EPA-600/2-77-171
August 1977
Environmental Protection Technology Series
HEAVY METAL POLLUTION FROM SPILLAGE
AT ORE SMELTERS AND MILLS
ial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECH-
NOLOGY series. This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-77-171
August 1977
HEAVY METAL POLLUTION FROM SPILLAGE
AT ORE SMELTERS AND MILLS
by
Staff, Environmental Systems Department
Calspan Corporation
Buffalo, New York 14221
Contract No. 68-01-0726
Project Officer
John E. Brugger
Oil and Hazardous Materials Spills Branch
Industrial Environmental Research Laboratory - Cincinnati
Edison, New Jersey 08817
INDUSTRIAL ENVIRONMENTAL RESEARCH LABORATORY
OFFICE OF RESEARCH AND DEVELOPMENT
U. S. ENVIRONMENTAL PROTECTION AGENCY
CINCINNATI, OHIO 45268
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DISCLAIMER
This report has been reviewed by the Industrial Environmental Research
Laboratory--Cincinnati, U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily
reflect the views and policies of the U.S. Environmental Protection Agency,
nor does mention of trade names or commercial products constitute endorse-'
ment or recommendation for use.
ii
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FOREWORD
When energy and material resources are extracted, processed, converted,
and used, the related pollutional impacts on our environment and even on
our health often require that new and increasingly more efficient pollution-
control methods be used. The Industrial Environmental Research Laboratory-
Cincinnati (lERL-Ci) assists in developing and demonstrating new and improved
methodologies that will meet these needs both efficiently and economically.
Thallium, lead, copper, cadmium, indium, and zinc were determined in
streams, sediment, biota, and land at twenty-five sites. The heavy_metals
are introduced partly during operations as effluents (water or particulates)
and partly as spillage during leaching, runoff, dike failure, etc. The
work was specifically undertaken to determine whether the thallium
solubilized in ore processing was, like mercury, finding its way into the
food chain. The problem is not as severe as anticipated, and proper
housekeeping and treatment of waste water with lime can significantly reduce
the problem that does exist. The results complement other work on air and
land pollution that results from smelting. The report will be of interest
to those concerned with the uptake, effect, and distribution of trace
metals, and to health authorities who need data on the level of toxic metals
in mill towns near smelters. For further information contact the Resource
Extraction and Handling Division.
David G. Stephan
Director
Industrial Environmental Research Laboratory
Cincinnati
iii
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ABSTRACT
Smelter and mill wastewater outfalls, receiving water, biota, slag
heaps, tailings ponds, streams, and coal-burning fly ash dumps were
sampled as part of this effort to determine the effect of effluent or
residual spillage on aquatic systems. Since concentration of heavy
metals in sediment was found to be greater at any given time than that
dissolved in water, flood water erosion of particulate matter presents
a hazard. Up to 17% lead, 0.1% cadmium and 5 ppm thallium were found
in sediments of streams used for irrigation and drinking water below
copper and zinc extractive industries in high runoff regions.
Groundwater infiltration in the Northwest and Ozarks provides
mine drainage water which is used as process water in mills. This water
transports potentially toxic wastes into naturally erosive bottom sedi-
ments thereby contaminating the food chain. Heavy metal concentrations
in water and biota tend to be higher in the fall at low water, following
benthic accumulation during the growing season.
Prevention techniques recommended here include separation of waste
streams, protection of tailing dams from flood erosion, and recycle of
mill and smelter wastewater. Excess water discharged can be treated
with lime at elevated pH to precipitate heavy metals and to prevent
leaching of sediment already in streams.
The overall sensitivity achieved for thallium by a method developed
and reported here is 0.1 ppb in water. The detection, limit for thallium
in biota was determined to be approximately 10 ppb and 80 to 90 ppb in
sediment. This was due primarily to the presence of high concentrations
of chloride and other interfering ions in the collected samples.
