Mercury in the

Environment

GEOLOGICAL SURVEY PROFESSIONAL PAPER 713

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
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.G. 20402
FOREWORD

Current interest in the distribution of mercury in the natural environment stems from two related concerns:

1. Mercury is an essential metal for industry, the known domestic resources 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 mercury as part of its basic mission of determining the occurrence and distribution 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. Furthermore, 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 distribution 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

CONTENTS

Page

Foreword __________________________________________ III 

Summary _____________________________________________ 1 

Summary of the literature on the inorganic geochemistry of mercury by

Michael Fleischer __ _________ 6 

Mercury content of rocks, soils, and stream sediments by A. P. Pierce, J. M.

Botbol, and R. E. Learned ___________________ _____ 14 

Mercury in sedimentary rocks of the Colorado Plateau region by R. A. Cadigan 17 

Chemical behavior of mercury in aqueous media by John D. Hem _______ 19 

Mercury contents of natural thermal and mineral fluids by D. E. White, M. E.

Hinkle, and Ivan Barnes _ ________ 25 

Sources and behavior of mercury in surface waters by R. L. Wershaw 29 

Biological factors in the chemistry of mercury by Phillip E. Greeson 32 

Mercury content of plants by Hansford T. Shacklette ___ 35 

Mercury in the atmosphere by J. H. McCarthy, Jr., J. L. Meuschke, W. H.

Ficklin, and R. E. Learned _____________ 37 

Atmospheric and fluvial transport of mercury by E. A. Jenne 40 

Analytical methods for the determination of mercury in rocks and soils by

F. N. Ward _______________________________________ 46

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, Blythe, 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 liparites 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
VI CONTENTS

TABLE 8-12. Analyses for mercury in Pafire

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

16. Mercury in coal ___ ________ 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

States __________________________ 61

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
MERCURY IN THE ENVIRONMENT

SUMMARY

Mercury, 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 131/2 times as heavy as 

water, and it is the only metal which occurs in liquid 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 ROCKS

Although there are more than a dozen mercurybearing 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 replaced quartz, in rocks near recent volcanic or hotspring 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 mercury and average 100 ppb. The mercury content of 

soils averages about 100 ppb and varies within relatively narrow limits. Sedimentary rocks resulting 

from weathering and deposited by physical, chemical, and biological processes also generally average 

less than 100 ppb of mercury and seldom exceed 200 

ppb except for certain organic-rich shales which 

may reach concentrations of 10,000 ppb or more.

In addition to organic-rich shales, other rocks 

with abnormally high mercury contents are known 

to exist. The Donets Basin, Kerch-Taman area, and 

the Crimea of the Union of Soviet Socialist Republics where both igneous rocks and sedimentary 

rocks commonly contain 100 times the normal maximum (up to 20,000 ppb), probably are the best examples, but similar anomalies can be found elsewhere. 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 California, 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 deposits 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/m8 

(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 IVs cubic yards. Expressed on a weight basis rather than on a volume 

basis (for comparison with contents of rocks) 

20,000 ng/m8 represents almost 16 pounds of mercury per billion pounds of air. Because of similarities in the mineral systems, the next highest nearground levels of atmospheric mercury occur over 

precious metal ores (up to 1,500 ng/m8 ) and copper 

ores (20 ng/m8 ) in that order.
MERCURY IN THE ENVIRONMENT

Whatever the source of natural atmospheric mercury, 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 surface of the land and diminishes with altitude. For 

example, a concentration of 20,000 ng/m3 of mercury at ground level near a mercury mine was observed to diminish to only about 100 ng/m8 at 400 

feet altitude, and a ground-level concentration of 

600 ng/m8 at noon has been observed to drop to only 

20 ng/m8 at 2:00a.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 essentially 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, AND 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 contain less than 0.1 ppb of mercury. This reflects the 

relatively low concentration of mercury in rainwater 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 has 

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. Finegrained muds from pots and mud volcanoes in Yellowstone 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 Sulphur Bank Spring in California.

Because of mercury's tendency to sorb readily on 

a variety of earth materials, particulate matter suspended 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 pollution. Sediments immediately downstream of mercury ore deposits and mercury-contaminated industrial 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 environmental 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 concentration 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 tendency of mercury to sink rapidly and combine with 

sulfide in anaerobic bottom sediments to form cinnabar, which is slightly soluble, appears to be a major 

scavenging mechanism. Another mechanism which 

keeps content of dissolved mercury low is the relatively high reactivity of mercury with organic sub-
SUMMARY 3

stances and the resulting uptake by living and nonliving organic matter.

Because they serve as sediment traps and habitats for aquatic organisms, lakes and ponds are 

likely to serve as traps for mercury which enters 

them. The significance of such accumulations depends 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 environment, such inorganics generally are utilized by low 

forms of life which in turn serve as steps in the 

food chain 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 chain, it is assimilated by organisms living in 

environments which contain it. This process is 

thought to be enhanced through conversion of inorganic mercury by certain anerobes to methyl mercury, a more soluble form. However, there still is no 

proof that proper energy gradients exist to promote 

such reactions. Mercury tends to concentrate in living tissue once it has been assimilated, and there is 

some evidence that the extent of concentration increases 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 concentrations of ethyl mercury showed mercury concentrations ranging from 4,000 ppb in muscle tissue to 

22,800 ppb in the blood; almost complete elimination 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, generally 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 compound. Human tolerance has not been thoroughly investigated, 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 quality of the environment and the genetic characteristics 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 extremely high say 40,000 ppb or more in the vicinity 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 metallic form. Droplets of pure mercury have been 

found in seed capsules of members of the chickweed 

family and similar droplets of mercury occur under 

moss covers of forest floors near mercury deposits. 

In plants, as in animals, mercury tends to concentrate in fatty parts so that vegetable fats are relatively rich in mercury whenever the metal is present 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 thermometers in greenhouses for fear of breaking them and 

poisoning the plants. On the other hand, the same 

roses can be sprayed with organic mercury fungicide with little or no ill effects.

FOSSIL FUELS

Throughout eons of time, the products and residues of geochemical processes and the life cycles of 

terrestrial and aquatic organisms have combined to 

yield very appreciable mercury contents and distinct regional patterns in fossil fuel deposits upon 

which the world depends for much of its energy. 

Typical samples of bituminous coal from the United
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 California 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 scientific 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 metric tons per year primarily from mines in seven or 

eight western states although it occurs as a minor 

constitutent 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 mercury compounds from industrial processes in this 

country are estimated at 600 tons per year and superimpose a significant amount of manmade pollution upon the pattern established by nature. Bacteriacides flowing down the sinks of hospitals, 

pesticides and fungicides leaching or eroding from 

agricultural land, and waste effluents from causticchlorine plants and other industries add waste mercury to the water and the air often as point 

sources of pollution which are particularly troublesome. Recent studies of an Interior Department 

task force revealed mercury contents of many industrial 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 concentrations of mercury. The death of about 50 people from eating mercury-tainted fish from Minamata 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 effort to develop better methods of detecting mercury ; better systems for assessing its pattern in the 

environment; better understanding of its behavior, 

including its effects on human beings; better legislation for whatever control appears to be desirable 

and practicable.

DETECTION

Although simple prospecting methods have been 

available for a long time, advanced analytical methodology 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 chemical dithizone colorimetric method, through a series 

of spectrographic, 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 procedure, which presently is preferred for water analysis, 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 conserve 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=l 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=l 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.
SUMMARY 5

/*g/l (micrograms per liter). Equivalent to parts per billion for concentration in the atmosphere. 1 ng/ms~l/l,000

in dilute solution such as relatively pure water. ppb.

mg/1 (milligrams per liter). Equivalent to parts per million > = greater than.

in dilute solutions such as relatively pure water. 1 _

mg/l = l,000 jig/lsl ppm=l,000 ppb. <=less than.

ng/m3 (nanogram per cubic meter (of air)). Generally used ~=approximately.
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 average 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 averages of abundance of doubtful significance.

Most sedimentary rocks have mercury contents 

less than 200 ppb Hg, except for shales, clays, and 

soils, for which the data show considerable variation with average contents of a few hundred parts 

per billion Hg. Shales rich in organic matter are notably 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 analyses 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 plausible 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 California.

Most natural waters (ground water, river water, sea water) contain less than 2 ppb Hg. High 

concentrations of mercury have been found in waters from hot springs and in brines from a petroleum field in California. Mercury is presumably dissolved by ground waters passing over rocks and is 

added to waters in considerable amounts by industrial 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 background values of less than 1 to a few nanograms 

(10-9 g) per cubic meter. Over metallic ore deposits, 

the content of mercury is appreciably higher. Volcanic emanations including those of mud volcano 

type, have high contents of mercury, and must contribute a large amount of mercury to the atmosphere. In addition to such "natural pollution," one 

must assume that mercury is added to the atmosphere by the burning of coal and petroleum and 

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 "man-made" pollution.

GENERAL GEOCHEMICAL CHARACTERISTICS 

OF MERCURY

Mercury has the atomic number 80 and atomic 

weight 200.59. It has seven stable isotopes with percent 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 mercury. 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 unusually high volatility accounts for its presence in 

the atmosphere in appreciable amounts. Its ionic 

radius (Hg+2 ) is generally given as 1.06-1.12 angstroms, so that in the lithosphere it might be expected 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.
SUMMARY OF THE LITERATURE

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 geochemical cycle of mercury or 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 per billion or parts per million.

Many methods have been used for the determination of these small amounts of mercury. Among 

them are the spectrographic method (usually with a 

sensitivity of 100 ppb, and extended to 10 ppb in 

improved procedures), separation of mercury by 

distillation followed by determination by measurement of the collected mercury globule or by a colorimetric method (the latter used in most of the analyses in the U.S.S.R.), separation by extraction and 

colorimetric determination, neutron activation analysis, and atomic absorption spectrophotometry.

Comparative data on precision and accuracy are 

available only for the last two methods. (See table 

I.1 ) Comparison of the data published by many investigators 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, for example, Friedrich and Hawjces (1966), 

James (1962), Ozerova (1962), Saukov (1946), 

and Warren and others (1966).) As a result, it is 

necessary to discriminate between normal samples 

and those from mineralized areas.

A further problem is that the data show very 

clearly that some areas in the world (notably the 

Donets Basin, Kerch-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 how many such areas 

there may be.

* Tables are in 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 are 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 silicic igneous rocks, although there is a slight suggestion 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 mercury, 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 minerals 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 certain 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 represent analytical error, but this seems unlikely because one of the laboratories reporting them has 

also reported low "normal" values for similar rocks 

from other areas (table 3). The two areas have 

some mercury mineralization; they also are near 

areas of mud volcanoes that 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 reported in table 6, even though the volcanic activity 

of this area also contributes considerable amounts 

of mercury.

MERCURY IN METAMORPHIC ROCKS

The few analyses available of mercury in metamorphic rocks (table 7) show the same wide variation 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.

MERCURY 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 lacustrine 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 averages 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 anomalously high. It has been suggested that these rocks 

might have been enriched in mercury by accumulation of the exhalations of mud volcanoes (tables 10, 

11, 13, 15). The data of table 11 and table 12 suggest that mercury is enriched in sedimentary Fe 

and Mn ores, perhaps by adsorption or coprecipitation. Bituminous shales are notably richer in mercury than other shales, suggesting the possibility 

that mercury may be present as some form of organic complex.

The analyses of soils in table 13 are similar in 

general range to those of shales and clays. High values in soils above mineralized zones have been reported by many investigators. It has been suggested 

that the widespread use of organic mercury compounds as seed fungicides has increased the content 

of mercury in cultivated soils, but no data on this 

have been found.

MERCURY IN COAL AND PETROLEUM

The data on coals (table 16) are unrepresentative. 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 samples contained less than 1,000 ppb Hg. Headlee and 

Hunter (1953) 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, Vasilev'skaya, Petrov, 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 variously 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 mercury 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 mercury are 

those of Bailey, Snavely, and White (1961), who 

found 1,900 to 2,900 ppb Hg in petroleum from the 

Cymric field, California.

MERCURY IN NATURAL WATERS

The available data on mercury in natural waters 

are given in table 14. Most contain tenths of a part 

per billion to a few parts per billion. Insufficient 

data are given to permit assessment of the contribution of contamination. The mercury content of Atlantic Ocean waters is stated to increase with the 

amount of suspended material. The suspended matter of three samples of river waters contained 0.03 

to 0.2 percent Hg, according to Kvashnevskaya and 

Shablovskaya (1963), but the proportions of mercury 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 solution when ground waters react with cinnabar or 

other mercury minerals, but this is removed almost 

completely when the solution is passed over mudstones. This is in accord with data of Dall'Aglio 

(1968) and with the experiments of Krauskopf 

(1956), who showed that mercury is removed almost quantitatively from sea water by adsorption 

on Fe(OH) 8 or clay; the analyses of oceanic manganese 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 deposit 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

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 mercury.

Industrial pollution, notably by alkali-chlorine 

plants using the mercury cell method and by the 

paper pulp industry, has been referred to extensively 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 lowest figures presumably represent unpolluted air, 

which apparently contains less than 1 to perhaps 10 

ng/m3 Hg. "Natural pollution" caused by the volatility of mercury from ore deposits of mercury or 

base metals gave values up to 62 ng/m3 . It is evident, however, that much higher concentrations and 

very large amounts of mercury reach the atmosphere from volcanic emanations, including those 

from mud volcanoes.

The effects of industrial pollution probably account for 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. Another 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 mercury 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, D. V., Divakov, K. S., and Rad'ko, V. I., 1965, Mercury 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.

Spectrographic analyses gave average contents of 90, 

700, 4,000, and 5,000 ppb Hg in four granosyenite porphyry intrusives. Argillaceous marls contained 10 to 

8,000 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.

Analyses of 23 igneous rocks are given.

Aidin'yan, N. Kh., 1962, Content of mercury in some natural waters: Akad. Nauk SSSR, Trudy Inst. Geol. Rudn, 

Mestorozhd., Petrog., Mineral., Geokhim. 70, p. 9-14 (in 

Russian); Chem. Abs. 57, p. 16336,1962.

Colorimetric analyses gave 0.4 to 2.8 jug/1 Hg (avg, 1.1 

fig/I) in 24 rivers, European SSSR. Fourteen waters 

from seas and oceans gave 0.7 to 2.0 ,/ug/l Hg (avg, 1.8 

/*/!).

 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 pg/l Hg; one 

contained 20 /tg/1 Hg.

Aidin'yan, N. Kh., and Belavskaya, G. A., 1963, The problem 

of supergene migration of mercury: Akad. Nauk SSSR, 

Trudy Inst. Geol. Rudn. Mestorozhd., Petrog., Mineral., 

Geokhim. 99, p. 12-15 (in Russian); Chem. Abs. 59, 

p. 8471, 1963.

Solutions passed over cinnabar dissolved appreciable 

amounts of Hg. This was removed almost completely by 

passing the solutions through mudstones.

Aidin'yan, N. Kh., Mogarovskii, V. V., and Mel'nichenko, 

A. K., 1969, Geochemistry of mercury in the granitic 

rocks of the Gissar pluton, central Tadzhikistan: 

Geokhimiya, p. 221-224; translation in Geochemistry Internat. 6, p. 154-158, 1969.

Analyses of 64 granites and granodiorites gave 10-75 

ppb Hg (avg, 30 ppb Hg).

*Aidin'yan, N. Kh., and Ozerova, N. A., 1964, Geochemistry 

of mercury during volcanism: Problemy Vulkanizma 

(Petropavlovsk-Kamchatski! Dal'nevost. Kn. Izd.) Sbornik, p. 30-32 (in Russian); Chem. Abs. 63, p. 2795,

1965.

See Ozerova and Unanova (1965).

 1966, Some genetic features of the formation of mercury-containing mineralization from the study of contemporary volcanic activity: Akad. Nauk SSSR, Inst. 

Geol. Rudn. Mestorozhd., Petrog., Mineral., Geokhim., 

Ocherki Geokhim. Endogenn. i Gipergenn. 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, Geochemistry of mercury: Problemy Geokhim. Kosmol. 1968, p. 

160-165 (in Russian); Chem. Abs. 70 (7), p. 148, 1969.

A review.

Aidin'yan, N. Kh., Ozerova, N. A., and Gipp, S. K., 1968, 

The problem of the distribution of mercury in contemporary sediments: Akad. Nauk SSR, Trudy Inst. Geol. 

Rudn. Mestorozhd., Petrog., Mineral., Geokhim. 99, p. 

5-11 (in Russian); Chem. Abs. 59, p. 7262, 1968.

Analyses are given of Atlantic Ocean waters, 0.4-1.6 

/ig/1 Hg (avg, 1.2 jug/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., Geokhim. 99, 

p. 16-25 (in Russian); Chem. Abs. 59, p. 7261, 1963.

Analyses of 179 alkalic rocks gave 30-4,000 ppb Hg 

(avg, 530 ppb Hg). Analyses of many minerals are 

given.

Aidin'yan, N. Kh., Shilin, L. L., and Unanova, 0. G., 1966, 

Contents of mercury in rocks and minerals of the Lovozero massif: Akad. Nauk SSSR, Inst. Geol. Rudn. 

Mestorozhd., Petrog., Mineral., Geokhim., Ocherki Geokhim. Endogenn. i Gipergenn. Protsessov 1966, p. 14-19 

(in Russian) ; Chem. Abs. 66, p. 5475,1967.

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. L, and Balavskaya, G. A., 

1964, Distribution of mercury in various soils of the 

U.S.S.R. and Vietnam: Geokhimiya, p. 654-659; translation 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: Grundforbattring, 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 /*g/l Hg and for 

subsurface waters 0.25-1.25 /tg/1.

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. 459- 

462, 1964.

High contents of Hg were found in coals and associated shales and sandstones in a mercury ore deposit. 

Analyses are given.

