100
8,000
660
1,000
60,000
<100
4,000
800
4
100
550
270
Preuss (11)40).
Stock and CucupI ri934a.).
Do.
Heide and Bokm ''1957).
Ozerova and Aidin'yan : 1966b).
Nekrasov and Timofeova ('1963').
Nikiforov, Aidin'yan and Kusevich ''1966).
Zav'yalov and Mal'tseva, quoted by Ozorova
and Aidin'yan (1966b),
Nikiforov, Aidin'yan, and Kusevich (1966).
Donnell, Tailleur, and Tourtelot (1967).
Ozerova and Aidin'yan (1966b).
Do.
Do.
Ozerova (1962).
Do.
Bulkin (1962).
Dvornikov and Klitchenko (1964).
Buturlinov and Korchemagin (1968).
Karasik and Goneharov (1963).
Bol'shakov (1964).
Morosov (1965).
Aidin'yan, Troitskii, and Balavskaya (1964).
-------
TABLES
Tabi.e 11.—Analyses for mercury, in parts per billion, in miscellaneous sedimentary rocks
57
Number of
Sample samples -
analyzed
Caucasus, not specified _ 14
Gornyi Altai, not specified 9
Kerch-Tuman area, near mud volcanoes _. . _
Kerch-Tuman area, away from mud volcanoes-
Cambrian, Tyan-Shan_ __ ...
Rock salt, anhydrite, gypsum, Donets Basin. 71
Phosphorites _ - _ . _ _ 20
Iron-rich laterites, Viet Nam
Manganese ores, Nikopol
Manganese ores, Chiatura
Manganese ores, Mangyshlak_ _ ... _ _
Bauxites 4
Kange
Average
50
Demidova, quoted by OzerovaandAidin'yan
(1966b).
40
100
Shcherban, quoted bvOzerova
(1966b).
500
2,800
Karasik and Morozov (1966).
400
600
"540
Do.
70
2,800
Shabalin and Solov'eva (1967)
<100
4,000
""700
Karasik and Goncharov (1963
20
800
70
Ozerova and Aidin'van (1966a,
1,000
2,700
Do.
2^800
Do.
360
530
Do.
65
95
Do.
120
600
460
Do.
Tabi.e 12.—Analyses for -mercury, in parts per billion, in oceanic and laeustrhle sediments
Sample
Red clay, Atlantic .. __
Red clay, Pacific
Red clay, Black Sea___ .
Foramin: feral ooze, Atlantic
Foramin feral ooze, Pacific
Foramin feral ooze, Indian .
Terrigenous ooze, Atlantic
Terrigenous ooze, Indian
Diatomaceous ooze, Pacific
Diatomaceous ooze, Indian __
East Pacific
Fjord sediments. _
Lacustrine sediments
Manganese nodules, Atlantic
Manganese nodules, Pacific. .
Manganese nodules, Indian
Manganese nodules, Atlantic
Manganese nodules, Pacific
1 On a of rbonate-free basis.
Number of
samples -
analyzed
Range
Max
Reference
4
500
1
.800
1,000
Aidin'yan, Ozerova, and Gipp (1963).
2
100
300
200
Do.
4
900
o
u
.000
1,200
Do.
7
80
300
170
Do.
1
50
Do.
O
u
70
150
110
Do.
6
80
550
210
Do.
1
70
Do.
2
60
100
80
Do.
2
200
Do.
1 1
I
400
Bostrom and Fisher t'1969).
2
1,400
2.
000
Landstrom, Samsahl, and Wenner (1969)
2
360
810
Do.
0
<1
810
Harriss (1968).
7
<1
775
Do.
4
<1
3
Do.
2,000
Ozerova and Aidin'yan (1966b).
100
150
Do.
TABLE 13.—Analyses of soils for mercury, in parts per billion
Number of
Sample samples -
analyzed
Most soils, California__
Soils, Franciscan Formation, California _
Soils, un nineralized areas, California
Unmineralized areas, British Columbia _ _ .
Near mineralization, British Columbia
Very nes.r mineralization, British Columbia.
Soils, Germany _ __ .
Topsoils, Sweden ____ __ 273
Topsoils. Africa _ 14
Soils, European U.S.S.R_ _ _ ISO
Soils, Donets Basin _ . _ _ _ _ _. 248
Soils, Donets Basin _
Soils, Kerch Peninsula... . -. ... __ 264
Soils, Kerch-Tainan area
Soils, Vi'3t Nam .. .... __ .
Range
Min
Average
Reference
20
100
40
10
50
250
30
40
<50
100
<100
240
20
40 Williston (1968).
200 Do.
60 Friedrich and Hawkes (1966).
50 Warren, Delavault, and Barakso (1966).
2 . 500 Do.
2 . 500 Do.
290 . Stock and Cucuel (1934a).
60 Anderssen (1967 ).
- . .. 23 Do.
5.800 Aidin'yan, Troitskii, and Balavskaya (1964),
10,000 300 Dvornikov (1963).
2,400 1,300 Dvornikov and Petrov (1961).
3,000 Morozov (1965).
1,900 Karasik and Morozov (1966).
1,000 300 Aidin'yan, Troitskii, and Balavskaya (1964).