IV
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CONTENTS
Foreword 11:L
Abstract fy
Figures V11
Tables . .*
Acknowledgments xm
1. Introduction 1
2. Summary . 4
3. Conclusions 6
4. Recommendations °
5. Approach '
Site Selection 9
Sampling Procedures and Techniques. 12
Sample Preparation 15
Sample Analysis '." 17
Atomic-Absorption Analysis 17
Electrochemical Analysis 20
Conclusions 20
6. Results 24
Scope of Section 24
Site Descriptions and Analysis 25
Western U.S 25
Tacoma, Washington 25
Kellogg, Idaho (Coeur d'Alene District) 28
East Helena, Montana.' ." . 33
Basin, Montana 35
Butte/Anaconda, Montana 37
Selby, California 44
Southwestern U.S ^4
44
Synopsis ...
Porphyry District y*
Planet Mine (Parker) Arizona j|l
Midwestern U.S °^
Mid-continent Lead/Zinc Region &3
Missouri New Lead Belt (Viburnum Trend) 63
Missouri Old Lead Belt 71
Herculaneum, Missouri 71
East St. Louis, Illinois 73
White Pine, Michigan 73
Eastern U.S 77
Perth Amboy and Sewaren, New Jersey 77
Palmerton, Pennsylvania 79
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CONTENTS (Cont.)
Other Known Thalliferous-Sulfide Accumulations. ... 79
Sites Not Requiring Sampling or Impossible
to Sample ................... 79
Steel Mills in Bethlehem, Pennsylvania, and
Elsewhere . . ................. 81
Sulfuric Acid Plants in Copper Basin, Tennessee . 81
Anthracite-Burning Powerplants Near Scranton
and Hazleton, Pennsylvania ........... 84
Bituminous-Coal-Burning Powerplant at
East Corning, New York ............. 86
Ecology of Thallium ................... 89
Purpose of This Subsection ............. 89
Abundance and Distribution of Thallium ........ 89
Behavior of Thallium in Natural Waters ........ 92
Thallium Exchange with a Montmorillonite Clay .... 92
Need for the Experiments ............. 92
Approach .................... 93
Results ..................... 93
Conclusions ................... 95
Biological Concentration of Thallium ......... 97
References
Appendix
A. Study of Alternative Solid-Sample-Preparation Methods ..... 104
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FIGURES
Number Page
1 Generalized flow chart showing industrial pathway of thallium
and related heavy metals and their transport to aquatic
environments ........................... 2
2 Locations of sites sampled ..................... 11
3 Generalized food web for a stream community ............ 14
4 Tacoma, Washington, sampling sites ................ 26
5 Sampling sites in Coeur d'Alene River area near Kellogg, Idaho. . . 30
6 Acidic effluent at zinc refinery in Government Gulch near
Kellogg, Idaho ......................... 32
7 Slag pile along south fork of Coeur d'Alene River near
Kellogg, Idaho ......................... 32
8 East Helena, Montana, sampling sites ................ 33
9 Hot-water stream running under slag pile (Prickly Pear Creek
near East Helena, Montana) ................... 34
10 Basin, Montana, sampling site ................... 37
11 Butte/Anaconda, Montana, sampling sites .............. 39
12 New stream channel through old slag pile (Silver Bow Creek
in Butte, Montana) ....................... ^1
13 Selby, California, sampling sites ................. 45
14 Hayden/Ray/Mammoth, Arizona, sampling sites ............ 47
15 Mineral Creek at the acid leach plant near Kelvin, Arizona ..... 49
16 Globe/Miami and Superior, Arizona, sampling sites ......... 51
17 Sampling sites in vicinity of Morenci, Arizona ........... 54
vn
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FIGURES (Cont.)
Number Page
18 Sampling sites near Fierro, Chino/Hurley, and Tyrone,
New Mexico 56
19 Santa Rita-Chino pit 57
20 Waste pile and acid leach runoff above Santa Rita-Chino pit ... 57
21 Sampling sites in vicinity of El Paso, Texas 59
22 Planet Mine (Parker), Arizona, sampling sites 61
23 Planet Mine acid leach 62
24 Missouri New and Old Lead Belts in relation to area of
Missouri sampled 64
25 Southeastern Missouri showing operations sampled and associated
features discussed in text 65
26 Tailings effluent at Bee Fork Creek 70
27 White Pine, Michigan, sampling sites 74
28 Native Creek (White Pine, Michigan) 75
29 Turbidity of Bannister Creek near junction of Mineral River
(White Pine, Michigan) 75
30 Perth Amboy/Sewaren, New Jersey, sampling sites 78
31 Palmerton, Pennsylvania, sampling sites 80
32 Copper Basin, Tennessee, sampling sites 82
33 Coal-burning sites sampled in Eastern Pennsylvania 85
34 East Corning, New York, sampling site 87
35 Chemical environments of metal deposition 90
36 Generalized flow of solubilized thallium in the environment .... 96
37 Concentration of the toxic metals thallium, cadmium, and lead in
biota, sediment, and water 98
38 Concentration of the toxic metals thallium, cadmium, and lead in
biota and sediment 99
Vlll
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FIGURES (Cont.)