Bostrom, Kurt, and Fisher, D. E., 1969, Distribution of mercury in east Pacific sediments: Geochim. et Cosmochim. 

Acta 33, p. 743-745.

Oceanic sediments contained 1-400 ppb Hg (carbonate-free basis).

Brandenstein, M., Janda, L, and Schroll, E., 1960, Rare elements in German coals and bituminous rocks: Tschermaks 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 spectrographic method used ).

Brar, S. S., Nelson, D. M., Kanabrocki, E. L., Moore, C. E., 

Gurnham, C. D., and Hattori, D. M., 1969, Thermal neutron activation analysis of airborne particulate matter 

in Chicago Metropolitan area: Natl. Bur. Standards 

Spec. Pub. 312, v. 1, p. 43-54.

Analyses for Hg in air were made at 22 stations.

Bulkin, G. A., 1962, The geochemistry of mercury in the Crimean 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).

DalFAglio, M., 1968, The abundance of mercury in 300 natural water samples from Tuscany and Latium (central 

Italy), in Origin and distribution of the elements: Internat. Earth Sci. Ser. Mon., 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 mineralization 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 distribution of mercury in soils and coals of the southeastern 

part of the Donets Basin: Akad. Nauk SSSR Doklady 

150, 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 coals contained 50-10,000 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 Russian); 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-Khrustalnaya basin (Donbass): Akad. Nauk
SUMMARY OF THE LITERATURE 11

RSR Dopovldl, Ser. B., 29, p. 293-298 (in Ukrainian); 

Chem. Abs. 56, p. 5298,1967.

Analyses showed 100 to 7,000 ppb Hg, which was concentrated in the iron sulfides.

 1968, Some features of geochemical anomalies in coals 

in the endogenic aureole of dispersion of the Nikitov 

mercury deposits: Akad. Nauk Ukrayin. RSR Dopovidl, Ser. B., 1968 (8), p 732-735 (in Ukrainian); Chem. 

Abs. 70, p. 145, 1969.

Analyses of coals associated with a mercury deposit 

showed 100 to 300,000 ppb Hg (avg, 46,000 ppb Hg).

Dvornikov, A. G., and Klitchenko, M. A., 1964, The distribution of mercury in intrusive rocks of the Nagolnyi 

Ridge: Akad. Nauk Ukrayin. RSR Dopovldl, p. 

1354-1357 (in Ukrainian); Chem. Abs. 62, p. 3841, 

1965.

Camptonite and plagiogranite in an 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. 

1021-1028, 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 

analysis: Geochim. et Cosmochim. Acta 31, p. 357-376.

Many analyses are given. Noteworthy are the high 

contents reported for eclogites and kimberlites.

Friedrich, G. H., and Hawkes, H. E., 1966, Mercury dispersion 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; Geokhimiya, p. 256-261 (in Russian).

Analyses of 70 samples gave an average of 28 ppb 

Hg.

*Hamaguchi, Hiroshi, Kuroda, Rokuro, and Hosohara, Kyoichi, 1961, Photometric determination of traces of mercury in sea water: Nippon Kagaku Azsshi 82, p. 

347-349 (in Japanese); Chem. Abs. 55, p. 15222,1961.

Analyses of waters from the Ramapo Deep, Pacific 

Ocean, gave 0.08-0.15 ng/1 Hg (avg, 0.1 /tg/1 Hg).

Harriss, R. C., 1968, 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 Engineering Chemistry, v. 45, p. 548-551.

Analyses of 596 samples from 16 seams, West Virginia, showed <100 to 260 ppb in the coal ash (ash content not given).

Heide, F., and Bohm, G., 1957, The geochemistry of 

mercury: Chemie Erde, v. 19, 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 Japanese) ; Chem. Abs. 56, p. 4535, 1962.

Analyses of four samples from the Ramapo Deep, Pacific Ocean gave 0.15-0.27 /ug/1 Hg.

*Hosohara, Kyoichi, Kozuma, Hirotaka, Kawasaki, Katsuhiko, 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 

/ug/1 Hg. Plankton contained 3,500-19,000 ppb Hg.

*Ishikura, Shunji, 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 

geochemical prospecting: Imperial Coll. Sci. Technol., 

Geochem. Prospecting Research Centre Techn. Comm., 

(41), p. 1-42. 

A review.

Jovanovic, S., and Reed, G. W., 1968, Mercury in metamorphic rocks: Geochem. 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, 1963.

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: Geokhimiya, p. 117-121; translation in Geochemistry Internat. 

2, p. 82-86,1965.

Analyses of 26 waters from evaporite beds showed 

<1 to 8.5 pg/l Hg, except for one sample with 220 ug/1 

Hg.
12 MERCURY IN THE ENVIRONMENT

Karasik, M. A., and Morozov, V. I., 1966, Distribution of 

mercury in the products of mud volcanism in the 

Kerch-Taman Province: Geokhimiya, p. 668-678; translation in Geochemistry Internat. 3, 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 Hg.

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 Donets Basin: Akad. Nauk Ukrayin. RSR Geol. Zhurn. 22, 

(2), p. 53-61 (in Ukrainian); Chem. Abs. 57, p. 2513, 

1962.

Ranges of Hg content are given for 488 coals; about 

half are well above background.

Krainov, S. R., Volkov, G. A., and Korol'kova, M. Kh., 1966, 

Distribution and mode of migration of the trace elements Zn, Cu, Hg, Li, Rb, Cs, As, and Ge: Geokhimiya, 

p. 180-196; translation in Geochemistry Internat. 3, p. 

108-123, 1966.

Analyses of waters in the Elbrus volcanic region 

showed <0.5 to 80 /ug/1 Hg; most samples had 1 pg/l Hg 

or less.

Krauskopf, K. B., 1956, Factors controlling the concentrations of thirteen rare metals in sea-water: Geochim. et. 

Cosmochim. Acta 9, p. 1-32B.

Experiments show that Hg may be removed from sea 

water by adsorption on Fe (OH)3 or clay, or by take-up 

by plankton.

*Kurmanaliev, K. K., 1967, Presence of mercury in Cambrian 

formations of Madygen village, southern 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, 0., Samsahl, K., and Wenner, C. G., 1969, An investigation 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 background content in the air over two porphyry copper deposits; seven to 13 times normal background content in 

air over two mercury deposits.

Morozov, V. L, 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 Otdel, 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, and 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., Geokhim., 

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 mineralization.

Ozerova, N. A. 1962, Primary aureoles of dispersion of mercury: Akad. Nauk SSSR, Trudy Inst. Geol. Rudn. Mestorozhd., Petrog., Mineral., Geokhim. 72, p. 1-135 (in 

Russian).

A review, with many new analyses of minerals, igneous 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 Mineral Resources, p. 312-318, 1966.

Analyses of 500 sedimentary rocks are given.

 1966b, Mercury in sedimentary processes: Akad. Nauk 

SSSR, Inst. Geol. Rudn. Mestorozhd., Petrog., Mineral., 

Geokhim., Ocherki Geokhim. Endogenn. 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 formation in the Mendeleev Volcano, Kurile Islands: Geol. 

Rudn. Mestorozhd. 11 (5), p. 17-33 (in Russian).

Analyses are given of lavas, opalite, and iron sulfldes 

from cinnabar-containing altered dacites in a solfatara 

area.

Ozerova, N. A., and Unanova, 0. 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 OP THE LITERATURE 13

Analyses are given of 63 basalts, 209 andesites, and 

two dacites.

*Panov, B. S., 1959, Mercury in volcanic rocks of the southwestern 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 contents of Hg.

Preuss, E., 1940, Spectrographic methods. II. Determination 

of Zn, Cd, Hg, In, Tl, Ge, Sn, Pb, Sb, and Bi by fractional 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., 1946, Geochemistry of mercury: Akad. Nauk 

SSSR, Trudy Inst. Geol. Nauk 78, p. 1-129 (in Russian.

A review.

*Shabalin, 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 1967, 

p. 103-108 (in Russian); Chem. Abs. 68, p. 502,1968.

Analyses of five series of sedimentary rocks.

Shcherbakov, V. P., Dvornikov, A. G., and Zakrenichnaya, G. 

L., 1970, New data on the forms in which mercury occurs in coals of the Donets Basin: Akad. Nauk Ukrayin 

RSR DopovidI, Ser. B, 32 (2), p. 126-130 (in Ukrainian) ; Chem. Abs. 73 (4), p. 180,1970.

A considerable part of the Hg present in these coals 

is present as organic compounds, in part humic acids.

Skinner, B. J., White, D. E., Rose, H. J., Jr., and May, R. 

E., 1967, Sulfides associated with the Salton Sea geothermal brine: Econ. Geology, v. 62, p. 316-330.

A brine contained 6 ppb Hg.

Stock, Alfred, and Cucuel, Friedrich, 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, Alfred, and Cucuel, Friedrich, 1934b, The determination of the mercury content of air: Deut. Chem. Ges., 

Ber., 67B, p. 122-127 (in German).

Analyses showed 8 ng/m8 Hg in two samples of uncontaminated air.

Tkach, B. I., 1966, Geochemical characteristics of the distribution 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.

Tunell, George, 1964, Chemical processes in the formation of 

mercury ores and ores of mercury and antimony: Geochem. et Cosmochim. Acta 28, p. 1019-1037.

A discussion, including the deposition of mercury sulfides from hot springs.

 1968, The geochemistry of mercury, in Handbook ef

chemistry: Berlin, Springer Verlag, 65 p. (In press). 

A review.

Warren, H. V., Delavault, R. E., 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 traverses from unmineralized to mineralized areas.

White, D. E., 1955, Thermal springs and epithermal ore deposits: 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., Buddington volume, p. 397-428.

Description, with analyses of hot springs depositing 

mercury sulfides.

*Wikander, Lambert, 1968, Mercury in ground and river 

water: Grundforbaettring 21, p. 151-155 (in Swedish); 

Chem. Abs. 70, (7), p. 208, 1969.

Analyses are given of 36 waters drained from cultivated soils and of four river waters; 38 samples showed 

0.02-0.07 jig/1 Hg (avg, 0.05 ftg/l Hg), two showed 0.2 

fig/IWilliston, S. H., 1968, Mercury in the atmosphere: Jour. 

Geophys. Research, v. 73, p. 7051-7055.

Analyses of air from California. Most s.ils have 

20-40 ppb Hg, but some have 100-200 ppb, even in apparently unmineralized areas.

Zautashvili, B. Z., 1966, The problem of mercury hydrogeochemistry, 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 <ug/l).
MERCURY CONTENT OF ROCKS, SOILS, AND STREAM SEDIMENTS

By A. P. PIERCE, J. M. BOTBOL, and R. E. LEARNED

Mercury is routinely determined in U.S. Geological Survey laboratories with atomic absorption 

equipment developed by Vaughn (1967). An independent check by J. H. McCarthy, Jr., of this 

method against the method of neutron activation is 

summarized below:

Determination of mercury in parts per billion in U.S. Geological Survey rock standards

Standard rock No.

J.

Investigator

H. McCarthy (in Flanaean. 1969}

Ehmann and Love-ring (1967) ___ ' ________ .

Method

 Neutron

absorption 

activation

G-2

50 

39

GSP-1

15 

21

AGV-1

15 

4

PCC-1

10

4

DT&-1

8

4

BCR-1

5

7

With the possible exception of standard rock 

AGV-1, the analyses with two entirely independent 

methods compare remarkably well, especially considering 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 available sources: analytical data that are computer 

stored and that are immediately available for processing, data that have already been published, and 

data that are in the process of publication and 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 central 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 materials.

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 mercury concentrations, or abundance, are relatively 

complex functions of geologic conditions and that 

criteria for either mercury mineralization or abnormal mercury contamination should be evaluated separately in any single area of interest.

The modal mercury values canvassed in table 17 

also indicate that mercury tends to occur most frequently at certain concentrations. For example, 

modes at about 50 ppb and at about 200 ppb are especially common. The tendency may be identified 

both with sample type and with the effects of specific geologic processes, occurring at or near the 

surface in the area sampled. The common occurrence of mercury ores in concentrations of about 0.1 

to 0.8 percent .mercury (1,000 to 8,000 ppm) (Lovering, 1969, p. 115) may be another instance of this 

tendency, although it represents the effects of geologic processes operating under rare geothermal 

conditions.

The percentile ranges of mercury distributions 

for the first 13 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 concentrations 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) mercury mineralization processes or (2) surface contamination 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 previously, firm criteria for determination of anomalous mercury values should be evaluated individually for each area of interest.

14
ROCKS, SOILS, AND STREAM SEDIMENTS 15

I0«

z 

o

CD (03

CC 

U 

Q.

V) \- 

CC

Q.

Z

o 

o:

UJ

10

1 1 1 1

ROCK

I I 

i i i |

""" |_j

i i

r- 1 i i

iiii ii i i eg

ii r-i ii

Ivanhoej"1^ \ \ |~^ tan II II ||

n > i ii

p^ ju3 > ^ i j rn ii

ii ii r"^ j j

B am ii

n i\ B

i i rs i i fl

^i ^^ H wI-H

1 1 *""

1 1

1 1

1 1 II

SOI L

Ivonhoe _

__lvanhoe '«*»

ea

Ivanhoe ^H

BZBB | |

1 1 

1 1 UJ

r i i i

n 1 1

,1 I-I

1 1

^ ^

1 1 1 1

1 1 1 1

STREAM SEDIMENTS

_ _

Gulf ^ - f=l

sediments<^| " ni i M "" n H i i

H

LJ ^J

till

r25 r50 r90 r25 50 r25 P50 r75

PERCENTILES 

FIGURE 1. Percentile ranges of mercury distribution in rock, soil, and sediments.

As a frequency distribution approaches normality 

the 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 neither arithmetic means nor medians were available, 

geometric means were used as measures of central 

tendency. These statistics are listed in the 50th percentile column of table 17 and in the graphical 

summary shown in figure 1.

We acknowledge the assistance of Lament T. 

Wilch, Theodore M. Billings, and Raoul V. Mendes 

for their aid in the computer processing for this report.

REFERENCES CITED

Clark, A. L., Condon, W. H., Hoare, J. M., Sorg., D. H., 

1970, Analyses of rock and stream-sediment samples 

from the Taylor Mountains C-8 quadrangle, Alaska: 

U.S. Geol. Survey open-file rept., 110 p.

Ehmann, W. D., and Lovering, J. F., 1967, The abundance of 

mercury in meteorites and rocks by neutron activation 

analysis: Geochim. et Cosmochim. Acta, v. 31, no 3, p. 

357-376.

Fischer, R. P., Luedke, R. G., Sheridan, M. J., and Raabe, R. 

G., 1968, Mineral resources of the Uncompahgre primitive area, Colorado: U.S. Geol. Survey Bull. 1261-C, 91 

p. [1969],

Flanagan, F. J., 1969, U. S. Geological Survey standards; 2, 

First compilation of data for the new U.S.G.S. rocks: 

Geochim. et Cosmochim. Acta, v. 33, No. 1, p. 81-120.

Gott, G. B., Botbol, J. M., Billings, T. M., and Pierce, A. P., 

1969, Geochemical abundance and distribution of nine 

metals in rocks and soils of the Coeur 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. 1230-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-D,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

Ratt£, W. C., Landis, E. R., Gaskill, D. L., and Raabe, R. G., Mineral resources of the Gore Range-Eagle Nest Primi1969, Mineral resources of the Blue Range primitive tive Area and vicinity, Summit and Eagle Counties, Colarea, Greenlee County, Arizona, and Catron County, orado: U.S. Geol. Survey Bull. 1319-C, 127 p. 

New Mexico, with a section on Aeromagnetic interpretation, by G. P. Eaton: U. S. Geol. Survey Bull. 1261-E, Vaughn, W. W., 1967, A simple mercury vapor detector for 

91 P- geochemical prospecting: U.S. Geol. Survey Circ. 540, 8

Tweto, Ogden, Bryant, Bruce, and Williams, F. E., 1970, p.
MERCURY IN SEDIMENTARY ROCKS OF THE COLORADO

PLATEAU REGION

By R. A. CADIGAN

Mercury content of sedimentary rocks in the Colorado Plateau region ranges from <10 ppb to 

> 10,000 ppb. Sedimentary rocks compose or immediately 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 various 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 Commission, 1948-56, and the Geological Survey's continuing Heavy Metals program which began in l'967. 

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 approximately 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

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 computed statistics are based; "Median," the middle 

value of each distribution (half of the values are 

larger and half are smaller); "Highest," the maximum value determined; "Lowest," the minimum 

value; and "Middle 68 percent of samples," the 

range of values grouped around the median, approximately 34 percent (one standard deviation) on 

each side. "Dominant rock types" refers to the textural rock type listed below in order of importance 

and which makes up 90 percent or more of the formation or the group. "Approximate average thickness" is given to provide an idea of the order of 

magnitude of the amount of rock involved. The statistical distributions of mercury values are approximately 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 due to 

erosion or nondeposition. The Duchesne River Formation 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 (Newman, 1962), outcrops of the Tertiary and Upper 

Cretaceous sedimentary rocks in the region are discontinuous because of erosion, but they occupy approximately 20 and 30 percent, respectively, of the 

surface area of outcropping sedimentary rocks. Jurassic 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 sedimentary rocks which form the surface or which immediately underlie soil-covered surfaces of the Colorado Plateau region is shown in figure 3. The figure

17
18 MERCURY IN THE ENVIRONMENT

401 

30

20

8 8 8 8

MERCURY, IN PARTS PER BILLION

FIGURE 3. Frequency histogram of percent of samples 

plotted over mercury content a composite of the formation 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: Median, 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 moment. 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 divided 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 Cretaceous receiving a weight of 3, the combined Jurassic 

and Triassic receiving a weight of 4, and the combined 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 occurrence. Most of the samples from the Morrison 

and Chinle which contain more than 1,000 ppb mercury were collected from localities near known uranium deposits. Stream-sediment samples collected 

from streams adjacent to and draining the mineralized 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 mercury (4,000 ppb).