-------
58
MERCURY IN THE ENVIRONMENT
Sample
Table 14.—Mercury content of natural wafers, in ¦micrograms per liter
\l microgram per liter —I part per billion mercury]
Range
Number of
samples —
analyzed
Min
Max
Average
Rpfprrnce
Rivers
Rhine River
Saale River, Germany 8 0.05 '0.19
Elbe River, Germany 1 _
Danube River 1 2
Sweden . . 4 .02 .2
European SSSR 24 .4 2.8
Armenian SSR VI 20
Armenian SSR_ 6 I 2 2,0
300 .01 3136
0.1
.07
.09
1.1
4.2
! 1.5
<.1
Stock and Cucuel (1934a).
Ileido and Bohm (1957), and Heide, Lerz,
and Bohm (1957).
Do.
Aidin'van and Balavskava (1968).
Wikander (1968).
Aidin'yan (1962).
Aidin'van (1963).
Do.
Atlantic, Indian, Red Sea, Black Sea, etc 14 0.7 2.0
Atlantic Ocean 9 .4 1.6
Pacific Ocean, Ramapo Deep .08 .15
Do 4 .15 .27
Minamata Bay, Japan 1.6 3.6
0.03
.03
1.1
1
Stock and Cucuel (1934a).
Heide and Bohm (1957).
Aidin'van (1962).
Aidin'yan, Ozerova, and Uipp (1963).
Hamaguchi and others (1961).
TTosohara (1961).
Hosohara and others (1961).
Ground water and miscellaneous samples
Rainwater
Spring water, Germany
Surface waters, Northwest Caucasus „
Subsurface waters, Northwest Caucasus ' ' \
Springs, Elbrus region . _37
(No data in abstract on nature of water.) _
Ground water, Kerch, U.S.S.R .
Ground water, near mud volcanoes, Kerch
Ground water, Abkhazia, U.S.S.R
Mine waters, Abkhazia, U.S.S.R,. . ... - .
Mineralized waters, Abkhazia, U.S.S.R,
Waters of Permian salt beds, Donets Basin... 26
Brines associated with petroleum, Cymric oil-
field, California.
Brine, geothermal well, Sal ton Sea, Calif 1
0.05
.01
< .C
0
<1
1
1
<1
100
0.48 0.2 Stock and Cucuel (1934a).
.05 . Do.
.68 Baev (1968).
1.25 _. _ Do.
80 --1 Kraiaov, Volkov, and Korol'kova (1966!
140,000 Ishikura and Shibuya (1968).
2.5 Morozov (1965).
2.5 __ Karasik and Morozov (1966).
<.5 Zautashvili (1966).
3 .. _ Do.
5 Do.
'8.5 . Karasik, Goncharov, and Vasilevskava
(1965).
400 . Bailey and others (1961).
6 Skinner and otners (19671.
1 The value 0.19 (next highest 0.08) is ascribed to waste water from an industrial
piant.
' ii!xeludi:ig the highest value?.
i Values above 0.1 ppfr were in the drainage area of mercury deposits.
4 Another sample, a concentrate:!. orme, contamec: ppu
-------
TABLES
59
Table 15.—Mercury in air and in volcanic emanations, in nanograms per cubic meter
(1 nanogram ~ 10_} grams]
Number of Range
Sample samples ; Average Reference
analyzed Min Max
''Unpolluted air" _
2
8
Stock and Cucuel (1934b).
Over Paei ic Ocean, 20 miles offshore.
0.6
0.
7
Williston (1968).
California, winter .
1
25
Do.
California, summer . . . _
1.5
50
Do.
.Background, Arizona and California
1.6
7,
9
4.5
McCarthy and others (1969).
Chicago a*ea.. . .. . _ .
22
3
39
9.7
Brar and others (1969).
Kamchatka ... ... ... _ _
10
190
Aidin'van and Ozerova (1966).
Moscow a id Tula regions (no ore deposits) .
80
300
Do.
Over porphvrv copper deposit_ _
12
30
18.8
McCarthy and others (1969).
Do
18.5
53
28
Do.
Over mercury deposit .
12
57.
5
31.4
Do.
Do
58
66
62
Do.
Do .
200
1,200
Karasik and Bol'shakov, quoted by
Aidin'yan and Ozerova (1966).
Volcanic
Air of vent breccias of mud volcanoes
300
700
Karasik and Morozov (1966).
Gases of mud volcanoes. . .. . .
700
2,000
Do.
Gases, Mendeleev and Sheveluch Volcanoes
300
4,000
Aidin'yan and Ozerova (1966).
Gases from hot springs, Kamchatka and
10,000
18,000
Do.
KuriJes.
Condensates from fumaroles and volcanic .
- .2
' 72
Do.
emanations, Kamchatka and Kuriles.
Waters fiom hot springs, Kamchatka and
1 .5
- 4
Do.
Kuriles.
1 Parts per billion.
Table 16.— Mercury in coal, in parts per billion
Number of Range
Sample samples Average Reference
analyzed Min Max
Germany .. 11 1.2 25
Donets Btisin, U.S.S.R 4,500 70,000
Ho _ 140 300,000
Do 206 50 10,000
Donets Basin, U.S.S.R. (in lenses within mer- 2,500 6,500
cury ore body).