Number
39 Concentration of the toxic metals thallium, cadmium, and lead in
fauna and algae .........................
40 Concentration of the toxic metals thallium, cadmium, and lead in
fish and larvae .... .....................
IX
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TABLES
Number
1 Thallium Concentrations (ppm) 7
2 Sites Studied 10
3 Organic-Complexation Method for Thallium 16
4 Typical Results of Atomic-Absorption Analyses of Thallium Using
Organic-Complexation Method 21
5 Locations of Selected Samples Analyzed for Thallium by
Organic-Complexation Method 22
6 Results of Comparative Analyses of Representative Water Samples
from Kellogg, Idaho 22
7 Concentrations of Thallium (ppm) at Selected Sites near Tacoma,
Washington (ASARCO Copper Smelter/Refinery--Puget Sound,
September 1972) 27
8 Concentrations of Heavy Metals (ppm) at Sites near Tacoma,
Washington (ASARCO Copper Smelter/Refinery--Puget Sound,
May 1973) 27
9 Concentrations of Heavy Metals (ppm) at Sites near Kellogg, Idaho
(Coeur D'Alene River, May 1973) 31
10 Concentrations of Heavy Metals (ppm) near East Helena, Montana
(ASARCO Zinc Smelter) 36
11 Concentrations of Thallium (ppm) at Sites near Butte/Anaconda,
Montana (1972) 40
12 Concentrations of Heavy Metals (ppm) at Sites near
Butte/Anaconda, Montana (May 1973) 42
13 Concentrations of Heavy Metals (ppm) near Hayden/Ray, Arizona
Area (Kennecott Copper Co. and ASARCO) 48
14 Concentrations of Heavy Metals (ppm) near Mammoth, Arizona
(Magma Copper Co.) 50
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TABLES (Cont.)
Number Page
15 Concentrations of Heavy Metals (ppm) near Globe/Miami, Arizona
(Inspiration Consolidated and AMAX) 52
16 Concentrations of Heavy Metals (ppm) near Superior, Arizona
(Magma Copper Co.) 52
17 Concentrations of Heavy Metals (ppm) near Morenci, Arizona
(Phelps-Dodge Co.) 53
18 Concentrations of Heavy Metals (ppm) near Fierro, Chino/Hurley,
and Tyrone, New Mexico 58
19 Concentrations of Heavy Metals (ppm) near El Paso, Texas
(ASARCO Smelter) 60
20 Concentrations of Heavy Metals (ppm) near Planet Mine, Parker,
Arizona (Powdered Metals Corp., January 1973) 63
21 Concentrations of Heavy Metals (ppm) near Viburnum, Missouri. ... 67
22 Concentrations of Heavy Metals (ppm) near Bixby, Missouri
(MOLOC/Magmont Complex) 68
23 Concentrations of Heavy Metals (ppm) near Fletcher Mine/Mill,
Missouri (St. Joe Minerals Corp.) 69
24 Concentrations of Heavy Metals (ppm) near Flat River (St. Joe
Minerals Corp.) and Glover (ASARCO) 72
25 Concentrations of Heavy Metals (ppm) near White Pine, Michigan
(Copper Range Co., August 1972) 76
26 Results of Thallium Analyses for New Jersey Samples 77
27 Concentrations of Heavy Metals (ppm) in Copper Basin, Tennessee
Region 83
28 Anthracite-Burning Power Plants (Pennsylvania) 84
29 Results of East Corning, New York, Water Sample Analyses (ppm)... 88
30 Results of East Corning, New York, Sediment, Vegetation, and
Biota Sample Analyses (ppm) 88
31 Thallium Minerals
89
XI
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TABLES (Cont.)