No significant correlation appears to exist between 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 formations. Regional distribution of mercury in the Navajo was previously studied (Cadigan, 1969). The 

Wingate Sandstone, similar in structure to the Navajo 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 formations. 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, Mancos, Morrison, and Chinle 

Formations, contain higher amounts of mercury 

than do the rocks that contain little volcanic detritus.

Limestones in the Hermosa 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 information to modify or supplement data and conclusions 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 sedimentary rocks of the Colorado Plateau A preliminary report: 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 complicated 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 reasonably 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 water-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 temperatures and which has a distinct tendency to vaporize. 

The other two forms are ionic; the more reduced of 

the two ions is the mercurous ion Hg/2 , where the 

average valence of mercury is +1. In oxidizing conditions, especially at low pH, the stable form is the 

mercuric ion, Hg*2 .

Although chemical oxidation does not necessarily 

require the presence of oxygen, this element is the 

most common oxidizing agent and systems in contact 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 systems 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 theoretical solubility and stability of many elements can be 

usefully calculated in a similar way, by considering

the interrelationships of oxidation-reduction equilibria 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 potentials that were taken from published literature. Potentials are given only for redox reactions. Data on 

additional species can be obtained from the compilation of Sillen and Martell (1964). These kinds of 

data are useful in calculating mercury behavior and 

solubilities. Table 20 contains standard free energies of formation of the mercury species that are 

reported in the literature. These permit calculation 

of the relative stability of different forms of mercury in aqueous media under a wide range of conditions.

STABILITY AND SOLUBILITY CALCULATIONS

As the data in tables 19 and 20 imply, mercury 

forms many solute species. Some of these are complex ions with a high degree of stability. A calculation of solubility for mercury must take into account a large number of possible forms. This 

situation is further complicated because of the possible existence of different oxidation states. Mercury in the form of liquid metal is somewhat volatile 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 soluble in organic liquids than in water.

Data from tables 19 and 20 were used to construct 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 po1 Tables are in the back of the report.

19
20 MERCURY IN THE ENVIRONMENT

-.60

-.80

0 8 10 12

PH

FIGURE 4. Fields of stability for solid (c) and liquid (1) mercury species at 25°C and 1 atmosphere pressure. System includes water containing 36 ppm Cl~, total sulfur 96 ppm as SO4"2.
CHEMICAL BEHAVIOR IN AQUEOUS MEDIA 21

tential under which water itself is chemically stable. 

The existence of mercuric chloride, calomel, and cinnabar depend on the presence of chlorine and sulfur 

species in the system. Values arbitrarily selected 

are KH moles per liter of each. This concentration 

is equivalent to 36 ppm Cl- and 96 ppm S04- 2 . No 

single value for mercury concentration need be 

specified for locating the boundaries. Calculation 

techniques used in preparing Eh-pH diagrams have 

been described extensively in the literature. Solid 

species are identified by the abbreviation "c", gases 

"g", liquids by "1", and dissolved species by superscript plus or minus signs or by the abbreviation 

"aq " The calculations are for the standard temperature of 25°C. Effects of temperatures 10 to 15 degrees 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 (cinnabar) are the principal ones likely to enter into 

equilibria affecting the solubility of mercury. The 

organometallic 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 thermodynamically 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 predominant solute species at any area of interest in the 

diagram. Figure 5 represents the areas of dominance 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 pH 5 the predominant mercury species in solution 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, about 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 Pariaud 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, cinnabar. This compound has an extremely low solubility. 

In the fields of Mg(HS) 2 aq and HgS2 '2 near neutral 

pH, the equilibrium solubility of mercury may be 

lower than .002 ppb. Very strongly reducing conditions, 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 increased by the formation of the uncharged HgCl2 

complex, or anionic complexes such as HgClr2 . The 

area of dominance shown for chloride complexes 

would be enlarged if chloride had been increased 

above 10~3 molar. Inorganic mercury complexes in 

waters in Sweden were reported by Anfalt and 

others (1968) to include HgCl2 °, HgOHCl0, and 

Hg(OH) 2°, with predominant forms depending on 

chloride concentration and pH. Stability data for the 

HgOHCl0 species were not 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 dissolved 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 described 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
22 MERCURY IN THE ENVIRONMENT

1.20

1.00

,80

.60

.40

-.80

Water oxidized

aq

HIGH SOLUBILITY

- Hg2~ 

Hg(OH)2°aq

PH

FIGURE 5. Fields of stability for aqueous mercury species at 25°C and 1 atmosphere pressure. System includes 

water containing 36 ppm C1-, 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 seldom attained in natural water.

ORGANIC COMPLEXING EFFECTS

The relative importance of organic solute complexes of mercury in the aqueous chemistry of the 

element cannot be fully decided at present. The information 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 generally less 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 natural water 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 mercury. 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(CH8 ):. would 

be the most stable phase.

Methyl mercuric ion, HgCH3+, is cited in publications by various authors as the most important 

form in fish and various other food products of animal 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 HgCH3+ could 

be found, and no firm basis for calculating or estimating such a value seems to be available. This species 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 important areas where available information is inadequate to permit full acceptance of the theoretical 

model without further testing. The frequent departure of natural systems from equilibrium is well 

known, and must be kept in mind when using equilibrium calculations. There are two aspects of mercury 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 biochemical processes has been mentioned already. However, it has not been proved conclusively that 

methyl mercury is produced in abundance in sediment by bacterial activity; the energy that the organisms would have to expend is large, which is contrary to most metabolic processes.

A second property of importance is the tendency for mercury to participate in dismutation 

reactions that is, in reactions of the type 

Hg:.+2 :=Hg0 +Hg+2 . This and similar reactions are 

well known, and provide a means whereby mercury could be converted to the liquid form and escape as vapor. The oxidation and reduction reactions 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 predict at times. The combination of oxidized mercuric 

ion with the reduced sulfide ligand to form cinnabar, 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 understanding 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

Anfalt, Torbjorn, Dyrssen, David, Ivanova, Elena, and Jagner, Daniel, 1968, State of divalent mercury in natural 

waters: Svensk Kern. Tidsskr., v. 80, no. 10, p. 340-342.

Helgeson, H. C., 1969, Thermodynamics of hydrothermal systems at elevated temperatures and pressure: Am. Jour. 

Sci., v. 267, p. 729-804.

Latimer, W. M., 1952, Oxidation potentials: Englewood 

Cliffs, N. J., Prentice-Hall, Inc., 352 p.

Moser, H. C., and Voigt, A. F., 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 solubilitS des 

metaux dans 1'eau: Soc. Chim. France Mem. 99, p. 

454-456.
24 MERCURY IN THE ENVIRONMENT

Silten, L. G., and Martell, A. E., 1964, Stability constants of 

metal-ion complexes [2d ed.]: Chem. Soc. [London] 

Spec. Pub. 17, 754 p.

Wagman, 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.

Waugh, T. D., Walton, H. F., and Laswick, J. A., 1955, lonization constants of some organomercuric hydroxides and 

halides: Jour. Phys. Chemistry, v. 59, no. 5, p. 395-399.

Westoo, Gunnel, 1967, Determination of methylmercury compounds in foodstuffs; 2, Determination of methylmercury 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, Synthesis of methylmercury compounds by extracts of & 

methanogenic bacterium: Nature, v. 220, no. 5163, p. 

173-174.
MERCURY CONTENTS OF NATURAL THERMAL AND MINERAL FLUIDS

By D. E. WHITE, M. E. HINKLE and IVAN BARNES]

VOLCANIC FUMAROLES

Data on mercury contents of fumaroles are lacking 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 (sO.3 ppb); at 220°C, the mercury content is about 1.5 ppb, and at 270°C, it is about 6 

ppb. Residual gases (not condensed in water) contain 3xlO:7 to 4xlO~6 g/m8 (grams per cubic 

meter) of gas.

SUBLIMATES FROM FUMEROLES

Sublimates are commonly more enriched in mercury 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 contents.

HOT SPRINGS

The relationships of hot springs to mercury deposits 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 successful 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-mercury amalgam was heated in 

an induction furnace and the mercury vapor determined in a mercury vapor detector by photo absorption. The detection limit is 0.01 ppb. The results are 

given in table 21.2

1 Incorporates data from W. W. Vaughn, Howard McCarthy, F. N. 

Ward, and R. 0. Founder and background data from the literature, mainly 

Russian.

GASES

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. Superheated steam from steam wells at The Geysers, 

Calif., contains a measurable amount of mercury. 

An early analysis of condensed steam showed a content 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 hotspring gases is not adequately known and needs detailed 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 summarized by White (1967). Although various analytical procedures were used, these values are probably 

much too high they range from <20 ppb (stated 

detection limit) to 400 ppb. In contrast, recent analyses of the same type of water range from <0.05 to 

20 ppb mercury.

Tentative generalizations on mercury contents reported 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 saline 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 content 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 cinnibar-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 extreme 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 temperature. Mercury contents of water of the major geyser 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 Amedee 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 cinnabar 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 average 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 sediments 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 Sylvan Springs, Gibbon Basin, Yellowstone, 5,000 ppb; 

and elemental sulfur precipitated from condensed 

steam of P.G. & E. powerplant No. 2, The Geysers, 

California, 5,000 ppb.

The fine-grained muds of the mudpots and mud 

volcanoes of Yellowstone National Park commonly 

show similar concentrations. Nine analyses show a 

range of 5,000 to 150,000 ppb. These muds are 

products of hydrothermal alteration of adjacent 

rocks; the only reasonable mechanism for enrichment in mercury is condensation from the hot vapor 

that streams up through these muds (White and 

others, 1970). Some steam and much of the mercury 

evidently condenses in the surface pools. Even 

though Yellowstone National Park fluids are low in 

mercury, as compared to those of other areas, they 

are transporting and depositing measurable quantities of mercury.

Large mercury anomalies have been found by 

Dall'Aglio and others (1966) in stream sediments 

around the Italian geothermal steam fields of Larderello and Monte Aniata; more than 50 percent of 

all their analyses ranged in mercury content from 

200 to 50,000 ppb. Most anomalies could not be 

traced to mercury deposits and are interpreted as 

indicators of geothermal steam. Transportation by 

vapor appears to be the most logical explanation.

PETROLEUM, NATURAL GAS, AND 

OIL-FIELD WATERS

Only a few waters associated with petroleum 

have been analyzed for mercury; contents reported 

from the Cymric oil field, Calif. (Bailey and others, 

1961; White, 1967), range from 100 to more than 

200 ppb, but these are probably too high and should 

be redetermined by current methods of analyses. 

Mercury analyses of Cymric crude oils range from 

1,900 to 21,000 ppb, which is in the range of elemental mercury solubilities in hydrocarbons (Spencer and Voight, 1968). The natural gas of the Cymric field is saturated with mercury vapor, thus 

indicating saturation with elemental mercury. During transport in a pipeline, mercury vapor evidently
NATURAL THERMAL AND MINERAL FLUIDS 27

combines with H2 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 hydrocarbons, contained 500,000 ppb. Hydrocarbons extracted from fault gouge from the Abbott mine by 

organic solvents contained 1,000 to 5,000 ppb, but a 

sample 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 the nearby Wilbur oil test well (table 23) contained 1,000 ppb mercury.

Some additional evidence for enrichment of mercury 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 contents of Tertiary argillaceous rocks.

SUMMARY

Dilute thermal springs contain readily detectable 

mercury. The springs include high-temperature waters of Yellowstone National Park, which are 

closely associated with extensive Pleistocene volcanism. Some California thermal waters, and nonthermal waters of appreciable salinity (>5,000 ppm 

total disolved solids) but not closely associated with 

volcamsm, contain mercury in the range of 1 to 3 

ppb, concentrations notably higher than Yellowstone National Park waters. Sediments associated 

with some of these springs are rich in mercury, 

containing about 50 to 5,000 times the mercury content 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 especially 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 mercury deposits, petroleum and hydrocarbon gases apparently played a role, but the origin and nature of 

the fluids that have formed most large mercury deposits are not yet clearly understood. Our data are 

incomplete for hot spring and volcanic gases, especially in view of anomalous contents of mercury in 

associated solid phases which indicates vapor transport.

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., Snavely, 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 hydrologic sciences: U.S. Geol. Survey Prof. Paper 

424-D, p. D306-D309.

Barnes, Ivan, 1970, Metamorphic waters from the Pacific 

tectonic belt of the west coast of the United States: Science, v. 168, no. 3934, p. 973-975.

Brannock, W. W., 1948, Preliminary geochemical 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, Prospezione geochimica del mercurio; distribuzione del mercurio nelle alluvioni della Toscana: 

Industria Mineraria, v. 17, no. 9, p. 391-398.

Dickson, F. W., and Tunell, George 1968, Mercury and antimony 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 Engineers, p. 1673-1701.

Dupuy, L. W., 1948, Bucket-drilling the Coso mercury deposit, 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, TJalifornia, a spring of unique chemical character: 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, in 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 

Kerch-Tamin' province: Geokhimiya, no. 6, p. 668-678.

Spencer, J. N., and Voight, A. F., 1968, Thermal dynamics 

of the solution of mercury metal, 1. Tracer determinations 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 

geochemical prospecting: U.S. Geol. Survey Circ. 540, 8 p.

White, D. E., 1955, Thermal springs and epithermal ore de-
28 MERCURY IN THE ENVIRONMENT

posits, in Part 1 of Bateman, A. M., ed., Economic geol- White, D. E., Muffler, L. J. P., and Truesdell, A. H., 1970,

ogy, 50th anniversary volume, 1905-1955: Econ. Geology Vapor-dominated hydrothermal systems compared with

Publishing Co., p. 99-154. hot-water systems: Econ. Geology (in press).

 1967, Mercury and base-metal deposits with associated White, D. E., and Roberson, C. E., 1962, Sulphur Bank, Calithermal and mineral waters, in Barnes, H. L., ed., Geo- fornia, a major hot-spring quicksilver deposit, in Petrochemistry of hydrothermal ore deposits: New York, logic studies A volume to honor A. F. Buddington: 

Holt, Rinehart, and Winston, Inc., p. 575-631. Geol. Soc. America, p. 397-428.
SOURCES AND BEHAVIOR OF MERCURY IN SURFACE WATERS

By R. L. WERSHAW

NATURAL LEVELS OF MERCURY IN 

SURFACE WATERS

Before one declares a water body polluted with 

waste mercury from man's activities, it is necessary 

to know the natural background level of the metal. 

The data in table 241 were obtained on water samples 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 absorption method discussed by F. N. Ward (this report) . 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 detectable concentration (0.1 ppb). Of the remainder, 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 meicury contamination would appear 

to indicate that mercury concentrations in surface 

waters generally do not exceed tolerable limits except in the immediate vicinity of waste outfalls.

Table 25 shows that the mercury levels measured 

in surface waters in other parts of the world generally 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 (1934) 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 exceeding 5 ppb. Kvashnevskaya and Shablovskaya (1963) 

found mercury minerals in the suspended particulate 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 deposits (table 25). Mercury concentrations in these 

waters were found to decrease as a function of distance 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, Gomcharov, 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 waters.

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 principally in California, Nevada, Idaho, and Oregon. The 

United States imported 860 metric tons of mercury 

in 1968 so that together with imports and seven hundred 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 estimated 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 calendar 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. Mercury also finds very widespread use as a fungicide, 

bacteriacide, and slimicide. For example, the paint 

industry uses phenyl mercuric compounds for mildew-proofing and mercury organic compounds are 

used as seed dressings in agriculture. Mercury compounds are also used in the paper industry to prevent 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 employed to a limited extent as catalysts in the production of many organic materials in pharmaeutical and dental preparations, and, because of its 

conductive properties in the liquid state, in a variety 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 industrial outfalls are not properly scavenged for 

mercury, or if mercury-bearing materials are improperly disposed of, some of the waste inevitably 

finds its way into surface waters. For example, Anderssen (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 representative 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 samples, 28 percent had less 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 concentrations which were within the range of Public Health 

Service mercury content allowable for drinking 

water supplies despite the fact they represented industrial areas. An additional 12 percent of the samples 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 compounds introduce additional mercury into surface 

waters. Whatever its source, the concentration of 

mercury compounds, dissolved or suspended, is reduced rapidly by sorption and by complexing reactions with clays, plankton, colloidal proteins, humic 

materials, and other organic and inorganic colloids 

(J. D. Hem, E. A. Jenne, this report.) These reactions tend to keep the concentration of dissolved 

mercury at levels near the normal background except at points of actual mercury discharge.

SELECTED REFERENCES

Aidin'yan, N. Kh., 1962, Content of mercury in some natural 

waters: Trudy Inst. Geol. Rudn. Mestorozhd., Petrog., 

Mineralog. i Geokhim., no. 70, p. 9-14; Chem. Abs., v. 

57, no. 16336e.

 1963, The mercury contents of some water in the Armenian 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. Belavskaya, G. A., 1963, Supergene 

transfer of mercury: Trudy Inst. Geol. Rudn. Mestorozhd., Petrog., Mineralog. i Geokhim., no. 99, p. 12-15; 

Chem. Abs., v. 59, no. 8471e.

Anderssen, Arne, 1967a, Mercury in the soil: Grundforbattring, v. 20, nos. 3-4, p. 95-105; Chem. Abs., v. 69, no. 

51225J.

 1967b, Mercury in decayed sludge: Grundforbattring, 

v. 20, nos. 3-4, p. 149-150; Chem. Abs., v. 69, 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 natural water samples from Tuscany and Latium (central 

Italy), in Ahrens, L. H., ed., Origin and distribution of 

the elements A symposium, Paris, 1967: New York, 

Pergamon Press, p. 1065-1081.

Hamaguchi, Hiroshi, Kuroda, Rokuro, and Kyoichi, Hosohara, 1961, Photometric determination of traces of mercury in sea water: Nippon Kagaku 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 mercury content of water from the Saale River]: Naturwissenschaften, v. 44, no. 16, p. 441-442.