Donets Bi.sin, U.S.S.R ... . .. 75 20 20,000
Do 100 7,000
Do 13 100 300,000
12
11,100
46,000
1,100
3.700
46,000
Stock and Cueuel (1934a).
Karasik and others (1962).
Ozerova (1962).
Dvornikov (1963).
Bol'shakov (1964).
Dvornikov (1967a).
Dvornikov (1965, 1967b).
Dvornikov (1968).
-------
Tabus 17.- -Mercury content, in part* per biUum, of selected rocks, smk, and sir,-am sediments
[Type of Hiimple: mine and dump sumples ar« mineral UKRri^ali's, Percentiles: 25, SO, 7I>, and 00 percent, respeetmilv, of the total samples. in »ui'ri set. of data have rm-reary
wnUmt equal In ui Iran I hum Idle Ifeted mercury value; percern ilea were computed tiring a linear mlet;>t»lation of the roimiMivn frequency rtWrtbnllon ol logarithms
of mercury vslunt for each data net. Primary miwlp: the mint. frequent observed mercury content in the Frequency distributions for eaeli set of data' wmwhn nn.de
13 the second m.wl frequent. Kmrn-e of statistical data: »mrn» not shown as published or otherwise explained represent informedion ('on-, computer «toraRci *
ffii
o
Area
Typo of sample
Gila Wilderness, N. Mox Reek ........
Salmon-Trinity, Alps Primitive Area, California . ..Ho _. ...... „
Occur d'Alene, Idaho... . _ ..do .. _
Soil - . ........
Dump .
Bob Marshall Wilderness, Mont Stream sediment .
Ktlna Mountains, Nev ... Hock .. . ...
Stream sediment...
Mine ...
Dump.
Aurora district, California-Nevada __ Rock _
Mine __ .
Dump. _
IvanluKj (mercury district), Nevada. . _ Rock. ._ .. _
Soil.
North Battle: Mountain, Nev.. ____ , . _ Rock
Soil. . . .
Dump. . . --
Mi'ias, Nkv. . . . _ Rock . .......
Soil .... .
1 >ump
Gull of Mexico „ ... Unconsolidated sediment.
Drum Mountain*. Utah _ _ R«ok
Ely, Nev. .do.... _
Rowe Canyon, Nev ...do. ...
Ventana primitive area, Calif .... Metamorphie ruck
Intrusive rock . ....
Sedimentary rock .
Altered ruck. ..., ~ -
Stream sediment. _.
Uncompahgro primitive area, Colorado Vein and mineralized material... _
Altered rock...
I buillered rock .
Stream sediment
Mission Mountains Primitive Area, Munt. ... ... Intrusive rock
Metasedimontary rock
Vein material and altered rock..
Blue Range primitive urea, Ariz, and New Mox _ _ Unaltered rock.
Altered rock... ...... .
Stream sediment. . _ ....
Core Range-Eaglea Nest Primitive Area, Colo, .. Mainly altered rock and vein
material.
San Rafael Wilderness, Calif Sedimentary rock
Carbonate vein material
Fault, gouge and breccia. . .
Stream sediment. _ _
Consejo area, Puerto Rico Sol!
Taylor Mountains, Alaska:
C 8 quadrangle... Outcrop and mineral occurrence.
Stream sediment. . . .
D-8 quadrangle .. do .....
R-ft quadrangle . Outcrop and mineral occurrence.
A-6 and south-half H 6 quadrangles...... do
Stream sediment. w _ ......
Nation River, Alaska Organic-rich shale. _
Brooks Range (north side), Alaska do
Western Missouri Shale _ _
Eastern Minsouri
Missouri (summary) .... Rock.
Kansas City, Mo .. Soil...
Carbonate rock.
Sandstone.
Kentucky. Chattanooga Shale.
North end of Sierra CttcluiUs, N. Mex Arroyo sediment
Silver ("'reek area, Baker, Nev . . ....do.
Luis Lopez district, Socorro, N. Mex Manganese. oi« . .
Little Florida Mountains, N. Mex... .... _do_.._
Colorado Plateau _.Sedimentary rock.
Minimum
Percentile
Number
-
- Maximum
of
Primary
Secondary
Source of statistical data
detected
P'.'i
Pjh
J'Tfi
P.n
detected
samples;
mode
mode
10
41
K4
200
400
7 ,((00
7S1
200
50
J. O. Ratte,
1 0
21
53
too
22:)
500
3ti
50
100
10
10
AO
70
150
57,91)0
2,515
30
<10
G-.jtt nod ot,Iters (19B9).
10
50
100
220
3.SD
ISO,000
5,617
200
f>0
Do.
15
5h
40
230
730
3 , 500
13
200
50
Do.
ID
21
36
1)0
m
220
30S
50
M. R. Mud^e.
10
4:i
•n>
220
f)0i>
9,000
1 . 094
50
20(.)
40
fil
77
170
2,000
2,200
37
70
150
Do,
2(1
45
230
2,400
2,500
27
50
>2,000
Do.
lo
64
InO
KKO
2.500
172
70
200
Do.