Number
32 Exchange Capacity of Hectorite with Thallium, Copper, and Zinc
(10 g/liter Hectorite) 94
33 Exchange Capacity of Hectorite with Thallium, Copper, and Zinc
(1 g/liter Hectorite) 94
34 Exchange Capacity of Potassium-Treated Hectorite with Thallium,
Copper, and Zinc 94
35 Solubilities of Selected Heavy-Metal Salts in Water 95
A-l Sample Digestion with Various Acids 105
A-2 Analytic Results (in ppm) of Sample-Preparation Trials 107
A-3 Sulfide Precipitation Procedure 108
XI1
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ACKNOWLEDGMENTS
During the course of this study, the investigators were aided greatly by
Mr. Ned Rathbun of the Arizona Fish and Game Department, Mr. Clancy Gordon of
the University of Montana, and Mr. Frank Munshower of Montana State University.
In addition, we thank personnel at the Copper Range Company, White Pine,
Michigan and the Anaconda Company, Butte, Montana for their cooperation. The
cooperation of Mr. E.G. Wixson in indicating sampling points and providing
data on lead concentrations in Missouri is greatly appreciated. The following
personnel of the Environmental Systems Department participated in various parts
of the study and report preparation: D.B. Dahm, R.J. Pilie", E.W. Hodgson,
R.P. Leonard, G. Lewandowski, J.G. Michalovic, T.R. Magorian, S.L. Pek,
E.L. Privitera, P.M. Terlecky, M.W. Van Lier, M.A. Wilkinson, K.G. Wood, and
j'. Fisher. Many thanks are due also to M. Prezyna and H. Fabrizzi, who typed
the manuscript and to R.G. Swan and E. Jachimiak, who edited the manuscript.
Xlll
•
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SECTION 1
INTRODUCTION
Toxic metals are widely distributed in their natural state. Traces
of these compounds are found in a wide variety of rocks and fuels, and
commonly occur in association with ores of commercial importance, such
as the ores of copper, lead, and zinc. One such group of toxic metal
compounds involves the element, thallium (Tl).
Actual production and use of thallium in the United States is
small: 6,000 to 7,000 pounds per year (in 1972). Since the demand for
Tl is limited by its toxicity and price, the American Smelting § Refining
Company (ASARCO) supplied the domestic market from its Denver, Colorado,
cadmium smelter. Other Tl concentrates are dumped on cinder banks and
into tailing ponds where they present a potential pollution hazard.
Commercially, the small amount of thallium produced is recovered
from the cadmium-bearing flue dusts of zinc smelting operations. Most
of these flue dusts are returned to the smelter but may be stored in
waste cinder banks, which are thus a source of pollution due to the
leaching action of rainwater upon the soluble thallium salts present, or
to erosion of the waste banks. Thallium pollution may also result from
the sudden discharge of residues and spillage of waste liquors from a
variety of refining and chemical operations, including lead and copper
refining, sulfuric acid and pigment manufacture, and almost all fuel-
burning processes. Additional damage to the aquatic environment may
also result from accidental spills during the manufacture, transport,
storage, and use of commercially produced thallium and its compounds.
The toxic compounds of other metals such as copper (Cu), cadmium (Cd),
lead (Pb), zinc (Zn), arsenic (As), indium (In), and selenium (Se),
which are related to, or associated with, thallium-bearing ores, are
concentrated in similar waste deposits and can also pollute the aquatic
environment.
Tl tends to be concentrated in the tailings, waste liquors, and
dusts of smelters, refineries, and pigment plants using sphalerite
(ZnS), galena (PbS), and chalcopyrite (CuFeS2), which are processed in
the greatest quantities.
Figure 1 is a chart showing the flow of thallium and related heavy
metals from mines to disposal areas and their suspected entry into
aquatic environments.
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MINING
PYRITE
(FeS2)
1
1
SULFURIC
ACID
PLANT
H2SO
i
V^
r
ORES
*
SIZE REDUCTION
t
SULFIDE
CONCENTRATION
1
SPHALERITE (ZnS),
CHALCOPYRITE (CuFeS2»,
GALENA (PbS), ETC.