Hosohara, 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, Katsuhiko, 

and Tsuruta, Tokumatsu, 1961, Total mercury content 

in sea water: Nippon Kagaku Zasshi, v. 82, p. 

1479-1480; Chem. 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.

Karasik, 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.

Kvashnevskaya, 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 public-health hazards of chemicals in the environment: Columbus, 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. Sei.- 

Natl. Eng. Pub. NMAB-258, 37 p. [For sale by Clearinghouse for Federal Sci. and Tech. Inf.]

Reutov, 0. A., and Beletskaya, I. P., 1968, Reaction mechanisms of organometallic compounds: Amsterdam, 

North-Holland Publishing Co., 466 p.

Stock, Alfred, aid Cucuel, Friedrich, 1934, Die Verbreitung 

des Quecksilbers [The occurrence of mercury]: Naturwissenschaften, 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, Synthesis of methyl-mercury compounds by extracts of a 

methanogenic bacterium: Nature, v. 220, no. 5163, p. 

173-174.

Zautashvili, B. Z., 1966, Problem of mercury hydrogeochemistry (as illustrated by the mercury deposits of Abkhasia) [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 utilization. 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 inorganic materials dissolved in the water or the insoluble materials that can be readily converted to bodily 

needs. The chlorophyll-bearing phytoplankton and 

higher plants are the principal organisms for conversion of these ultimate basic materials to living 

matter. They, therefore, are called the primary 

producers of the system and all other organisms depend upon their existence.

Those organisms that feed upon the plants, such 

as zooplankton, insects, snails, and small fish, are 

known as primary consumers. Secondary consumers 

feed upon the primary consumers and are represented by the larger fish, such as trout, pike, bass, 

and salmon. Every organism in an aquatic community may, by death and decomposition, contribute directly to the dissolved materials, or may be consumed as food by other organisms. Micro-organisms 

are responsible for the breakdown of organic 

materials and the releasing of dissolved substances 

for reuse. Figure 6 is a simplified representation of 

the flow of materials through an aquatic food chain.

Although mercury is not considered to be an essential food material for organisms, it is incorpoBacteria

Dissolved' 

substances

Phytoplankton

1

Zooplankton

Small fish 

« Insects

'Higher plants- Herbivores

Large fish

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 organic mercurial wastes from industrial effluents are 

converted by anaerobes into methyl mercury, 

CH3Hg% or dimethyl mercury, (CH3 ) 2Hg. This finding was confirmed by Wood, Kennedy, and Rosen 

(1968), who stated that the methylation of mercury 

is due to bacterial activity. The latter authors concluded that dimethyl mercury is the ultimate product but that in situations where an excess of mercuric ion Hg+2 ) exists, methyl mercury is also 

produced.

Dimethyl mercury, although stable in alkaline solutions, dissociates to ionic methyl mercury at low 

pH values. Such low pH 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 secondarily 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 assimilation from the surrounding medium (Rucker 

and Amend, 1969). In either event, when mercury 

is introduced into a food chain, it becomes available 

to all organisms of the chain.

TOXICITY

Mercury compounds inhibit the growth of bacteria, 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 Hermann (1959) to cause a 50-percent decrease in the 

5-day utilization of oxygen by sewage. Ingols

32
BIOLOGICAL FACTORS 33

(1954) reported that a concentration of 2,000 ppb 

results in complete bacteriostasis. 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 producers, 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 Macrocystis pyrifera during a 4-day exposure. A concentration of 500 ppb caused a 15-percent decrease 

in photosynthesis in 1 day and complete inactivation in 4 days.

Uk6les (1962) reported 0.6 ppb of ethyl mercury 

phosphate as the threshold concentration for inhibiting the growth of marine phytoplankton and that 

60 ppb was found to be lethal to all marine species. Burrows and Combs (1958) concluded that 

ethyl mercury phosphate was an effective algicide at 

1,000 ppb. In contrast, Hueper (1960) reported that 

the threshold of lethal concentrations of mercury 

salts for phytoplankton ranged from 900 to 60,000 

PPb.

Clendenning and North (1960) reported that 

mercury was found to be more toxic to aquatic organisms than copper, hexavalent chromium, zinc, 

nickel, or lead. Corner and Sparrow (1956) emphasized that the toxic effects of mercury salts are increased appreciably by the presence of copper.

Glooschenko (1969) showed that the accumulation of 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 illustrate an important ecological principle. Aquatic 

organisms, as well as man, will concentrate mercury 

within their bodies when the intake rate exceeds the 

elimination rates. The result, under these conditions, is a buildup with time to the extent that the 

accumulated mercury can become toxic and, eventually, lethal.

Rucker and Amend (1969) studied the accumulation of mercury in fish. They exposed rainbow 

trout, Salmo gairdneri, for an hour a day to nonlethal concentrations of ethyl mercury phosphate. 

After 10 days, several fish were sacrificed, and their

tissues were analyzed for mercury. The results 

showed the following concentrations in the tissues:

Tissue

Blood . Kidney 

Liver . 

Brain . 

Gonad . Muscle

Mercury (ppb)

22,800

17,300

16,700

10,100

4,100

4,000

The remaining fish were maintained in mercuryfree water. The authors found that after 45 weeks, 

mercury had been eliminated from all tissues except 

the liver and kidney, where concentrations had stabilized 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." Extensive investigations revealed that the deaths were 

caused by the consumption of mercury-contaminated 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). Similar 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 Administration has declared that fish and other foods 

which contain more than 500 ppb of mercury are 

unsafe for human consumption.

REFERENCES CITED

Burrows, R. E., and Combs, B. D., 1958, Lignasan as bactericide and algaecide: Prog. Fish Culturist, v. 20, p. 

143-145.

Clendenning, K. A., and North, W. J., 1960, Effects of 

wastes on the giant kelp, Macrocystis pyrifera,, in Pearson, E. A., ed., International conference on waste disposal in the marine environment, 1st, Berkeley, Calif., 

1959, Proceedings: Pergamon Press, v. 1, p. 82-91.

Corner, E. D. S., and Sparrow, B. W., 1956, The modes of 

action of toxic agents; 1, Poisoning of certain crustaceans by copper and mercury: Marine Biol. Assoc. 

United Kingdom Jour., v. 35, p. 531-548.

Glooschenko, W. A., 1969, Accumulation of mercury-203 by
34 MERCURY IN THE ENVIRONMENT

the marine diatom Chaetoceros costatum: Jour. Phycology, v. 5, no. 3, 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 artificial water pollutants, in Conference on physiological 

aspects of water quality, Proceedings: Washington, 

U.S. Public Health Service, p. 181-193.

Ingols, R. S., 1654, Toxicity of mercuric chloride, chromium 

sulfate, and sodium chromate in the dilution B.O.D. 

test: Sewage and Indus. Wastes, v. 26, p. 536.

Jenson, S. R., and Jernelov, A., 1669, Biological methylation 

of mercury in aquatic organisms: Nature, v. 223, no. 

5207, p. 753-754.

Kurland, L. T., Faro, S. N., and Siedler, H. S., 1960, Minamata 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 retention of organic mercurials by rainbow trout and chinook and sockeye salmon: Prog. Fish Culturist, v. 31, p. 

197-201.

Ukeles, Ravenna, 1962, Growth of pure cultures of marine 

phytoplankton in the presence of toxicants: Appl. Microbiology, v. 10, no. 6, p. 532-537.

Westoo, Gunnel, 1967, Determination of methylmercury compounds in foodstuffs; 2, Determination of methylmercury 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, Synthesis 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 

grown in soils that typically are low in amounts of 

this element contain very little mercury in their tissues. 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 conditions, however, plant samples may contain larger 

amounts of mercury that can be readily detected by 

less rigorous analytical methods. The discussion 

that follows distinguishes typical chemical environments for plants from those that, because of naturally 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 suggest 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 literature of the "average" mercury content of plants.

In a recent U. S. Geological Survey biogeochemical 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 (Junipems 

mrginiana 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 environment. 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 A2 and B horizons (Shacklette, 1965, p. CIO). In a study of mercury 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 following results:

Plant species

Plant Number

part of (Ppb of dry

analyzed samples plant)

Alder (Alnus crispa subsp. 

crispa Hult.) ................

Black spruce (Pisea mariana 

(Mill.) Britt., Sterns & Pogg.) .

Dwarf birch (Betula nana L.)

Labrador tea (Ledum palustre 

subsp. decumbens (Ait.) Hult.) .

Spiraea (Spiraea beauverdiana 

Schneid.) ...................

Stems

Stems 

and 

leaves

Stems

Stems

Stems

and 

leaves

1

4

6

7

1

1,000

1,000-1,500

500-1,000

1,000-3,500

3,000

White birch (Betula papyrifera 

subsp. humilis (Regel) Hult.) Stems . 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 noteworthy 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 contained 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 mercury 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 determining the presence of mercury in soils and 

plants.

The toxicity of mercury to plants apparently depends on the chemical state of the element. Very 

small amounts of volatilized elemental mercury are 

believed by some floriculturists to be toxic to certain 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 production 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 bryophytes [mosses and liverworts] and vascular plants appeared 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 undamaged. No undisturbed outcrops of cinnabar that bryophytes 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 growing near it. We exposed 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 * * * 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. Novick (1968, p. 4) stated that mercury compounds are 

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 environments that have significantly larger amounts of 

mercury because of the natural occurrence of mercury-bearing deposits, the plants may contain between 500 and 3,500 ppb mercury in their dried tissues. 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 application of mercury compounds or from contamination.

REFERENCES CITED

Goldschmidt, V. M., 1954, Geochemistry: Oxford Univ. Press, 

730 p.

Hawkes, H. E., and Webb, J. S. r 1962, Geochemistry in mineral exploration: New York, Harper & Row, Publishers, 

415 p.

Malyuga, D. P., 1964, Biogeochemical methods of prospecting : New York, Consultants Bur., 205 p.

Novick, Sheldon, 1&69, A new pollution problem: Environment, v. 11, no.* 4, p. 2-9.

Rankama, Kalervo, and Sahama, T. G., 1950, Geochemistry: 

Chicago Univ. Press, 912 p.

Shacklette, H. T., 1965, Bryophytes 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 distribution of mercury in the atmosphere. The mercury 

content of air over scattered mineralized and nonmineralized 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 previously (McCarthy and others, 1969); additional 

data are reported here. Several factors that influence 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 locations 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 and precious metal mines, and still lower concentrations over porphyry copper mines. The concentration of mercury in air over nonmineralized 

areas ranged from 3 to 9 ng/m3 in the areas investigated.

Neville (1967) reported that in the mercury mine 

at Idria, Yugoslavia, the mercury vapor concentration is 1-20 X105 ng/m3 , and that the concentration 

of mercury vapor in air of the mercury processing 

plant is 0.6-9.7X105 ng/m3 . Sergeev (1961) found 

that mercury vapor in soil air collected from boreholes 1-2 meters deep contained 0-100 ng/m3 

whereas air collected 1 meter above the surface contained 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 collected at the same site in late April show no apparent 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 evening. 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 disturbances exist, the pressure record transcribes an ap1000

900

800

700

i 600 

j

: 500

LU 

O

0400

< 300

200

100 -

Jan. I, 1968 

o

April 27, 1968

\

\\

X -\

I 2 345678 9 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 /

I 7 1 I ? 1 1 7I 1 I 7 I I7 7 1 7 7 7 7 ] 7 I 1

UJ

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 barometric 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/m3 of mercury found near midday and a 

minimum of 20 ng/m3 found at 2:00 a.m. The minimum mercury concentration occurred during the 

time when the rate of increase in barometric pressure was greatest. Thus the daily content of mercury 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 maximum 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 collected 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 rainstorm. On the following morning, several hours 

after the rain, no mercury was detected in the air. 

Rankama and Sahama (1950) also reported that 

mercury in the atmosphere is removed by precipitation. Stock and Cucuel (1934) reported an average 

content of 0.2 ppb of mercury in rain water compared 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 report). Mercury in the atmosphere is derived from 

surface rocks and soils and from continuing hypogene 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 temperature. 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 concentrations 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 mercury 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 &t the surface and 24 to 108 

ng/m3 at 400 ft). I

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, Geochemical 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 Sergeev, Y. A., 1961, Methods of mercurometric investigaCirc. 609, 16 p. tions: Internat. Geology Rev., v. 3, no. 2, p. 93-99.

Neville, G. A., 1967, Toxicity of mercury vapor: Canadian Stock, Alfred, and Cucuel, Friedrich, 1934, Die Verbreitung

Chem. Education, v. 3, no. 1, p. 4-7. des Quecksilbers: Naturwissenschaften, v. 22, p. 390-393.

Rankama, Kalervo, and Sahama, T. G., 1950, Geochemistry: Williston, S. H., 1968, Mercury in the atmosphere: Jour.

Chicago Univ. Press, 912 p. 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 deposits, industrial wastes and exhausts, and applications of agricultural chemicals serve locally to increase 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 sufficiently high that air drying at 20 °C for 2 days in 

a sealed box through which previously dried air was 

passed resulted in losses of 15, 24, 42, and 42 percent of the mercury originally present in minus 200 

mesh fractions of four soils (Koksoy and others, 

1967). These authors also note "the detectable mercury 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 mercury."

The rate of vaporization of mercury and certain 

of its inorganic compounds decreases in the sequence 

Hg>Hg2Cl2 >HgCl2 >HgS>HgO according to the 

data of Koksoy and Bradshaw (1969). Vapor pressure of mercurial fungicides is much greater for the 

methyl and ethyl forms (0.8 to 23 times lO^mm 

(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 (23xlO-3mm

1 Methylmercury chloride, mercury (gray powder with talc), ethoxyethyl 

mercury silicate (tech.), methoxyethyl mercury silicate (tech.), ethylmercury chloride, ethylmercury isothiourea hydrochloride, methoxyethyl 

mercury chloride (tech.), ethoxyethyl mercury chloride (tech.), mercuric 

chloride, ethylmercury dicyandiamide (tech.), methylmercury dicyandiamide, 

bis-ethylmercury phosphate, tolylmercury acetate (mixed isomers?), phenylmercury acetate, phenylmercury oxinate, phenylmercury iso-urea, phenylmercury salicylanilide (tech.), phenylmercury fluoroacetate, phenylmercury 

chloride, bis-phenylmercury methanodinaphthodisulphnate (tech.), phenylmercury nitrate, phenylmercury salicylate, NN-dimethyldithlocarbamate.

mercury at 35°C). The methyl and ethyl forms 

tested, other than methylmercury chloride, have a 

volatility similar to metallic mercury (1.2 to 3.4 

times 10-3mm mercury (Phillips and others, 1959).

Gaseous and particulate mercury are commonly 

contained in the exhaust fumes from various industrial and smelting processes. Dust from sulfidebearing mineral deposits may occasionally be a significant 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, particularly from mineralized areas, by radiant energy. 

The saturation level of mercury in air in equilibrium with metallic mercury, increases logarithmically 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/m3 . By comparison of 

these values with the value of 10e ng/m3 for air saturated with metallic mercury vapor at 17°C 

(Vaughn, 1967), the soil air sampled by Sergeev 

would appear to have been undersaturated by a factor of about 104 . The high degree of undersaturation 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 compounds. McCarthy and others (1969) concluded that 

mercury in soil air samples was unrelated to the 

mercury content of the soil from which it was sampled, 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 mercury (P. E. Greeson, this report) will increase the 

vapor phase loss of mercury. Although monomethyl 

mercury is the principal product of biological meth40
ATMOSPHERIC AND FLUVIAL TRANSPORT 41

ylation (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 materials 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 reaction with air-borne particulate matter and with 

the land surface. Mercury that enters the atmosphere 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 Cucuel (1934) reported five rainwater samples whose mercury contents 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 samples, whose mercury content was significantly 

greater than the background value, was 0.2 ppb; 2 

the maximum value found was 0.48 ppb. The atmospheric mercury yield by rainfall was estimated by 

Anderssen and Wiklander (1965), who reported 1.2 

grams 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 (fungicide). Near industrial areas, more mercury may 

possibly be deposited by dry fallout than by rainfall 

during dry seasons. Thus, Dams and others (1970) 

found 2,y% 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.

FLUVIAL TRANSPORT OF MERCURY

The oxidation of mercury-bearing sulfide ores presumably results in the formation of both mercuric 

and mercurous ions. Mercurous chloride (Hg2Cl2 ) 

is only slightly soluble (0.002 g/l (gram per liter) 

or 2,000 ppb). It has a strong tendency to dismutate 

according to the reaction Hg2+2-»Hg°+Hg+2 under 

aqueous conditions (Sidgwick, 1950, p. 294). This 

reaction may be promoted by ultraviolet radiation 

(Sidgwick, 1950, p. 295). James (1962) sug-

* Incorrectly cited by Rankama and Sahama (1950, p. 718) as 2 ppb.

gested that the rather insoluble basic sulfate salt 

Hg2S04 -HgOH2 0 is also likely to form as the result 

of oxidation of mercury-bearing sulfide ores. Mercuric chloride, HgCl2 , being highly soluble (69 g/l 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, previously 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 conte'nt 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 hundreds 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 commonly 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 incised mercury-bearing deposits, both solute and particulate mercury are released 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 antimony (Koksoy and Bradshaw, 1969), mercury appears 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 enrichment of some soil horizons over mercury deposits and the very considerable increase in mercury 

concentration in fluvial sediments immediately 

below industrial outfalls that contain mercury
42 MERCURY IN THE ENVIRONMENT

wastes. Likewise, the affinity of certain soils for 

mercury is indicated by the failure of mercury applied 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 applied (Ross and Stewart, 1962). A further indication of the tendency of mercury to be sorbed by solids 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 observed 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 organic 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 report) and notably in petroleum fluids (D. E. White 

and others, this report). Inasmuch as mercury 

forms many stable organo-metallic compounds including sulfur-containing proteins, probably a very 

significant part of the cationic mercury that has resided in natural fresh waters for times on the order 

of hours to days will be in some organic form. Furthermore, one may in some cases find a greater 

amount of mercury in the particulate fraction than 

in the solute fraction where the amount of suspended solids is relatively high and especially where 

the relative quantity of particulate organic matter 

is high relative to the soluble organic matter. Hinkle and Learned (1969) found from five to 25 times 

as much mercury in a 1 N hydrochloric acid extraction 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 105 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 finding of Krauskopf (1956) that initially divalent mercury was effectively sorbed by microcrystalline iron 

oxides. In solutions containing 30,000 ppb of 

Fe2 03 -nH,0 and initial mercury concentrations of 

200 ppb, 90 to greater than 95 percent of the mercury 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 Mountains 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 microcrystalline iron and, to a lesser extent, manganese oxide 

coatings present on the clays (Jenne, 1968; Anderson and Jenne, 1970). James (1962) has postulated 

the sorption of mercuric chloride anion complexes 

(HgCl3~, HgClr2 ) by clays; sorption of molecular 

salts (Hg2Cl2 , HgCl2 ) is also a possibility. The hydrous 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+2 radius=1.10 angstroms) from waters and 

soils solutions are the possible isomorphous substitution 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 electronegativity 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 Vershkovskzia (1956, cited by Ginzburg, 1960, p. 19).