10
76
180
490
1,400
150.000
1 ,23H
200
100
N. J. Silberman.
30
.'140
940
2,100
4,900
K, 000
199
1,000
2,000
Do.
10
57
110
290
"HO
150,000
10,000
519
5,000
1,000
10
K2
200
780
3,230
>10,000
I5K1
70
2,000
Do.
20
100
240
550
2 ,070
>10.000
151
300
100
G, B. Gott.
20
51
7!
100
M0
350
103
70
Do,
40
2*0
420
4, 200
», 900
1 f>, 9i>0
15
300
6,000
Do.
20
90
2 on
HuO,
2,500
S, 790
300
290
70
J. M. Kotbol.
20
K8
120
210
340
3,yoo
152
100
Do.
40
420
740
1, 2S0
3,410
6,490
53
1.000
200
Do.
70
95
110
150
220
27
100
10
H6
260
900
4,230
95,000
1)28
200
500
J. IL ^McCarthy, Jr.
10
20
60
170
620
14,000
1,466
20
70
G. B. Gott.
10
30
100
300
660
15,000
445
200
50
Do.
10
25
..
320
35
IVarson ami other* (i967>.
10
... _
40
020
40
Do.
10
30
350
25
Do.
10
.....
40
2,000
134
l>o.
10
HO
290
i 64
Do.
20
260
30,000
225
Fi-schcr and others (1908),
10
_
1 HO
3,800
334
Do,
to
m
710
92
Do.
10
100
700
101
Do.
20
20
00
y
Harrison and others-(1969).
20
20
3K0
254
Do.
20
20
120
40
Do.
10
....
30
ISO
OK
Rati ?• and others (1969).
10
m
11,000
120
Do.
10
50
1 ,200
64H
Do,
10
80
>10,000
796
- -
Tv/eto and othem (1970),
10
40
3,300
192
Gowcr and others (1966),
45
75
520
11
Dt\.
25
22 f>
1 ,000
7
I)n.
10
60
>4,000
91
Do.
10
120
-
1 ,500
57f>
R. K. Learned (this report).
800
14,200
15,000
2-8
Clark and others (1970),
60
' 190
3.000
220
Do.
70
' 540
9,000
199
Do.
240
S, 000
22
Do,
2(H)
. -. _
• 320
700
19
Do.
K0
• 360
_
10,000
59
Do.
40
_
-
•
650
15
. ... _
E, E. Brabb (written commun.,
20
2 570
2.HD0
253
If. A. Tourt-clot (written com-
mun„ 1970).
20
¦ 70
160
5
J. J. Connor (written eommun.,
19V0).
HO
2 40
50
6
Do.
10
_
* 20
.
40
5
Do.
10
M0
1 ,000
19
Do.
HO
1,300
30
Do.
20
: 550
1,500
213
H. A. Tourteiot and J. «T, Connor
(written eommun., 1970).
10
= 19
4M
74
_ .....
W. ii. Griihits and 11. V. Alminan
(written eojumun., 1970).
10
....
'J 2i)
.
54
50
D:».
IB
161
1.000
72
Do.
100
1 ,900
10.000
51
no.
10
160
- - -
10,00s)
3,012
...
R. A. Cadigan (this re{>orU.
PI
a
<3
50
(-H
H
I-T4
K-H
M
M
<1
3
o
ss
g
M
Z
H
5 Oecmetric mean.
-------
TABLES
61
Table 1.?.—Mercury content, in parts per billion, of some sedimentary straiigrajihic vniln in the Colorado Plateau reman of ike. United State?
[Units are arranged in order of youngest (Tertiary} to oldest ^ Permian and rennsylvaniaiii]
Stratigraphie unit
Number
of
samples
Median
Highest
Lowest
Middle
68 percent
of samples
Dominant rock types
Approximate
avorage
'-Viickr.L'SS ffeet)
Tertiary, northern Colorado Plateau region
Duuhesre River Formation
Uinta and Green River Formations
Wasatcl. and Colton Formations
62
60
180
15
260
100
4,000
15
19S
280
1,100
80
37-100 Sandstone
44-240 Shale, sandstone ..
150 520 Mudstone, sandstone _
Mesaverde Group and Mancns Shale
250
CretareouM, northern Colorado Plateau roRion
1,500 30 140 400 Mudstcme, sandstone
240
Jurassic, Colorado Plateau region
Morrison formation 653
Etitrada Sandstone . 258
C arm el Formation ... 80
Navajo Sandstone. 91
Wingate Sandstone . _ 160
Dolores Formation 42
Chinle formation .. — 538
Moenko ii Formation 323
Cutler Formation (Permian) . . - 30
Rico and Hcrmosa Formations (Permian 61
and Pennsvlvanian).
190
170
100
40
>6,000
5,000
700
500
10
30
10
; 10
Triasssic, Colorado Plateau region
260
210
260
110
1,900
760
>6,000
>10,000
SO
80
GO
< 10
Upper Paleozoic, Colorado Plateau region
170
200
1,300
2,200
50
20
90-300
100 370
Sandstone, conglomerate
Limestone, siltstone
1 Sampled only in east part, of region.
- Sampled only in central part of region.
1, 500
8,000
2,000
84-420 Sandstone, mudstone
80-360 Sandstone, _
53-170 Sandstone, siltstone
10 150 Sandstone
140-370 Sandstone
120 370 Sandstone, siltstone
140-460 Mudstone, sandstone
40 320 Siltstone. sandstone...
.000
1.000
500
300
1,000
300
1 300
1 ,000
1,000
11 .000
2 2',000
Tabj.f. 19.—Equilibrium constants and stav
Constant
Equilibrium iK)
Hg^ + :!e=2ng°L __ .... ...
2Hg+'+3e=Hg=+'
•'Is: -2 1:1 .. . _ ... ... _
Hg°l-*-Hg+==Hg,,+' 10===
Hgc 1- tig' aq .. . . ... 10~fi-"a
HgO c-211 1+2e = Hg° 1+H,0
Hg.CU t =Hgn'2+2Cl . 10-!; W
HgCl,°-Hg-2+2Cl-... .
HgClj" ~ Hg'12 + 3C1 ... lO-"-*
HgC!4~2+2e = Hg° 1 +-4C1" ..
HgSO(° aq =Hg l2 + S" =.. ... 10 145
HgS,CiI1I,[b„r1=IIg+=-( S"- 10
HgS.:„„.,„:i;l.la)j.,r, = Hg+= + S....... . ... 10";,3GS
HgS c+3-==HgSr- ... 4.57
Hg(HS)»° — Hg+= + 2IIS . _ 10-17.-3
I i,; \ 11 : • ; 1 g ' • • IN11 a . 10 1535
Hg(CH3C02l'; c + 2H 1 = IIg+!+2CH3COOH aq .. 10-5-l:
Hg(CH3)2 l+2H! =Hg,!+2CHi aq 10- -1"
TIg(CHa)21 + H«0 = CH< aq + CHjOH aq + Hg 1 1019 'J
CH3Hg' +OH" = CHsHgOH aq._ ...... 10J»
C6H6Hg1-+OH-=C(iHsHgOH aq 10"'
CH3HgCl 1 =CH3HgCl aq . 10 1 in
CH3HgCl aq = CH3Hg"'"+Cl- 10-° «
rd potential* at %5°C ami 1 atmosphere pressure
solids,, ag = uitwnsvt'd
E"
{volts] kSoUn-(; of data
0.789 Latimer {1952).
. 921 Do.
. 855 Do.
Do.
Calculated from data in Wagman and others (1969 i.
.925 Latimer (19.-.2).
Do.
Helgeson (1969''.
Do.
.386 Latimer ('1952 i.
Calculated from data in Wagman and others (1869).
Helgeson (1969).
Do.
Calculated from data in Wagman and others 11969),
Do.
. .. _ Do.
Calculated from data .n Latimer (1952) and Wagman
and others (1968).
Calculated from data in Wagman and others (1969).
Calculated from data in Wagman and others (1969).
Waugh and others (1955).
Do.
Do.
Do.
-------
MERCURY IN THE ENVIRONMENT
Table 20.—Standard free energies of formation of certain mercury species, in kilocalories per mok
[Lwadery iinliraU' no eojiunon narruw. I = liquids, g = gases, ct = soHdt;, j»q = dissolved species.
Data, from Latimer (1952) and Wagman arid others (1969)1
Dpsrvriptinn
Hg'J 1 Metallic mercury..
Hg" g Mercury vapor
HgJ aq Dissolved mercury.
Hg,+
Hg«
HgiCli c _
HgCL c
HgO c
HgO c .
HgOH +
HgO OH"....
HglOHaq..
Hgs
HgS c
Hi: SO. c
HgSO.," aq
HgoCOj c
HgCl«° aq
HgClr-
TIgfCHsij 1
Mercurous ion.
Mercuric ior.
Calomel -
Mercuric chloride
Red oxide
Yellow oxide...
Cinnabar.
Metacinnabar
Frw; rju?rgi(is
w°f)
0
16
9
36.
39.
-50
-42
-13.
— 13.
-12.
-45.
-65.
-12.
-11
-149.
-140.
-105.
— 41 .
-107.
0
3
4
70
30
35
7
995
964
5
5
70
1
4
589
6
8
4
Table 21. Mercury concentrations from results of analyses of selected thermal a nd mineral irafers
and their deposits, Northern California. mercury district
"De jt, ! 1 |.:ut ;tcr billion. N.d., not. detected. Analyses by M. [!. llmkiel
Sample
Condensates, condenser coil packed in ice
Mercury
concentration
(in ppb)
McKinley well 1 Lake.
McKinley well 3. _ . . . .do
Waters of low to moderate salinity, T <40°C
Allen Spring. . ... ...... Lake.
Bartlet Spring _ .do
Spring east, of Alice mine.__ . . Colusa.
Waters of high salinity, T <40^0
Grizzly Spring Lake
Abbott Mine water _ . _.do___
Dead Shot Spring .... Colusa
Wilbur oil test, well ..do
Salt spring north of Wilbur Springs . .do
Complexion Spring Lake
Salt Spring north of Stonyford - Glenn
Redeye Spring [Fonts Springs) . Colusa..