Little information is available on the cation exchange properties of mercury. Ginzburg (1960, p. 

155) stated that "Divalent ions form the following 

series, in reference to their uptake by montmorillonite from aqueous solutions Pb>Cu>Ca>Ba> 

Mg>Hg, and in reference to the facility of the replacement, Mg>Ba>Ca>Cu>Pb. The energy of adsorption series of heavy metals by kaolinite are as 

follows: Hg>Cu>Pb; the calcium replacement 

series Pb>Cu>Hg." Thus, it appears that the sorption 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 observed by Dall'Aglio (1968). The mercury concentration 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 

samples; presumably they were filtered). Wisconsin 

River sediment contained 560,000 ppb at a chemical 

company outfall but only 50,000 ppb 4 miles downstream (Chemical and Engineering News, 1970). 

The mercury concentration in the sediment had decreased to 400 ppb 21.4 miles downstream (Francis 

H. 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 possible seasonal variations, Heide, Lerz, and Bohm 

(1957) concluded that such variations did not occur 

in the mercury content of the Saale River (Germany) 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 mercury concentration in the Saale River due presumably to industrial pollution is indicated by their data.

EXPERIMENTAL DATA

Recent experimental data indicate that the sorption of mercury by membrane filters is minimal 

and that mercury sorption by peat moss, microcrystalline oxides, and soils is rapid (V. C. Kennedy, unpub. data, 1970). Solutions containing 1 

and 10 ppb of mercury (originally divalent) were 

made up in tap water prefiltered through a 0.1 micron 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 pH 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 \ hour by i/2 -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 samples, by filtered tap water and subsequently by onehalf normal sodium chloride (to approximate estuary 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 filtered 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 both the 1-hour and the 24- 

hour sorption sets. However, a slightly lesser percentage of the mercury originally sorbed was desorbed from the other samples which were exposed 

to mercury containing solutions for 24 hours. From 

2 to 7 percent was desorbed in tap water aiid 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 sodium chloride. However, it is not known to what extent the uptake by these earth-material samples is 

due to sorption of cationic mercury and to what extent the uptake may be due to a reduction to metallic mercury. The Eh-pH diagrams of Symons 

(1962) and the discussion of J. D. Hem (this report) indicate that metallic mercury is the stable 

form in most natural fresh waters. In very well oxygenated acid to neutral waters the mercurous ion 

may be the stable ion whereas under alkaline conditions 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 introduced into streams is quickly transformed to the 

particulate form by reduction to metallic mercury, 

by sorption on to inorganic sorbates, by complexatioh with nonviable particulate organics, and by 

sorption and ingestion by viable biota. The available 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 mineralogical-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 formation of strong inorganic* complex ions. Considering 

the known ability of natural soluble organics to extract 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 organics present. Thus, mercury may have greater 

mobility in waters containing large amounts of dissolved organics. 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 transporMs the second 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 complexing 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. (However, 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 conditions where the mercurous ion is stable, is generally 

less than 2 ppb (J. D. Hem, this report). However, 

the total solubility of both dissociated and undissociated species is from 20 to 30 ppb (Sidgwick, 1950, 

p. 287; Pariaud and Archinard, 1952). Thus, mercury can be expected to be released to the stream 

water rather slowly. The apparent ease of microbial 

transformation of inorganic mercury in bed sediments 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 conditions, may markedly affect the mobility of mercury. 

The precipitation of the rather insoluble mercuric 

sulfide, HgS (1.25X10- 24 g/1, Sidgwick, 1950, p. 

293), will tend to concentrate mercury in the sediment. In those unusual instances wherein alkaline 

reducing conditions exist, and hence greater sulfide 

concentrations occur, the formation of the rather 

soluble HgS2-2 ion may facilitate mercury transport. 

Although mercuric mercury is generally unstable 

with respect to metallic mercury in stream waters 

(Synions, 1962), mercuric sulfide is formed by the 

reaction Hg2S-»Hg° + HgS (Sidgwick, 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.

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ATMOSPHERIC AND FLUVIAL TRANSPORT 45

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des Quecksilbers: Naturwissenschaften, v. 22, no. 22/24, 

p. 390-393.

Symons, D., 1962, Stability relations of mercury compounds, 

in Schmitt, H. H., ed., Equilibrium diagrams for minerals at low temperature and pressure: Cambridge, Geological Club of Harvard, p. 164-175.

Vaughn, W. W., 1967, A simple mercury vapor detector for 

geochemical prospecting: U.S. Geol. Survey Circ. 540, 8 

PWarren, 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. H., 1964, The mercury halo method of exploration: 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 report. Hence, to be useful, any analytical method 

must be at least sensitive enough to detect as little 

as 10~8 gram and in some analyses one or two orders of magnitude less. With the exceptions of the 

techniques described by Ward and Bailey (1960) and 

by L. L. Thatcher (written commun., 1970), both discussed 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. (Although not rigorously defined, trace amounts may 

be considered as those occurring at 0.01 percent 

(100,000 ppb) or less.) Among the applicable techniques, including kinds of separations as well as 

final measurements, are those based on molecular 

and atomic absorption, molecular and atomic emission, catalysis, nephelometry, polarography, and activation to produce measurable decay products. Several analytical methods for determining trace 

amounts of mercury in geologic materials based on 

some of these techniques are discussed below. Gravimetric and volumetric methods are not generally 

applicable, but under certain conditions large samples can be taken and the separated mercury measured 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 determining mercury in soils and rocks is voluminous, 

especially when one considers that most of this literature covers less than a half century. Interests of 

agricultural chemists in the effects of trace elements 

in agriculture and of a few scientists like Goldschmidt and the Noddacks in trying out a new technique the spectrograph utilizing emission phenomena account in part for the literature becoming so 

large in such a short time. Fischer's (1925) research on the newly discovered large molecular compounds, such as dithizone, that were capable of reacting with 10~6 gram and less of certain metals 

(especially mercury) to produce highly colored 

products triggered the development of trace analytical methods.

Because of the vast literature available no claim 

is made of complete coverage herein, and the mention of a particular method to the exclusion of others 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, spectrophotometric, 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 related to the initial concentration of mercury in a 

homogeneous, isotropic medium; most often it is an 

organic solvent. Immiscible organic solvents are especially useful for enriching the species to a threshold level and for removing it from other compounds 

so as to inhibit or prevent interfering side reactions.

Dithizone is one of the most common organic 

reagents that forms a highly colored and extractable 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 difference in percent transmission as usually measured 

instrumentally). Differences of such magnitude are 

easily measured, and the dithizone procedure therefore is applicable to mercury concentrations found 

in soils and rocks. The dithizone reaction was the 

basis of the first practicable field method for determining traces of mercury in such materials 

(Ward and Bailey, 1960). Briefly, the procedure involved treatment of a finely powdered sample with 

sulfuric and hydrobromic acid and bromine in a test 

tube. The acidity of the sample solution was adjusted to pH 4 and treated with dithizone in n-hexane. Separation of the organic from the aqueous solution and subsequent removal of unreacted 

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 nontechnically 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 elements became commercially available in the early 

1960's and since then even more chemical elements 

can be determined by atomic absorption. Sample introduction 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 second technique, which is unique to mercury, the sample 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 Tindall (1967) and variants of the second are used by 

Brandenberger 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 extracted 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, mercury in soils and rocks is measured by an instrumental atomic absorption method described by 

Vaughn and McCarthy (1964) and Vaughn (1967). 

The sample is heated to about 500°C in an rf (radio frequency) field to drive off mercury and particulate 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 ultraviolet 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 photocell. The decrease is amplified in a differential amplifier causing a meter deflection that is proportional to the concentration of mercury. Under 

routine conditions the sensitivity achieved is about 

1 ppb, which is quite adequate for signaling anomalous 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 released mercury vapor is measured in a mercuryvapor absorption detector. The technique is described by Hinkle and Learned (1969).

A similar method for sediment free water samples (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 sorption 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 aspirator and the absorption is plotted on a recorder. 

Samples containing between 0.1 and 1.5 ppb of mercury can be analyzed directly; samples containing 

more than 1.5 ppb must first be diluted.

Much of the data given in this report, and especially 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 described.

Analytical methods based on optical emission 

spectrography are seldom used in the U.S. Geological Survey when many geologic samples must be an-
48 MERCURY IN THE ENVIRONMENT

alyzed and time is short. Without specialized techniques 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 Russian workers have exercised the patience and skill 

needed to utilize the potential of optical emission 

spectrography in measuring trace amounts of mercury 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 spectrography to determine mercury in ordinary materials such as soils, rocks, and vegetation.

Analytical methods based on catalysis are potentially 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 reaction of potassium ferrocyanide with nitrosobenzene to give a violet-colored compound, whose intensity is proportional to the mercury concentration. 

The color can be measured instrumentally or visually. As little as 3X1Q-8 gram (10° ppb) of mercury is readily measured, and starting with a 1- 

gram sample, the analyst can measure concentrations as little as 30 ppb.

Until recently, gravimetric methods of chemical 

analysis have not been useful in determining constituents occurring in amounts of 0.01 percent 

(100,000 ppb) or less. Owing to recent improvements in the sensitivity of analytical balances and 

especially the improvements that permit accurate 

weighing to a microgram or less, gravimetric methods should be evaluated, and the Eschka gravimetric method for assaying mercury in soils and rocks 

shows new promise.

The Eschka method consists of heating a sample 

in the presence of copper (Cu+2 ) oxide and lime in a 

closed system and amalgamating the volatilized 

mercury onto gold foil. With the improved analytical balances the amalgamated mercury can be measured by weight, and the increase resulting from 

amalgamation is proportional to the mercury content of the sample.

Mass spectrometry has quite recently been used 

for determining trace amounts of mercury in geologic materials. The method is sensitive and fast, especially 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 others (1970). The sensitivities achieved by these authors 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 Hg197 (65-hour half life) after irradiation for 70 hours with a flux of 1012 nanograms per 

square centimeter per second yields an absolute sensitivity of about 5 nanograms in a nondestructive 

procedure devised by L. G. Erwall and T. Westermark (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 extracting mercury from the stable complexes with which 

it may be associated in water, and (2) a more general method for toxic heavy metals including mercury. 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 

Hg197m (24-hour half life) and Hg197 (65-hour half 

life) are generated. After irradiation the mercury 

isotopes are isolated by performing a carrier precipitation with added mercury salt followed by stannous chloride. The latter reduces the mercury and 

radio-mercury compounds to the free metal including any radio-mercury that may be tied up as a stable complex. The activity of Hg197 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 determination 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 precipitate is activated (lead does not activate) in polyethylene or quartz as above. The lead sulfide protects 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 depends on the ability to make a lead sulfide precipitate 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 determination of mercury in waterborne materials, such 

as sediment and biota, by dissolving the irradiated 

material in hydrofluoric or oxidizing acids and following through with the carrier precipitation.

REFERENCES CITED

Brandenberger, H., and Bader, H., 1967, The determination 

of nanogram levels of mercury in solution by a flameless atomic absorption technique: Atomic Absorption 

Newsletter, v. 6, no. 5, p. 101-103.

Brune, Dag, 1966, Low temperature irradiation applied to 

neutron activation analysis of mercury in human whole 

blood: Stockholm, Aktiebolaget Atomenergi AE-213, 7 

PDams, R., Robbins, 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.

Fischer, H., 1925, Compounds of diphenythiocarbazone with 

metals and their use in analysis: Wiss. Veroeflf. Siemens-Konzern, v. 4, p. 158-170.

Fishman, M. J., 1970, Determination of mercury in water: 

Anal. Chemistry, v. 42, p. 1462-1463.

Hatch, W. R., and Ott, W. L., 1968, Determination of submicrogram 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 inorganic analysis, with special reference to the analysis of 

metals, minerals, and rocks [2d ed.]: New York, John 

Wiley and Sons, Inc., 1034 p.

Hinkle, Margaret, Leong, K. W., 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., 1969, Determination of 

mercury in natural waters by collection on silver screens: 

U.S. Geol. Survey Prof. Paper 650-D, p. D251-D254.

Sjostrand, Bernt, 1964, Simultaneous determination of mercury 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 

geochemical prospecting: U.S. Geol. Survey Circ. 540, 8 

PVaughn, W. W., and McCarthy, J. H., Jr., 1964, An instrumental 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 501-D, p. D123-D127 [1965].

Walsh, A., 1955, Application of atomic absorption spectra to 

chemical analysis: Spectrochim. 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, Metall., and Petroleum Engineers 

Trans., v. 217, p. 343-350.

TABLES 1-28

TABLES

TABLE 1. Determinations of mercury in U.S.G.S. standard rocks by different laboratories 

[Method: NA, neutron activation; AA, atomic absorption]

53

Sample

Granite G-l, Rhode Island 1 __ ...._.....

Diabase W-l, Virginia 1 _ -_--__----_---_.

Granite G-2, Rhode Island _ __ ._._____.

Granodiorite GSP-1, Colorado. ....._......

Andesite AGV-1, Oregon __ _____________

Basalt BCR-1, Washington................

Peridotite PCC-1, California.. .. _ -..-.

Dunite DTS-1, Washington. _.............

Mercury

content

(Ppb)

......... 340

130

245

120

70

97

80

.......... 170

340

110

330

94

280

290

.____._ 39

29

50

50

40

120

.......... 21

41

15

17

15

......... 4

16

25

26

15

......... 7

4

18

10

5

......... 4

4

5

11

10

......... 4

6

12

10

8

Year

1964

1965

1967

1968

1969

1970

1970

1964

1965

1967

1968

1969

1970

1970

1967

1969

1970

1970

1970

1970

1967

1969

1970

1970

1970

1967

1969

1970

1970

1970

1967

1969

1970

1970

1970

1967

1969

1970

1970

1970

1967

1969

1970

1970

1970

Method

NA

AA

NA

NA

NA

AA

AA

NA

AA

NA

NA

NA

AA

AA

NA

NA

AA

AA

AA

NA

NA

NA

AA

AA

AA

NA

NA

AA

AA

AA

NA

NA

AA

AA

AA

NA

NA

AA

AA

AA

NA

NA

AA

AA

AA

1 It has been suggested that some of the samples analyzed had become contaminated by mercury during long storage 

in the laboratory.

TABLE 2. Analyses for mercury, in parts per bittion, of basatts, gabbros, diabases, andesites, dacites, and lipantes

[Compare with table 6]

NunSample e 

a

Basalt BCR-1, Washington. ......._.......

Diabase W-l, Virginia............ ....

Three basalts, two dolerites, Iceland, Hawaii, 

and Tasmania. 

Basalts, oceanic sediments near Iceland __ ..

Gabbro, Quebec. ...._..___..

Composite 1 1 gabbros, Germany __ ........

Composite 1 1 gabbros, Germany __ ........

Gabbros, Yakutia __ .........

Gabbros, northern Caucasus. ..............

Gabbros. ._............__..

Basalt, Germany.. ................. _____

iber of

nalyzed

1 

5

1 

1 

1 

11 

13 

6 

1

Range

Min

4 

94 

5

180

0 

20

Max

18 

340 

21

300

50 

250 

500

Average

9 

231 

13

1 

100 

80 

26 

100 

240 

190

Reference

Five labs. 

Eight labs. 

Ehmann and Lovering (1967).

Aidin'yan, Ozerova, and Gipp (1963). 

Jovanovic and Reed (1968). 

Preuss (1940). 

Stock and Cucuel (1934a). 

Nekrasov and Timofeeva (1963). 

Afanas'ev and Aidin'yan (1961). 

Ozerova (1962). 

Stock and Cucuel (I934a).
54 MERCURY IN THE ENVIRONMENT

TABLE 2. Analyses for mercury, in parts per billion, of basalts, gabbros, diabases, andesites, dacitest and liparites Continued

Sample

Number of 

samples - 

analyzed

Range

Min Max

Average Reference

Basalt, Yakutia.--__-_---__-__--_______-_ 3

Basalt, Kamchatka and Kuriles____________ 63

Basalts, Andesites, Mendeleev Volcano,

Kuriles. 

Lavas, central Kamchatka.________________ ____

Lavas, eastern Kamchatka_______________ _.__

Granophyre, associated with dolerite, Tas- 1

mania. 

Andesite, AGV-1, Oregon__...___________ 1

Andesites, Kamchatka and Kuriles________ 209

Trachytes, northern Caucasus_-___-._______ 5

Trachytic tuffs, northern Caucasus._________ 19

Eruptive breccia, northern Caucasus 

Keratophyres, northern Caucasus 

Dacites, Kamchatka.__________

Dacites, Yakutia,____-.-_______

Liparites, Yakutia.____________

Liparites, northern Caucasus.___ 

Ignimbrites, northern Caucasus. _

6 40 20 Nekrasov and Timofeeva (1963).