3.0
1 .0
N.d.
N.d.
N.d.
N.d.
1 .0
N.d.
0.2
.1
1.5
N.d.
N.d.
Waters of low salinity, T >4DCC
Castle Rock Spring Lake-
Anderson Spring.. _ ..do.
Seigler Spring _ _ do _
N.d.
N.d.
N.d.
Waters of moderate to high salinity, T>40°C
Sulphur Bank Lake.--
Wilbur Springs Colusa.
1.5
1.5
folids
Sulfur floating on Wilbur Springs Colusa..
Magnesia-silica gel from Complexion Spring Lake
Silica-magnesia gel from Aqua de Ney. Siskiyou.
30,000
800
500
-------
TABLES
Table 22.—Mercury concentration* in thermal inters from Yellowstone National Park
"Detection limit, 0.01 part per billion. N.d., not -detected. Analyses by M. E. Hinkle)
Mercury
Location concentration
(,m ppo;
Ojo Caliente Midway Basin 0.14
Bar Spring - do . - - .22
Bonita Spring __do .07
Chinaman Spring do .10
Steady Geyser Lower Basin .07
Snort Spring .. Porcupine Hills __ . .10
Beryl Spring Gibbon Canyon .IS
Little Whirligig Spring Norris Basin._ .07
Cinder Pool _ ..do .28
Spring, base of Porcelain Terrace do ..... .10
Echinus Geyser . . .do .11
Cistern Spring . ..do . _ .08
Primrose Spring Sylvan Soring area . .31
Sulfur Pool do . .. .27
Green Spring do . . .20
Blue Spring ..do .20
New Highland Terrace Mammoth Spring. _ .05
Table 23.—Mercury concentrations from a.nalyses of petroleum from the Wilbur Springs area,
northern California
[Detection limit, 0.01 part per billion. Ami'ysni? by M. "R. Hinldc]
Sam pie
Tarry petroleum, Abbott mine..
Petroleum, Wilbur oil test well.
County
Lake ,.
Colusa.
Mercury
ltration
wb)
iM> 000
1 .000
TABLfci 24.—Mercury in selected rivers of the United States, 1970
'Analyses by M. J. Fishman (U.S. Geological Survey, written commun.. 1970)!
Time sample collected
Source and location
Month-day
Hour
- Mercury
(in ppb)
Gold Creek at Juneau, Alaska.
... 6-
-10
1350
<0
.1
Colorado River near Yuma, Ariz
. _ 6-
-18
<
.1
Welton Mohawk Drain near Yuma, Ariz ... _ .
. _.. 6-
-19
<
.1
Ouachita River downstream from Camden, Ark _
S-
-18
0900
<
.1
St. Francis River at Marked Tret?, Ark
6
19
1000
.1
Santa Ana River below Prada Dam near Riverside, Calif
.... 6-
-29
<
.1
South Platte River at Henderson, Colo _ _
. .. 5-
-19
1410
.3
Blue River upstream of Dillon Reservoir, Colo ... ...
.. . 6-
-22
<
1
French Creek near Breckenridge, Colo _ _
6-
-22
<
.1
Animas River at Silverton, Colo _ . _ _
... 6-
-22
,1
Cement Creek at Silverton, Colo ..
.... 6
OO
<
.]
Red Mountain Creek near Ourav. Colo
6-
-22
17
Red Mountain Creek at Ironton, Colo . .. . _
6-
-22
<
.1
Nuuanu Stream near Honolulu, Hawaii. .....
... _ 6-
-8
0930
.6
Honolii Stream near Papaikou, Hawaii , _
.. .. 6-
-8
1405
<
.1
North Fork Kaukonahua near Wahiawa, Hawaii
.... 6
11
1800
.4
Ohio River near Grand Chain, 111
... 6-
26
1040
.1
Floyd River at Sioux City, Iowa
6-
-9
1645
.2
Kansas River downstream from Topeka, Kans
.... 5-
-19
1130
3
.5
Mississippi River near Hickman, Ky . _
... 6-
-25
1030
<
.1
Merrimack River above Lowell, Mass
... 6-
-8
1100
1
.2
Wolf Creek near Cedar Lake, Mich ... __ _
6-
-7
1100
<
.1
Unnamed tributary to Wolf Creek near Edmore, Mich _ .. .
... 6-
¦7
1000
.1
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MERCURY TN THE ENVIRONMENT
Tablr 24.—Mercurn in selected river* of the. United States, 1970—Continued
[Analyse-.1; by M n (U.S. Geological Survey, written comrnun., 1970)]
Time sample collecteil
Sou 1 1 ation
iVltm
•.-•i-dui'
ft our
Mercurv
t in ?>pb)
Rninv River at International Falls, Minn _ _
r>
14
1245
<
.1
St. Louis River at Scanlon, Minn .. .
(!-
-8
1015
<
.1
Pearl River at Rvram, Miss ..
0
-17
1445
.1
Pascagoula River at Merrill, Miss -
6
¦9
1500
o
.0
Yellowstone River near Billings, Mont
5
14
1500
.1
Missouri River near Great Falls, Mont
5-
-18
1730
<
.1
Missouri River near St. Louis, Ma .. . _ _
6
23
1430
2
.8
Missouri Kiver at Her/nanti, Mo .
6
24
1030
_ 2
Salt Creek near Lincoln, Neb .
6-
-24
0915
. 0
Las Vegas Wash at Henderson, Nov . _ . _
5-
-14
—
<;
.1
I'emigowasset River at Woodstock, N.H
6-
-8
1700
3
.1
Canadian River near Glenrio, N. Mex . . .. .. .
6-
¦10
1100
<
.1
Hudson River downstream from Poughkeepsie, N.Y . _
4-
-7
.1
Hoosic River near North Pownal, Vt., in Rennsselaer County, N.Y
4-
-7
.1
Wappicger Creek near Wappiiigcrs Falls, N.Y
4
23
1045
<
.1
Delaware River at Port .Jervis, N.Y
4-
-23
1420
<
. 1
Beaver Kill at Cooks Falls, N.Y . _ _ ..
4
24
1320
.1
Deer River near Helena, N.Y ... ... __
5
-5
0735
.1
Kaquette River at Kaymocdville, N.Y .
5
5
0945
9
Oswegatehie River at Gouverneur, N.Y . ..
5-
-6
0800
. 7
Osweeatchio River at. Gouverneur, N.Y .. .
6
•16
1200
i
.2
Black River at Watertown, N.Y _ . . . .
-6
1015
A
Black Rive:- near Watertown, N.Y
6
1155
<
.1
Lake Champ.aiu near Whitehall, N.Y .
<
.1
T.ake Champlain near Ticonderoga, N.Y
.1
Lake Champlain near Crown Point, N.Y ..
.1
Raqueite River at Massena. N.Y .
6
16
0840
<'
.1
Raquette River at Raymond ville, N.Y .. ..
fi-
-1f>
0910
<
.1
Raqnette River at Potsjdani, N.Y .
6-
-16
OlioO
.1
Gswegatc-hie River below Natural Dam, St. Lawrence County, N.Y .
6-
-16
1130
<
.1
Oswegatehie River at Hailsboro, N.Y
6
16
1230
2
Chemung River near WeUsburg. N.Y .. .
7-
-6
1015
. 2
Susquehanna River at Johnson Citv, N.Y
7-
-6
1330
.1
Maumee River at Antwerp, Ohio .. . _
6-
-10
i 21 5
0
.0
Scioto River near Chi'lieothe, Ohio
6-
-25
1115
<
.1
Great Miami River near Miamisburg, Ohio..__
6-
_i i
1815
.9
North Canadian River near ITarrah, Okla ......
6-
-30
1000
1
1
North Canadian River near Oklahoma Citv, Ok'.a .
6-
-30
1345
'.i
Whitewood Creek near Vale, S. Dak ...... ...
5
22
1100
<
.i
Paper Mill Creek near Herty, Tex -.
6-
¦9
1015
,i
San Antonio River near Elmendort, Tex
6
11
1100
< .
,i
Blaekwater River at Franklin, Va _ _
6-
-15
0930
1.
.i
Jackson River near Covington, Va .... . ...
6-
-16
0820
<
,i
Bailev Creek near Hopewell, Va .
6-
-IS
0945
.4
Snohomish River near Monroe, Wash . _
7-
-1
1050
< .
.1
North Branch Potomac River near Barnum, W.Va _ _
6-
-3
1600
1.
,2
Wisconsin. River at Wisconsin Rapids, Wis _
6-
-10
1300
.9
Wisconsin River near Nekoosa, Wis . .
6
10
1230
2
.4
North Platte River near Casper, Wvo .... ...
6
23
1215
1
Bighorn River at Kane, Wvo __ ...
6-
-30
1600
< .
1
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TABLES
65
Table 25.—Mercury lereh in natural '/'(tiers ovtslde !)\e. United States
Concentration
Location IhvhIk Rof«'i>nec
('in ]) pb 1
Sea water, vicinity of Helgoland
Lamapa Deep _
Ramapo Deep (Pacific Ocean, southeast of
Honshu, Japan).
Minamata Bay, Japan..
Sea waters of LT.S.S.R
Volga, Don, Araks, and Danube Rivers .
Rivers of European U.S.S.R .
Armenian rivers and Swan Lake Armenia)
Rivers near the mercury deposits of Abkhazia,
U.S.S.R.
Natural waters of Germany.
Saale River, Germany
Uneontaminated river waters of Tt.aly__
Rivers near mercury deposits of Italy
11.03 Stock and Cticuel f] 934;.
.08-0.15 Hainaguchi and others (1961)
.l.>- .2" Hosohara (l'JfilJ.
1.6-3.0 Hosohara and others (1961).
.7 2 Aidin'yan (1962 k
1-2 Aidin'yan and Belavskaya (1963)
.4 2.8 Aidin'yan (1962i.
1-3 Aidin'yan (1963).
..5 3.6 Zautashvili (1966).
.01 .0.) Stock and Cucuel fl934).
.03:V-.l-t." ITeide, Lerz, and Biihm (1957;.
(avg, .067)
.01 •, 0;" Dall'Aglio (1968)'.