20 100 47 Ozerova and Unanova (1965).

100 120 ------ Ozerova and others (1969).

. _ _ _ ______ 460 Aidin'yan and Ozerova (1964).

.... ______ 640 Do.

.___ ______ 26 Ehmann and Lovering (1967).

4 26 17 Five labs. 

20 400 75 Ozerova and Unanova (1965). 

60 200 130 Afanas'ev and Aidin'yan (1961). 

70 500 160 Do. 

	--.-__ 500 Do. 

20 300 100 Do. 

20 150 83 Ozerova and Unanova (1965).

2 30 10 Nekrasov and Timofeeva (1963).

15 200 70 Do.

40 80 60 Afanas'ev and Aidin'yan (1961).

40 80 65 Do.

TABLE 3. Determinations of mercury, in parts per billion, in granitic rocks

[N.f., not found. Compare with table 6]

Sample

Granite G-l, Rhode Island. __________ _ _ Granite G-2, Rhode Island, _ _ ..________

Granodiorite GSP-1, Colorado --------- __

Composite 14 German granites. _ _ _ _ -------

Composite 1 4 German granites ------ ______

Granite, Karelia. _._______. _ ______

Granites, diorites, granodiorites, 

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 ._ .._____-__

Number of

analyzed

1 

1 

1 

1 

1 

1

64

68 

45 

26 

8 

18 

2 

4 

4 

5

Range

Min

70 

29 

15

10

5 

N.f. 

N.f. 

2 

<100 

130 

100 

60 

60

TABLE 4. Determinations of mercury, in parts per

Ni 

Sample

Peridotite PCC-1 , California. ....-_._..__..

DuniteDTS-1, Washington......... __.--._

Serpentinites. ----_._ _____ _________ _ _ Kimberlite, South Africa __ ______ ________

Eclogite inclusion in kimberlite, South AfricaGarnet peridotite in kimberlite, South Africa . 

Eclogite inclusion in pipe, Australia. ________

Granulite inclusion in pipe, Australia. _ -

imber of

analyzed

1 

1 

4 

1 

1 

1 

1 

1

Range

Min

4 

4 

<20

Max

340 

120 

41

75

180 

80 

40 

20 

400 

200 

200 

50 

200

billion,

Max

11 

12 

500

155 

55 

22 

58 

100 

160 

30

28 

20 

13 

5 

190 

165 

150 

110 

130

Reference

Seven labs. 

Six labs. 

Five labs. 

Stock and Cucuel (1934a). 

Preuss (1940). 

Aidin'yan, Troitskii, and Balavskaya (1964). 

Aidin'yan, Mogarovskii, and Mel'nichenko 

(1969). 

Golovnya and Volobuev (1970). 

Nekrasov and Timofeeva (1963). 

Do. 

Do. 

Ozerova (1962). 

Afanas'ev and Aidin'yan (1961). 

Do. 

Do. 

Do.

in uUramafic and deep-seated igneous rocks

7 

8 

140 

200 

640 

780 

1,480 

1,230

Reference

Five labs. 

Do. 

Ozerova (1962). 

Ehmann and Lovering (1967). 

Do. 

Do. 

Do. 

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

Min Max

Average Reference

Average for four granosyenite porphyries, ____

Caucasus, 90, 700, 4000, 5000. 

Nepheline syenites, etc., Lovozero massif, Kola 640

Peninsula, U.S.S.R. 

Nepheline syenites, etc., Khibiny massif, Kola 179

Peninsula, U.S.S.R. 

Nepheline syenites._______________________ 72

50 80,000 90-5,000 Abuev, Divakov, and Rad'ko (1965).

140 580 273 Aidin'yan, Shilin, and Unanova (1966).

30 4,000 530 Aidin'yan, Shilin, and Belavskaya (1963).

60 200 200 Ozerova (1962).

TABLE 6. Determinations of mercury, in parts per billion, in igneous rocks of areas of very high content, mainly from the Crimea and

Donets Basin, U.S.S.R.

[Tr., trace]

Diabases, Crimea. ________ _ _ ____.

Spilites, Crimea ... _______ _.._ .. . Basalts, Donets Basin. _______ ____ _ .

Trachy dolerites, D onets B asin _ _ _ _ . . _ .

Andesite-basalts, Donets Basin ._.. -....

Camptonites, Donets Basin . ____--_-_..

Do

Basaltic andesite, Viet Nam _ _ _ _ _ _ _ _ .

Andesites, Donets Basin -.-_.._-.

Tuffs, Crimea..-...---..-.....-.......

Keratophyres, Crimea. . ________ ____.

Granodiorites, Crimea..---. ________ _.

Porphyry, Crimea. ______-_______-_.__.

Plagiogranite, Donets Basin --------- _ .

Plagioporphyry, Donets Basin. . _ _ _ _ _ _ _ . Granite, Donets Basin _ . ______________

Monzonites, Donets Basin _-_._-_----

Pyroxenites, Donets Basin. _____________

Shonkinites, Donets Basin --.. _.______.

Nepheline syenites, Donets Basin. ._

Number of

analyzed

33

3

8

4

.... 4

18

1

5

8

7

5

13

6

1

3

4

12

11

Rf

Min

Tr.

500

200

200

300

60

3,000

10,200

Tr.

Tr.

Tr.

Tr.

3,400

200

400

100

200

400

inge

Max

500,000

5,600

1,500

540

490

550

7,000

30,600

24,000

5,000

1,000

5,000

7,000

900

640

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. Determinations of mercury, in parts per billion, in metamorphic rocks

N' 

Sample i

8

Quartzites, Valdai Series, Russian platform _ 

Paragneisses, Valdai Series, Russian platform . 

Granitic, Valdai Series, Russian platform. ... 

Orthoamphibolites, Valdai Series, Russian 

platform. 

Phyllites and schists, Irtysh zone. __________

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 __ ..-- -_ --..-

umber of

tnalyzed

2 

5

7 

5

100

1 

14 

13 

10

1

Range

Min

55 t 

25

30 

30

7

2.5 

2.5 

70

Max

60 

100 

65 

90

28

2,535 

942 

600

Average

57 

51 

47 

51

18 

360 

193 

407

60

Reference

Ozerova and Aidin'yan (1966a, 1966b). 

Do. 

Do. 

Do.

Do. 

Jovanovic and Reed (1968). 

Do. 

Do. 

Aidin'yan, Shilin, and Belavskaya (1963).

Afanas'ev and Aidin'yan (1961).
56 MERCURY IN THE ENVIRONMENT

TABLE 8. Analyses for mercury, in parts per bittion, in limestones

I

Germany. _______________________________

Nineteen Composites, Russian platform.

Argillaceous marls, Cauascus,

background = 50. 

Limestones, Crimean highlands. ____________

Marls, Crimean highlands __ --------------

Donets Basin __ ___________________ _____

Kerch-Taman area, near mud volcanoes.

Limestones and dolomites, southern Ferghana. 

Northeast Yakutia.. _ ___________________ _ Kazakhstan

Marble, Viet Nam. ._______--___._-_______

lumber of

analyzed

1

14

19

8

5

314

22 

26

nOO

1

Ra

Min

28

10

10

100

500

<100

2,000

20 

<2

nge

Max

220

90

8,000

6,400

5,000

10,000

5,000

150 

70

33

66

31

2,300

1,500

900

75 

18

<20

500

Stock and Cucuel (1934a).

Heide and Bohm (1957).

Ozerova and Aidin'yan (1966a).

Abuev, Divakov, and Rad'ko (1965).

Bulkin (1962).

Do.

Karasik and Goncharov (1963).

Karasik and Morozov (1966).

Nikiforov, Aidin'yan, and Kusevich (1966). 

Nekrasov and Timofeeva (1963).

Fursov, as quoted by Ozerova and Aidin'yan

(1966b). 

Aidin'yan, Troitskii, and Balavskaya (1964).

TABLE 9. Analyses for mercury, in parts per billion, in sandstones

>

Composite of 23. _--_----_---_---_---._-_-..

Sandstones, mudstones, Russian platform _ . 

Effusive-sedimentary, Kamchatka. ._.--.---

Kazakhstan, _____________________________

Northeast Yakutia. --____--__----.-_______

Sandstones, Crimean highlands. .-_-.--._-__

Conglomerates, Crimean highlands. .. -------

Donets Basin __ -__-__.__--__-_--_.______

Donets Basin __ _________________________

Donets Basin, contact with dike .---______-_

Donets Basin, from mercury deposit. __ ....

Sandstones with limestones, southern Ferghana. 

Viet Nam... _.._.......__..___....__._...

lumber of

analyzed

2

1

45 

9

nOO

6

83

10

77

1

4

Rang

"Min

26

0

<-9

100

100 ^ ^wi

<100

3,000

3,000

280

P

Max

40

95

30

11,000

7,000

1,000

7,000

10,000

10,000

1,000

33 

100

39 

97

20

12

5,700

2,300

300

870

600

6,000

620

Stock and Cucuel (1934a). 

Preuss (1940).

Ozerova and Aidin'yan (1966b). 

Do.

Fursov, quoted by Ozerova and Aidin'yan

(1966b). 

Nekrasov and Timofeeva (1963).

Bulkin (1962).

Do.

Dvornikov and Klitchenko (1964).

Karasik and Goncharov (1963).

Buturlinov and Korchemagin (1968).

Bol'shakov (1964).

Kurmanaliev (1967).

Aidin'yan, Troitskii, and Balavskaya (1964).

TABLE 10. Analyses for mercury, in parts per billion, in shales and clays

Sample

Number of 

samples - 

analyzed

Range

Min Max

Average Reference

Composite 36 German shales. -__-____

Composite 26 German shales.________

Shales..-----_-------------------.-

Marly clays.__.-________-______-_._

Clays, Russian platform..___________

Shales, northeast Yakutia._-__.__._ 

Shales, sandstones, southern FerghanaShales, Komi A.S.S.R.._..__-..-_.__

Argillites, sedimentary-volcanic, Kamchatka. _ 

Bituminous shale, Alaska..--------_-_-----

Oil shales, Baltic region_____-_.__--_---.-

Oil shales, Povolzhe 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, KerchPeninsula.--.----.-----...---

Clays, Viet Nam_.____..__.___.-___._-_-._

1

I 

4 

3 

58 

6

36 

26

II 

2

10

11

2

48

0

8

55

130

100

0

15

20

42

630

170

200

50

<100 

nO

<100

<50

<200

<100

1,000

<100

100

250

320

130

80

150

230

2,800

1,500

1,600

100

200

nOOO

19,000

80

500

8,000

60,000

4,000

550

300 Preuss (1940).

510 Stock and Cucuel (1934a).

182 Do.

188 Heide and B6hm (1957).

35 Ozerova and Aidin'yan (1966b).

50 Nekrasov and Timofeeva (1963).

70 Nikiforov, Aidin'yan and Kusevich (1966).

------ Zav'yalov and Mal'tseva, quoted by Ozerova

	and Aidin'yan (1966b). 

85 Nikiforov, Aidin'yan, and Kusevich (1966).

------ Donnell, Tailleur, and Tourtelot (1967).

_----_ Ozerova and Aidin'yan (1966b).

440 Do.

75 Do.

______ Ozerova (1962).

______ Do.

2,300 Bulkin (1962).

50 Dvornikov and Klitchenko (1964).

350 Buturlinov and Korchemagin (1968).

660 Karasik and Goncharov (1963),

--_.-. Bol'jhakov (1964).

800 Morosov (1965).

270 Aidin'yan, Troitskii, and Balavskaya (1964).
TABLES 57

TABLE 11. Analyses for mercury, in parts per billion, in miscellaneous sedimentary rocks

Ji

Caucasus, not specified-.._______.._._ ._.

Gornyi Altai, not specified ._ _________ ____

Kerch-Taman area, near mud volcanoes.

Kerch-Taman area, away from mud volcanoesCambrian, Tyan-Shan _ _-.__.______ _____

Rock salt, anhydrite, gypsum, Donets BasinPhosphorites -. -_ -_._ -__--.____________

Iron-rich laterites, Viet Nam. ... __________

Manganese ores, Nikopol ___ .-_. .___ __ Manganese ores, Chiatura _________ ____

Manganese ores, Mangyshlak. ___ ____..__

Bauxites. .-__----_____ ._---.____________

lumber of

analyzed

14

9

----

71 

20

4

Rai

Min

40

500

400 

70

<100 

20

1,000

360

65

120

ige

Max

100

2,800

600 

2,800

4,000 

800

2,700

530

95

600

verage

50

540

700 

70

2,800

460

Demidova, quoted by OzerovaandAidin'yan

, (1966b). 

Shcherban, quoted by OzerovaandAidin'yan

(1966b). 

Karasik and Morozov (1966).

Do.

Shabalin and Solov'eva (1967).

Karasik and Goncharov (1963). 

Ozerova and Aidin'yan (1966a, 1966b).

Do.

Do.

Do.

Do.

Do.

TABLE 12. Analyses for mercury, in parts per billion, in oceanic and lacustrine sediments

Red clay, Atlantic. ________________

Red clay, Pacific __ _-... _________

Red clay, Black Sea _ _ .-_--_._____

Foraminiferal ooze, Atlantic. _______

Foraminiferal ooze, Pacific _ _______

Foraminiferal 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. ________

Number of

analyzed

_..____ 4

_______ 2

_--.-.- 4

___-._- 7

_______ 1

.__-__. 2

_______ 6

_______ 1

_______ 2

._._-._ 2

_______ 2

-___-.- 2

-__--.- 5

_______ 7

---_-_. 4

Ranee

Min

500

100

900

80

70

80

60

'1

1,400

360

<1

<1

<1

100

Max

1,800

300

2,000

300

150

550

100

MOO

2,000

810

810

775

3

150

1,000

200

1,200

170

50

110

210

70

80

200

Aidin'yan, Ozerova, and Gipp (1963).

Do.

Do.

Do.

Do.

Do.

Do.

Do.

Do.

Do.

_._.._ Bostrom and Fisher (1969) .

______ Landstrom, Samsahl, and Wenner (1969).

2,000

Do.

Harriss (1968).

Do.

Do.

Ozerova and Aidin'yan (1966b).

Do.

> On a carbonate-free basis.

TABLE 13. Analyses of soils for mercury, in parts per billion

Sample

Number of 

samples - 

analyzed

Range

Min Max

Average Reference

Most soils, California__-__._-__-________ _.__ 20 40

Soils, Franciscan Formation, California____ ____ 100 200

Soils, unmineralized areas, California.----._. __._ 40 60

Unmineralized areas, British Columbia. --------- 10 50

Near mineralization, British Columbia___. _.__ 50 2,500

Very near mineralization, British Columbia. _ _ _ _ _ 250 2,500

Soils, Germany...________________________ ____ 30 290

Topsoils, Sweden.________________________ 273 ______ ______

Topsoils, Africa________________________ 14 ______ ______

Soils, European U.S.S.R._______....._.____ 130 40 5,800

Soils, Donets Basin_______--_______.______ 248 <50 10,000

Soils, Donets Basin__-__---._________.____ ____ 100 2,400

Soils, Kerch Peninsula...--___.____________ 264 <100 3,000

Soils, Kerch-Taman area____..-.._.__._.. .... 240 1,900

Soils, Viet Nam___________.______________ .____ 20 1,000

60

23

300

1,300

""366

Williston (1968).

Do.

Friedrich and Hawkes (1966). 

Warren, Delavaiilt, and Barakso (1966).

Do.

Do.

Stock and Cucuel (1934a). 

Anderssen (1967).

Do.

Aidin'yan, Troitskii, and Balavskaya (1964). 

Dvornikov (1963). 

Dvornikov and Petrov (-1961). 

Morozov (1965). 

Karasik and Morozov (1966). 

Aidin'yan, Troitskii, and Balavskaya (1964).
58 MERCURY IN THE ENVIRONMENT

TABLE 14. Mercury content of natural waters, in micrograms per liter

[1 microgram per liter ~1 part per billion mercury]

1

Sample

lumber of

analyzed

Range

Min Max

_ge Reference

Rivers

Rhine River __ _ _________________________

Saale River, Germany. -.--_-..--_.__..-__

Elbe River, Germany.-.-..... _ -._______

Danube River. ___________________________

Sweden _______________________________

European SSSR. --------------.-.-.-.....

Armenian SSR_ __----------___-----_--___

Armenian SSR_ __----__---____---_--_____

8 

1

4 

24 

7 

6 

300

0

1 

1

.05

1 

.02 

.4

.01

_..-.... 0

'0.19

2 .....

.2

.1 

.07

.09

2.8 1.1 

20 4.2 

2 2.0 »1.6 

"136 <.l

Stock and Cucuel (1934a). 

Heide and Bohm (1957), and Heide, Lerz, 

and Bohm (1957). 

Do. 

Aidin'yan and Balavskaya (1963). 

Wikander (1968). 

Aidin'yan (1962). 

Aidin'yan (1963). 

Do.

Sea water

Atlantic, Indian, Red Sea, Black Sea, etc.... 

Atlantic Ocean. _______________________ ._

Pacific Ocean, Ramapo Deep _ ____________

Do..__... ...........................

Minamata Bay, Japan __ ________________

14 

9

4

0 

1

Ground water

Rainwater. ______________________________

Spring water, Germany _ -.----_____-___-_

Surface waters, Northwest Caucasus. _______

Subsurface waters, Northwest Caucasus. ....

Springs, Elbrus region. ... ________________

(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 _

Brines associated with petroleum, Cymric oilfield, California. 

Brine, geothermal well, Salton Sea, Calif ....

7,000{ 

37

26

1

0 

<

0

<

1

1

100

.7 

.4 

.08 

.15 

.6

........ 0

2.0 1 

1.6 1 

.15 

.27 

3.6 .....