Up to 136 Do.
TABLE 26. —Mercury consumption, in kilograms, in the United States for calendar year 19S9 and the first quarter of calendar year 1970
[Fmm "Mineral Industry Surveys,'' Tj.S, nf Minos, first quarter, 1970]
1%9
RiMlisvtillpci S( r*onxti
Tejf.al
92,YYO
6,72K
102,0.51
105.32K
034.425
714,840
70,414
2in,s.44
S.41K
327.267
19.251
24,9Y«
334,270
, 690,5.-,6
38, E02
Primary
K«'disl.illijt:
SiH'Ondary
Total
26,462
26.462
4,036
104
1,140
10,941
414
207
20,562
242
9, S32
6 ,210
16,284
106,77*
20,45*
14,076
141 312
125,752
3,692
129.444
12,699
2,1)36
5,692
20.424
16,2.50
20,252
3,070
39,572
1 ,173
1,173
*7,S72
R7.872
9,280
9.280
2,346
3,416
621
6.382
140,036
5,17.3
1.104
146,314
44S
1, 587
4.520
6,555
- 563,902
- 69.690
¦ 11,055
- 674,647
jato total consiirnptio
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MERCURY IN THE ENVIRONMENT
Tablr 27.—Lethal conevixtmlions of mercnry compound* for various aquatic orga.ni.sms and man
[Data summarized from numerous published reports]
Lethfil
Organism
concen ration
MeTC'iry compound
(ppb)
Aquatic organism
Bacteria:
Escherichia coli
200
Mercuric chloride.
200
Mercuric cyanide.
.100
Ethylmercuric bromide.
300
Phenylmercuric chloride.
300
Ethylmercuric oxalate.
Phytoplankton:
Marine mixture _ _ . .
60
Ethyl mercury phosphate.
Scenedesjnus
30
Mercuric chloride.
150
Mercuric cyanide.
Protozoa:
Microregma _ _ _
150
Mercuric c-hloride.
160
Mercuric cyanide.
Zooplankton:
Vaphnia pidex ..
0
Phenylmercuric acetate.
Daphnia magna
20
Mercuric cyanide.
6
Mercuric chloride.
Amphipod:
Mannogammaru# marinm . .
100
Mercuric chloride.
Isopod:
Meaospheroma oregonensk..
15
Mercuric nitrate.
Flatworm:
Polycelis nigra __ ..
270
Mercuric chloride.
Polychaete:
Mercieretta enigmaiica
1,000
Mercuric nitrate.
Mollusca:
Bivalve larvae.. _
... 27
Mercuric chloride.
Australorbis glabratus _ -
1,000
Do.
Fish;
Stickleback .. -
20
Mercuric nitrate.
4-020
Mercuric chloride.
Guppv__ _____
20
Mercuric nitrate.
20
Mercuric chloride.
Shiner
800
Ethyl mercury phosphate.
Eel
27
Mercuric chloride.
Channel catfish
580
Phenylmercuric acetate.
1,300
Ethyl mercury phosphate.
Rainbow trout.
2,000
Pyridylmercuric acetate.
9,200
Mercuric chloride.
Salmon,. , . . _
20
Phenylmercuric acetate.
50
Mercuric acetate.
Man
Adult, death
'1.0
Mercuric chloride.
Adult, chronic illness _
1 ,i
Do.
1 Gram.
-------
TABLES
Table 28.—Maximum mercury concentration in air measured at Mattered mineralized and non-
mineralized areas of the Western United Stales
[ , no clata available]
Sample location
Maximum Hg concentration (ng/m1)5 'l
Ground 400 fpet abovo
surface the ground i
Mercury mines
Ord mine, Mazatza.1 Mtns., Ariz 20,000 (50) 108 (4)
Silver Cloud mine, Battle Mtn., Nev 2.000 (50) 24 (8)
Dome Ruck Mtns., Ariz 128 (6.) 57 (20)
Base and prnclnus metal mines
Cerro Colorado Mtns,, Ariz 1,500 (15) 24 (2)
Cortez gold mine, Crescent Valley, Nev 180 (60) 55 (4)
Ooeur d'Alene mining district, Wallace, Idaho . 68 (40)
San Xavier, Ariz 25 (3)
Porphyry copper mities
Silver Bell mine, Arizona 58 (3)
Ksperanza mine, Arizona.. .. . . 32 (3)
Yekol Mtns., Ariz 32 (4)
Ajo mine, Arizona . . . . 30 (3)
Mission mine, Arizona 24 (3 )
Twin Buttes mine, Arizona - . . . 20 22 (3)
Pima mine, Arizona 13 (3)
£ afford, Ariz 7 (2)
Unmineraiized areas
Blvthe, Calif . 9 (20)
Gila Bend, Calif . .. 4 (2)
Salton Sea, Calif ....... - 3.5 (2)
Arivaca, Ariz 3 (2)
1 rig/m' =nanograms (10-J grams) per cubic meter of air. 1 ng/rn* =10_G ppb,
2 Number of measurements shown in parentheses.
3 Samples taken from single-engine aircraft.
U.S. GOVERNMENT PRINTING OFFICE; 1070 €>—409-302
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