.03 

.03 

.1 

.2 

.1 

.2

Stock and Cucuel (1934a). 

Heide and Bohm (1957). 

Aidin'yan (1962). 

Aidin'yan, Ozerova, and Gipp (1963). 

Hamaguchi and others (1961). 

Hosohara (1961). 

Hosohara and others (1961).

and miscellaneous samples

.05 

.01 

.27 

.25 

.05

1

.5

0.48 0 

.05 .....

.68 --.-.

1.25 .....

80 

140,000 .....

2.5 .....

2.5 .....

3 .....

5 .....

<8.5 .....

400 .....

........ 6

.2

=1

.5

Stock and Cucuel (1934a). 

Do. 

Baev (1968). 

Do. 

Krainov, Volkov, and Korol'kova (1966). 

Ishikura and Shibuya (1968). 

Morozov (1965). 

Karasik and Morozov (1966). 

Zautashvili (1966). 

Do. 

Do. 

Karasik, Goncharov, and Vasilevskaya 

(1965). 

Bailey and others (1961).

Skinner and others (1967).

1 The value 0.19 (next highest 0.08) is ascribed to waste water from an industrial 

plant. 

* Excluding the highest value.

* Values above 0.1 ppb were in the drainage area of mercury deposits. 

4 Another sample, a concentrated brine, contained 220 ppb Hg.
TABLES 

TABLE 15. Mercury in air and in volcanic emanations, in nanograms per cubic meter

[1 nanogram = 10-' grams]

59

Sample

Number of 

samples 

analyzed

Range

Min Max

Average Reference

Air

"Unpolluted air"-. __._............._._.._

Over Pacific Ocean, 20 miles offshore.- .

California, winter,.. ._...__.___. __

California, summer _ ... ....

Background, Arizona and California __ ....

Chicago area.-.-. ______ .___

Kamchatka _...___ ..____._._

Moscow and Tula regions (no ore deposits)

Over porphyry copper deposit. ...__..__..

Do______________ ____

Over mercury deposit. ___-__-._____ _.

Do........:-. ______________ ... '

Do.......................

2

22 

10

0.6 0.7 

1 25 

1.5 50 

1.6 7.2 

3 39

80 300 

12 30 

18.5 53 

12 57.5 

58 66 

200 1,200

8 Stock and Cucuel (1934b). 

________ Williston (1968).

____..._ Do.

Do.

4 . 5 McCarthy and others (1969). 

9.7 Brar and others (1969). 

190 Aidin'yan and Ozerova (1966). 

...-__-_ Do.

18 . 8 McCarthy and others (1969). 

28 Do. 

31.4 Do. 

62 Do. 

._ . ... Karasik and Bol'shakov, quoted by

Aidin'yan and Ozerova (1966).

Volcanic

Air of vent breccias of mud volcanoes. __..__

Gases of mud volcanoes.--------. ... ._ .

Gases, Mendeleev and Sheveluch Volcanoes

Gases from hot springs, Kamchatka and 

Kuriles. 

Condensates from fumaroles and volcanic 

emanations, Kamchatka and Kuriles. 

Waters from hot springs, Kamchatka and 

Kuriles.

* Parts per billion.

TABLE 16. 

Ni 

Sample

Germany. ____________________

Donets Basin, U.S.S.R. _______

Do____._. __.__.........

Do______. _____________

Donets Basin, U.S.S.R. (in lenses within mercury ore body). 

Donets Basin, U.S.S.R. _ Do................ ....

Do......................

umber of 

samples - 

analyzed

11

206

75

13

300 700 

700 2,000 

300 4,000 

10,000 18,000

1 .2 i?2 

1 .5 U

._.----. Karasik and Morozov (1966).

........ Do.

.-_--_-. Aidin'yan and Ozerova (1966) .

........ Do.

________ Do.

........ Do.

-Mercury in coal, in parts per billion

Range

Min Max

1.2 25 

4,500 70,000 

140 300,000 

50 10,000 

2,500 6,500

20 20,000 

100 7,000 

100 300,000

Average Reference

12 Stock and Cucuel (1934a). 

11 , 100 Karasik and others (1962). 

46,000 Ozerova (1962). 

1 , 100 Dvornikov (1963). 

3,700 Bol'shakov (1964).

_.__..__ Dvornikov (1967a).

........ Dvornikov (1965, 1967b).

46,000 Dvornikov (1968).
TABLE 17. Mercury content, in parts per billion, of selected rocks, soils, and stream sediments

[Type of sample: mine and dump samples are mineral aggregates. Percentiles: 25, 50,75, and 90 percent, respectively, of the total samples in each set of 

content equal to or less than the listed mercury value; percentiles were computed using a linear interpolation of the cumulative frequency distri

of mercury values for each data set. Primary mode: the most frequent observed mercury content in the frequency distributions for each set of da

is the second most frequent. Source of statistical data: sources not shown as published or otherwise explained represent information from compu

Gila Wilderness, N. Mex _____ ..............

Salmon-Trinity, Alps Primitive Area, California 

Coeur d'Alene, Idaho.. _.-... .__----._

Bob Marshall Wilderness, Mont. .. ______ -.

Edna Mountains, Nev_. .-----..-.. --------

Aurora district, California-Nevada. . ...- . . . . .

Ivanhoe (mercury district), Nevada. .-.-_------

North Battle Mountain, Nev.___ ___ ... .. ...

Midas, Nev.. ___ _____________ .. .....

Gulf of Mexico.... -... __._

Drum Mountains, Utah ___....._.__ ._-__

Ely, Nev... .. ___ ... . ..

Rowe Canyon, Nev. .-.------........_. .....

VeittAW p«mitive area, Calif

Uncompahgre primitive area, Colorado . __ ...

Mission Mountains Primitive Area, Mont _ .. ..

Blue Range primitive area, Ariz. and New Mex..

Gore Range-Eagles Nest Primitive Area, Colo. . .

San Rafael Wilderness, Calif...... __ . .....

Consejo area, Puerto Rico. __ ------ _ ... _ _

Taylor Mountains, Alaska: 

C-8 quadrangle.. -.... _ __ _ ......

D-8 quadrangle..... ... __ .............

B-6 quadrangle.. .. ....-- ... 

A -6 and south-half B-6 quadrangles __ ....

Nation River, Alaska. _____ ___ __ __ .

Brooks Range (north side), Alaska... _ _ ....

Western Missouri. --------- __ _ .........

Eastern Missouri ___ ..-------. _ __ -------

Missouri (summary) . . .. . ...

Kansas fiity, Mo

Kentucky....... .. . __ . .. ...

North end of Sierra Cuchillo, N. Mex ------- 

Silver Creek area, Baker, Nev.... .

Luis Lopez district, Socorro, N. Mex._ _ __ ..

Little Florida Mountains, N. Mex __ 

Colorado Plateau.. _..-_ _ .... ___ .....

detected

Rock... ______ . ..........

..do......... ........... _ .. 

.-do.-.-..-. ._-.__..-. - 

Soil ___ ... _ _ -

Dump....... _.. ....------.

Stream sediment .. _..__-_---

Rock..... ______ .._. 

Stream sediment.. ._-----_.-_-

Mine... __ . ________ ...

Dump.------.--..---. - --.

Rock. ___-...__. 

Mine.. ---------------------

Dump...._---.-.---._. ... .

Rock... .. _ _ ...... ....

Soil................... ....

Rock. ___ 

Soil...... _ 

Dump...... --------.-. -_.

Rock-...---. ....... . 

Soil... __ .. _ ... - . .- 

Dump ----- - -------------

Unconsolidated sediment. . . _ . _ _

Rock.... __. 

..do ___ ....................

..do . _ _

Metamorphic rock. .. . ._.-...

Intrusive rock. _ -----------

Sedimentary rock. ------ - -

Altered rock.. ----------------

Stream sediment. .. -. - - ...

Vein and mineralized material 

Altered rock. __ ..__.__ . _

Unaltered rock _----------.--

Stream sediment....----- -

Intrusive rock .. . .-------..

Metasedimentary rock.. ... . .

Vein material and altered rock..

Unaltered rock...- - - -------

Altered rock. .............. _..

Stream sediment. ___.-.- . ...

Mainly altered rock and vein

material.

Sedimentary rock __ ----- . .

Carbonate vein material _ _ . . .

Fault gouge and breccia. ------

Stream sediment.-..--. ..-.-

Soil-. _ . __ .. _________

Outcrop and mineral occurrence.

Stream sediment. _____________

. _ do--... _____._.._._ .....

Outcrop and mineral occurrence. 

__ do....... ... ..-- _ ...

Organic-rich shale..... ... ---

-...do ______ ., ___ ___ ..

Shale...----.......----- _ ..

Carbonate rock ...... _ ______

Sandstone............ -------

Rock __ ..._..__._. _ ......

Soil ______ ... _____________

Chattanooga Shale. ___---_---_

Arroyo sediment....--.... ...

....do.. _ ...... ___ . _ ..

Manganese ore _ . _ _------.-

-...do . _ . . _ ... _ ...

Sedimentary rock __ ... ..

10

10 

10

10

15

10

10

40

20

10

10

30

10

20

10

20

20

40

20

20

40

70

10

10

10 

10

10

10

10

10

20

10

10

10

20

20

20

10

10

10

10

10

45

25

10

10

800

60

70

240 

200

80

40

20

20

30

10

10

30

20

10

10

16

100

10

Pii

41

21 

10

50

58

21

43

61

45

64

76

340

57

340

82

100

51

280

90

88

420

95

86

20

30

....

.---

Percentile

Pw

84

53

30

100

40

36

76

77

230

150

180

940

110

2,500

200

240

71

420

250

120

740

110

260

50

100 

25

40

30

40

80

260

160

90

100

20

20

20

30

60

50

80

40

75

225

60

120

14,200

1190

1540

1320

1360

2570

270

240

220

240

2550

219

229

2161

21,900

160

P?i

200

100 

70

220

230

50

220

170

2,400

860

490

2,100

290

780

550

100

4,200

850

210

1,280

150

900

170

300

__-.-

___._

.....

 

P,«

400

220 

150

380

730

66

600

2,000

1,400

4,900

780

3,230

2,070

140

9,900

2,500

340

3,410

4,230

620

660

....

___-_

-----

-----

-----

detected

7,000

500 

57,900

180,000

3,500

220

9,000

2,200

2,500

2,500

150,000

8,000

150,000

> 10, 000

> 10, 000

>10,000

350

15,900

8,790

3,900

6,490

220

95,000

14,000

15,000 

320

620

350

2,000

290

30,000

3,800

710

700

60

380

120

180

11,000

1,200

> 10, 000

3,300

520

1,000

>4,000

1,500

15,000

3,000

9,000

9,000 

700

10,000

650

2,800

160

50

40

1,000

1,300

1,500

48

54

1,000

10,000

10,000

Number 

of

samples

761

36 

2,515

5,617

13

309

1,694

37

27

172

1,298

199

684

519

681

151

103

15

300

152

53

27

928

1,466

445 

35

40

25

134

164

225

334

92

161

9

254

40

98

120

648

796

192

11

7

91

576

28

226

109

22 

19

59

15

253

5

6

5

19

30

213

74

50

72

54

3,012

mode

200

50 

30

200

200

50

50

70

50

70

200

1,000

60

5,000

70

300

70

300

200

100

1,000

100

200

20

200

m

>2

2

1

2

6

> Geometric mean. * Arithmetic mean.
TABLES 61

TABLE 18. Mercury content, in parts per billion, of some sedimentary stratigraphic units in the Colorado Plateau region of the United States

[Units are arranged in order of youngest (Tertiary) to oldest (Permian and Pennsylvania!!)]

Number 

Stratigraphic unit of Median 

samples

Highest Lowest

Middle 

68 percent 

of samples

Approximate 

Dominant rock types average 

thickness (feet)

Tertiary, northern Colorado Plateau region

Duchesne River Formation. . ________

Uinta and Green River Formations. . _.

Wasatch and Colton Formations __ ...

Mesaverde Group and Mancos Shale ____

62 

260 

198

256

60 

100 

280

Cretaceous,

240

180 

4,000 

1,100

15 

15 

80

37-100 

44-240 

150-520

Sandstone.

Shale, sane 

Mudstone,

Istone __ __--.-

sandstone.

1 

8 

2

,500 

,000 

,000

northern Colorado Plateau region

1, 500

Jurassic, Colorado Plateau

Morrison Formation ..__... _ ... ...

Entrada Sandstone __ . ....._.________

Carmel Formation. . .____._.........__

Navajo Sandstone. .-_--_..-. .......

653 

258 

80 

91

190 

170 

100 

40

>6, 

5,

000 

000

500 <

30

region

10 

10 :io

140-400

84-420 

80-360 

53-170 

10-150

Mudstone,

Sandstone, 

SandstoneSandstone, 

Sandstone.

mudstone.-----

siltstone _ _.._

5

1 

1

,000

,000 

500 

300 

,000

Triassic, Colorado Plateau region

Wingate Sandstone. ............_..__.

Dolores Formation.. . _.-_--._____._ .

Chinle Formation.. _-_.....-.._...___.

Moenkopi Formation _ . . _____________

160 

42 

538 

323

260 

210 

260 

110

1,

>6, 

>10,

900 

760 

000 

000 <

80 

80 

60 :io

140-370 

120-370 

140-460 

40-320

Sandstone .

Sandstone, 

Mudstone, 

Siltstone, sandstone ___.

300 

'300 

1,000 

1,000

Upper Paleozoic, Colorado Plateau region

Cutler Formation (Permian) ...........

Rico and Hermosa Formations (Permian 

and Pennsylvanian).

30 

61

170 

200 .; 300 200

50 

20

90-300 

100-370

Sandstone, 

Limestone,

conglomerate. . 

siltstone __ .__

»1 

*2 ,000 

,000

1 Sampled only in east part of region. * Sampled only in central part of region.

TABLE 19. Equilibrium constants and standard potentials at 25°C and 1 atmosphere pressure

[1 = liquids, g = gases, c = solids, ag = dissolved species]

Equilibrium

Constant 

(JO (volts) Source of data

Hg_+H-2e=2Hg°l_

[g° 1 .".

Hg°l=Hgaq__...___

HgO c+2H++2e=Hg

Hg2C-2C=Hg2+! +2Cl.

HgCl_°=Hg+*+2Cl-.__-_

HgCla-=Hg+*+3Cl-____.

HgClr! +2e =Hg8 1+4C1- HgS048 aq=Hg+*+S-*

HgS(metacinnabar) =Hg+! -

HgS c+S-2 =HgS2-!-

Hg(HSJ_° =Hg+*+2HS-................;....

'"'"O,), C+2H+ =Hg+«+2"CHaC60H aq"

Hg(CH_) z l+2H+ =Hg+*+2CH4 aq.._..._____

Hg(CHa) 2 1+H.O =CH4 aq+CHaOH aq+Hg 1. 

CH,Hg++OH- - CHaHgOH aq. ____________

C«HsHg+ +OH-=C6H5HgOHaq____________.

CHaHgCll = CHaHgClaq___. _______________

CHsHgClaq=CHaHg++Cl----____-__._.__.

1Q-6.89

i6^"~H

lQ-18.38 

IQ-IM

4.57

lQ-37.73 

10-3.11

1Q7.80

1Q19.74

1Q9.M

1Q1.0

1Q-1.70

10-5.46

0.789 Latimer (1952).

.921 Do.

.855 Do.

_____ Do.

----- Calculated from data in Wagman and others (1969).

.925 Latimer (1952).

_____ Do.

-.___ Helgeson (1969).

___-. Do.

.386 Latimer (1952).

-. __ _ Calculated from data in Wagman and others (1969).

_____ Helgeson (1969).

_____ Do.

_._. _ Calculated from data in Wagman and others (1969).

..__. Do.

_._.- Do.

.._-- Calculated from data in 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.
62 MERCURY IN THE ENVIRONMENT

TABLE 20. Standard free energies of formation of certain mercury species, in kilocalories per mole

ite no common names. 1 = liquids, g = gases, c = solids, aq = d 

Data from Latimer (1952) and Wagman and others (1969)]

[Leaders indicate no common names. 1 = liquids, g = gases, c = solids, aq = dissolved species.

	Free energies 

Formula Description (&G0/)

Hg° 1____________________._______ Metallic mercury ____________________ 0.0

Hg° g__________________________ Mercury vapor - - - - 16.3

Hg° aq________________________ Dissolved mercury_________________ 9.4

Hg2+2____. _______________________ Mercurousion-.. ___---_---- 36.70

Hg+2_____-_._____________________ Mercuric ion___--_.----------_---_-_ 39.30

Hg2Cl2 c......................... C^\OTcie\............................ -50.35

HgCl2 c--_-_---_-__---_______.___ Mercuric chloride__________________ 42.7

HgO c-____---_____-_:__.________ Red oxide_____---------------__--__- -13.995

HgO c----------__--_-__--___.___ Yellow oxide----------.----....--.- -13.964

HgOH+._____.___________________ ___________________________________ -12.5

HgO OH-_____-__._______________ _-._--...-.---------------.---.-.- -45.5

Hg(OH) 2 aq___ ________________ ---------------------------------- -65.70

HgS c ----_------- __---- Cinnabar.--------------------.----- -12.1

HgS c__-_-----------_--__-____-_ Metacinnabar_ -___________________ 11.4

Hg2SO4 c -------------------- -.-------.--_------------------.--- -149.589

HgSCVaq- ______________________ ______________ _ ______ _ _ _______ -140.6

Hg2CO3 c___ -_-__---_-_-___-__ ----------------------------------- -105.8

HgCl2°aq ------_-------_-- .-------------------------_.---_-- -41.4

HgClr2 ----------------- _--_-_.-.-.-.--------------------- -107.7

Hg(CH3) 2 ________________________ ___________________________________ 33.5

TABLE 21. Mercury concentrations from results of analyses of selected thermal and mineral waters 

and their deposits, Northern California mercury district

[Detection limit, 0,01 part per billion. N.d., not detected. Analyses by M. E. Hinkle]

Mercury

Sample County concentration 

_____________ ____ _______________________(in ppb)

Condensates, condenser coil packed in ice

McKinley well 1_______.________________________ Lake________________ 3.0

McKinley well 3._-_-------_-----__----------.-- __do_-__________________ 1.0

Waters of low to moderate salinity, T<40°C

Alien Spring--- -_-__-___ __-_________________ Lake__________________ N.d.

Bartlet Spring-...-._______.-_-_._-_________-._. --do.---.------.----.--- N.d.

Spring east of Alice mine_______________________ Colusa- - -.__.-___. N.d.

Waters of high salinity, T <40°C

Grizzly Spring.......___________________________ Lake.......--. __________ N.d.

Abbott Mine water____________________________ -.do..__________________ 1.0

Dead Shot Spring _ __ Colusa__ ______________ N.d.

Wilbur oil test well______________________________ ..do.- --------------- 0.2

Salt spring north of Wilbur Springs. -------------- - -do. _____-._______---__ .1

Complexion Spring._____________________________ Lake__________________ 1.5

Salt Spring north of Stonyford ------- --- Glenn ---- ------- N.d.

Redeye Spring (Fouts Springs)_________________ Colusa------------------ N.d.

Waters of low salinity, T >40°C

Castle Rock Spring____________________________ Lake__________________ N.d.

Anderson Spring_____-__________________________ do - _ _-_- -- N.d.

Seigler Spring ____.--_________........_...__._ _.do-_---_--_----------- N.d.

Waters of moderate to high salinity, T >40°C

Sulphur Bank__-___--________________ --_-__ Lake_--_--------._--_- 1.5

Wilbur Springs.______ __ _________ _ Colusa.___----_-__._-._- 1.5

Solids

Sulfur floating on Wilbur Springs------ . ------ Colusa_ ___________ 30,000

Magnesia-silica gel from Complexion Spring.------- Lake__________________ 800

Silica-magnesia gel from Aqua de Ney_------------ Siskiyou_--___-____--_- 500
TABLES 63 

TABLE 22. Mercury concentrations in thermal waters from Yellowstone National Park

[Detection limit, 0.01 part per billion. N.d., not detected. Analyses by M. E. Hinkle]

Mercury 

Sample Location concentration

Ojo Caliente _ _________________________________ Midway Basin. _--__----_ 0.14

Ear 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...------- .18

Little Whirligig Spring _ ____________________ .__. Norris Basin.------------ .07

Cinder Pool. ____----___._.________---------_.__ _.do_-. ----------------- .28

Spring, base of Porcelain Terrace __ _________.... __do_---_-_------------- .10

Echinus Gey8er______-_. ________________________ ..do.----.-------------- .11

Cistern Spring. _________________________________ _. do. ------------------- .08

Primrose Spring_______. ________________________ Sylvan Spring 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 analyses of petroleum from the Wilbur Springs area,

northern California

[Detection limit, 0.01 part per billion. Analyses by M. E. Hinkle]

Mercury

Sample County concentration 

________ (in ppb)

Tarry petroleum, Abbott mine _ _________________ Lake __ __--_-__-_-_---- 500,000

Petroleum, Wilbur oil test well--___--_-----_-_-_- Colusa.----------------- 1,000

TABLE 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

Gold Creek at Juneau, Alaska _ ________________ . . ... .

Colorado River near Yuma, Ariz _ _ _ _ _ _ _ _ . ________

Welton Mohawk Drain near Yuma, Ariz _____ __..____._.

Ouachita River downstream from Camden, Ark .... - .

St. Francis River at Marked Tree, Ark ._- -..______

Santa Ana River below Prada Dam near Riverside, Calif - . .

South Platte River at Henderson, Colo _ _ _ .

Blue River upstream of Dillon Reservoir, Colo ______ _ -

French Creek near Breckenridge, Colo __ _ _ . __________

Animas River at Silverton, Colo __ _ _ _ ------------ _ . ._.

Cement Creek at Silverton, Colo ___ --------

Red Mountain Creek near Ouray, Colo _ --------

Red Mountain Creek at Ironton, Golo _ _ _

Nuuanu Stream near Honolulu, Hawaii _ _ ____________

Honolii Stream near Papaikou, Hawaii __ ._____._ . . - _

North Fork Kaukonahua near Wahiawa, Hawaii- - - _ . . _

Ohio River near Grand Chain, 111 _ _ ______________ _ _ .

Floyd River at Sioux City, Iowa. _____________ _ _....

Kansas River downstream from Topeka, Kans _____________

Mississippi River near Hickman, Ky_. ___________________

Merrimack River above Lowell, Mass _____________ _______

Wolf Creek near Cedar Lake, Mich ------ ____ ___ ______

Unnamed tributary to Wolf Creek near Edmore, Mich

Month-day

.---_ 6-10

.--._ 6-18

. . 6-19

....- 6-18

--._ 6-19

-.-_ 6-29

--.- 5-19

---. 6-22

.-.. 6-22

---. 6-22

.-.- 6-22

---. 6-22

-.-- 6-22

.--- 6-8

-_-. 6-8

---. 6-11

.--. 6-26

.__. 6-9

-.-- 5-19

.... 6-25

.... 6-8

-..- 6-7

.... 6-7

Hour

1350

-_--

0900

1000

__- _

1410

---_

0930

1405

1800

1040

1645

1130

1030

1100

1100

1000

(in ppb)

<0.1

<.l <.l

<.l.1

<.l

.3

<.l

<.l

.1

<.l

17

<.l

.6

<.l

.4

.1

.2

3.5

<.l

1.2

<.l

.1
64 MERCURY IN THE ENVIRONMENT

TABLE 24. Mercury in selected rivers of the United States, 1970 Continued

[Analyses by M. J. Fishman (U.S. Geological Survey, written commun., 1970)]

	Time sample collected

Source and location -T- Mercury

Month-day Hour (in ppb)

Rainy River at International Falls, Minn _ _________-_-_-_--__ 5-14 1245 <. 1

St. Louis River at Scanlon, Minn_..-.-_...__-.---.-._.. 6-8 1015 <.l

Pearl River at Byram, Miss _._..__.------._._____________ 6-17 1445 .1

Pascagoula River at Merrill, Miss _-_--.._________________ 6-9 1500 3.0

Yellowstone River near Billings, Mont ________________________ 5-14 1500' <.l

Missouri River near Great Falls, Mont ________________________ 5-18 1730 <.l

Missouri River near St. Louis, Mo _._____-________---_-_____ 6-23 1430 2.8

Missouri River at Hermann, Mo __-------_-_-_---_-_-_------_ 6-24 1030 .2

Salt Creek near Lincoln, Neb._________________.__-_._____ 6-24 0915 .5

Las Vegas Wash at Henderson, Nev-_--_------------------_-_ 5-14 .__- <.l

Pemigewasset River at Woodstock,N.H _----__-____--.____._ 6-8 1700 3.1

Canadian River near Glenrio, N. Mex _____________________ 6-10 1100 <.l

Hudson River downstream from Poughkeepsie, N.Y ____________ 4-7 ____ .1

Hoosic River near North Pownal, Vt., in Rennsselaer County, N. Y _ 4-7 . _ _ _ .1

Wappinger Creek near Wappingers Falls, N.Y _______________ 4-23 1045 <. 1

Delaware River at Port Jervis,N.Y ___________________________ 4-23 1420 <.l

Beaver Kill at Cooks Falls, N.Y __-_---_-_--_____---_-----___ 4-24 1320 .1

Deer River near Helena, N.Y ____------------_-------------__ 5-5 0735 <.l

Raquette River at Raymondville, N.Y ________________________ 5-5 0945 .2

Oswegatchie River at Gouverneur, N.Y _______________________ 5-6 0800 .7

Oswegatchie River at Gouverneur, N.Y _______________________ 6-16 1200 1.2

BlackRiveratWatertown, N.Y-__----_-_--___-._-_---------. 5-6 1015 <.l

Black River near Watertown, N.Y ____________________________ 5-6 1155 <.l

Lake Champlain near Whitehall, N.Y __-_----____--____-_-.___ ____ ____ <.l

Lake Champlain near Ticonderoga, N.Y_--____-------------. ____ .___ <.l

Lake Champlain near Crown Point, N.Y _---__-_--__------____ ____ .___ .1

Raquette River at Massena, N.Y _____________________________ 6-16 0840 <.l

Raquette River at Raymondville, N.Y ________________________ 6-16 0910 <.l

Raquette River at Potsdam, N.Y __-___-_-.--__-----_---_-__._ 6-16 0950 .1

Oswegatchie River below Natural Dam, St. Lawrence County, N.Y . 6-16 1130 <.l

OswegatchieRiveratHailsboro, N.Y __-__-________-_----.--__ 6-16 1230 .2

ChemungRivernearWellsburg, N.Y ___----___-_-___---._____ 7-6 1015 .2

Susquehanna River at Johnson City, N.Y _--_____-_-_--_._____ 7-6 1330 .1

Maumee River at Antwerp, Ohio___-__----____---_-_-___-__- 6-10 1215 6.0

Scioto River near Chillicothe, Ohio_-_---------_-_-____----___- 6-25 1115 <.l

Great Miami River near Miamisburg, Ohio__.--___-_______.__ 6-11 1815 .9

North Canadian River near Harrah, Okla ____________________ 6-30 1000 1.1

North Canadian River near Oklahoma City, Okla ______________ 6-30 1345 .1

Whitewood Creek near Vale, S. Dak ___--_--_____-__-___-__--. 5-22 1100 <.l

Paper Mill Creek near Herty, Tex--_-__----___._-_-_--------_ 6-9 1015 .1

San Antonio River near Elmendorf, Tex _.-_______-_____-_-_. 6-11 1100 <.l

Blackwater River at Franklin, Va __----------_---_---------_- 6-15 0930 1.1

Jackson River near Covington, Va-----_---------------------_ 6-16 0820 <.l

Bailey Creek near Hopewell, Va __--____----_-_-_--__-----.--- 6-18 0945 .4

Snohomish River near Monroe, Wash ___-_--__-_-___________._ 7-1 1050 <.l

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, Wyo ___-__-_____-____-_-_.___ 6-23 1215 .1

Bighorn River at Kane, Wyo ________________________________ 6-30 1600 <.l
TABLES 65

TABLE 25. Mercury levels in natural waters outside the United States

Location

Concentration

levels

(in ppb)

Reference

Sea water, vicinity of Helgoland.__._.__.._ 

Lamapa Deep ___________________________

Ramapo Deep (Pacific Ocean, southeast of

Honshu, Japan). 

Minamata Bay, Japan._--_--______-._-___

Sea waters of U.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 Abkhasia,

U.S.S.R. 

Natural waters of Germany. ___-______--__

Saale River, Germany.---...-..__________

Uncontaminated river waters of ItalyRivers near mercury deposits of Italy.

0.03 Stock and Cucuel (1934).

. 08-0.15 Hamaguchi and others (1961)

.15- .27 Hosohara-(1961).

1.6-3.6 Hosohara and others (1961).

.7-2 Aidin'yan (1962).

1-2 Aidin'yan and Belavskaya (1963)

.4-2.8 Aidin'yan (1962).

1-3 Aidin'yan (1963).

.5-3.6 Zautashvili (1966).

.01-.05 Stock and Cucuel (1934).

.035-. 145 Heide, Lerz, and Bohm (1957). 

(avg,.067)

.01-.05 Dall'Aglio (1968).

Up to 136 Do.

TABLE 26. Mercury consumption, in kilograms, in the United States for calendar year 1969 and the first quarter of calendar year 1970

[From "Mineral Industry Surveys," U.S. Bureau of Mines, first quarter, 1970]

Use

Agriculture 1 ___ __ . ___ ... _ -...-. ___ ....

Amalgamation. ... ______________________ ....

Catalysts _ ... ___ .... ___ . ___ .. _ . ___ ....

Dental preparations.... ___ ____ ...... ___ ...

Electrical apparatus. ___________________________ __

General laboratory use. ---_---_-----.--... . .

Industrial and control instruments. _. ... __ ___ ______

Paint: 

Antifouling. _ ___ ___ . ____ ...... __ ._

Mildew proofing __ .--_._-____-.-...

Paper and pulp manufacture ___ _ -......_._ _ ...

Other_________________. ___._.___.__._____.__.__._

Total known uses. __ ______________ _ _ _ _.

Total uses unknown. ... __ .. ___ ..........

Grand total __ . _ ____.. _ __ .

1969

Primary

O9 77«

6,693

77,108

7,383

... 457,470

... 664,574

42,504

97,704

8,418

... 327,267

19,251

4 n jinn

... 290,732

... 2,104,293

4,623

... 2,108,916

Redlstilled

34 

4,968 

49,059 

132,998

19,148 

120,198

12,558 

2,794

341,757 

3,691

345,448

Secondary

19,976 

48,886 

52,958 

50,266 

8,763 

22,942

40,744

244,536 

30,188

274,723

Total

92,770 

6,728 

102,051 

105,328 

634,425 

714,840 

70,414 

240,844

8,418 

327,267 

19,251 

24,978 

334,270

2,690,586 

38,502

2,729,088

Primary

26,462 

4,036 

19,941 

242 

106,778 

125,752 

12,696 

16,250

1,173 

87,872 

9,280 

2,346 

140,036

448

2563,902

First quarter, 1970

Redistilled

104 

414 

9,832 

20,458

2,036 

20,252

3,416 

5,175

1,587

269,690

Secondary

207 

6,210 

14,076 

3,692 

5,692 

3,070

621 

1,104

4,520

M1.055

Total

26,462 

4,140 

20,562 

16,284 

141,312 

129,444 

20,424 

39,572

1,173 

87,872 

9,280 

6,382 

146,314

6,555

2674,647

i Includes fungicides and bactericides for industrial purposes.

» The items do not add to the total which has been increased to cover approximate total consumption.
66 MERCURY IN THE ENVIRONMENT

TABLE 27. Lethal concentrations of mercury compounds for various aquatic organisms and man

[Data summarized from numerous published reports]

Organism

Lethal

concen ration 

(PPb)

Mercury compound

Aquatic organism

Bacteria:

Escherichia coli...................... 200 Mercuric chloride.

200 Mercuric cyanide. 

300 Ethylmercuric bromide. 

300 Phenylmercuric chloride. 

300 Ethylmercuric oxalate. 

Phytoplankton:

Marine mixture._____________________ 60 Ethyl mercury phosphate.

Scenedesmus- ________________________ 30 Mercuric chloride.

150 Mercuric cyanide. 

Protozoa:

Microregma.......................... 150 Mercuric chloride.

160 Mercuric cyanide. 

Zooplankton:

Daphnia pukx....................... 5 Phenylmercuric acetate.

Daphnia magna...................... 20 Mercuric cyanide.

6 Mercuric chloride. 

Amphipod:

Marinogammarus marinus............. 100 Mercuric chloride.

Isopod:

Mesospheroma oregonensis............. 15 Mercuric nitrate.

Flatworm:

Polycelis nigra....................... 270 Mercuric chloride.

Polychaete:

Mercierella enigmatica................. 1, 000 Mercuric nitrate.

Mollusca:

Bivalve larvae.---.-_-___.__----_-___ 27 Mercuric chloride.

Australorbis gldbratus................. 1,000 Do.

Fish:

Stickleback________________________ 20 Mercuric nitrate.

4-020 Mercuric chloride.

Guppy__---_---_-_.__-_.__-_-_-___ 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___________________________ ^.O Mercuric chloride.

Adult, chronic illness,---------___-------_ * .1 Do.
TABLES 67

TABLE 28. Maximum mercury concentration in air measured at scattered mineralized and nonmineralized areas of the Western United States

[..., no data available]

Maximum Hg concentration (ng/m»)» * 

Sample location

Ground 400 feet above 

surface the ground *

Mercury mines

Ordmine, Mazatzal Mtns., Ariz._______________________ 20,000 (50) 108 (4)

Silver Cloud mine, Battle Mtn., Nev_ ___________________ 2,000 (50) 24 (8)

Dome Rock Mtns., Ariz________________________________ 128(6) 57(20)

Base and precious metal mines

Cerro Colorado Mtns., Ariz____________________________ 1,500(5) 24(2)

Cortez gold mine, Crescent Valley, Nev_. _______....___ 180 (60) 55 (4)

Coeur d* Alene mining district, Wallace, Idaho _________ _ 68 (40) ______

San Xavier, Ariz____________._________________________ ________ 25 (3)

Porphyry copper mines

1 ng/m*-nanograms (10-> grams) per cubic meter of air. 1 ng/m'-10-( ppb. 

1 Number of measurements shown in parentheses.

I RftYnnlAQ talrAn tfnm ain<»lA_AMfln*ia airM~af+

- m umuer ui measurements snown in parem 

1 Samples taken from single-engine aircraft.

Silver Bell mine, Arizona___---__-_____________..______ ________ 53 (3)

Esperanza mine, Arizona___________________..-__.._ _._-_._. 32 (3)

Vekol Mtns., Ariz________.____________________________ ________ 32 (4)

Ajp mine, Arizona______________________________ ________ 30 (3)

Mission mine, Arizona_______________________________._ ________ 24 (3)

Twin Buttes mine, Arizona___________________________ 20 22(3)

Pima mine, Arizona.__________________________________ ________ 13

Safford, Ariz__-__--------_-_.____________________._ _._---.- 7

Unmineralized areas

Blythe, Calif_________________________________________ ________ 9 (20)

GilaBend, Calif____-_____.___________________________ ________ 4 (2)

SaltonSea, Calif_-_.__________________________________ ________ 3.5 (2)

Arivaca, Ariz_ ....................................^. ______ 3 (2)

GPO 903.789