1
^ S02
GAS
SMELTING E
•^-
BLISTER
H..SO to
I
REFINING
TO
ATMOSPHERE
i
L
STACK
GAS
PARTI-
CULATE ^ roTTRFii
VISIONS-*" C°£JST
_pb,Cd PRECIPITATORS
HE/
iVY
METALS*
5LAG i
~L
,
CINDER BANK
OR
TAILING POND
HEAVY
ELECTRO- "BLACK ACID" METALS*
LYTIC AND SLIMES
Cu, Zn (CONC.
1 Pb, Cd, Tl)
1 t
1
LEACHING,
SEDIMENT
TRANSPORT
r
TO MARKETS
TO BODIES OF WATER
TO GROUND WATER
*TI, Pb, Zn, Cd, In, As, Se, Te, and Cu.
Figure 1. Generalized flow chart showing industrial pathway of thallium and related heavy metals and
their transport to aquatic environments.
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A comprehensive program was conducted to determine the occurrence
and movement of thallium and related toxic metals from ore refining and
chemical operations to water bodies. This involved sampling and chemical
analysis of water sediments and biota from all possible sources and
sinks at a site. Sources included slag piles, cinder banks, land fills,
and effluent discharges.
Primary sinks include the water and sediments of receiving water
bodies and ground water. Aquatic biota serve as secondary sinks for
thallium and related metals by uptake, first as dissolved or complexed
ions and later by passage through food webs. The hydrology of the
disposal areas was of critical interest. Field examinations indicated
the potential pattern of runoff and erosion.
The sampling program was planned and carried out to elucidate the
extent of movement and concentration of thallium and related metals in
physical and biological compartments of the aquatic environment. The
potential magnification of heavy metal concentration through the food
chain has been carefully investigated at contaminated sites, clean
control sites, and in the laboratory.
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SECTION 2
SUMMARY
Samples of water, sediment, soil, and biota (algae, larvae, nymphs,
fish, rushes, reeds, etc.) were collected and analyzed. The samples
were taken from over 39 sites (operations) in 31 major regions of the
United States where copper, lead, and zinc are mined, milled, smelted,
and refined. The purpose of this sampling and analysis project was to
determine the potential for unrecovered (residual) spillage and leaching
of thallium and related heavy metals (Cu, Cd, Pb, Zn, and In) from
cinder banks, tailings ponds, and slag heaps associated with these
operations. Also sampled were a few coal-burning plants and chemical
works (i.e., the effects of leaching of flyash dumps and of toxic stack
emissions upon the environment were noted). The vulnerability of pro-
tective works (if any) for given volumes of toxic wastes is estimated
for each site.
The inland smelters and mills surveyed generally had extensive slag
heaps and tailing ponds along streams for waste disposal; estuarine and
riparian ore-refining facilities generally dispose of wastes directly
into water bodies through outfalls. Though some operations continuously
discharge very contaminated water, the greatest hazard is erosion of
particulate matter in stored wastes by floodwaters.
The concentration of any of the metals was greater in moving sedi-
ment at any time than that dissolved in water. Concentrations in water
and biota were higher in the fall at low water following benthic accumula-
tions during the growing season. Some bioaccumulation was observed but
the data are incomplete, and inconsistent since it was generally not
possible to obtain representative samples of appropriate trophic levels
in the food chain.
The pollution hazard from toxic metals is greatest in tailings,
slag, and the mud eroded from them. Up to 17% lead, 0.1% cadmium, and
5 ppm thallium were found in the sediments of streams used for irrigation
and drinking water below copper- and zinc-extractive industries in high-
runoff regions, particularly in the vicinities of East Helena and Anaconda-
Butte, Montana; Kellogg, Idaho; and Tacoma, Washington. Smaller amounts
of these toxic metals are present in effluent waters and biota below the
above sites, at open-pit copper mines on Mineral Creek and elsewhere in
Arizona, on Whitewater Creek, New Mexico, and at the new lead mills and
smelters in Missouri.
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Groundwater infiltration in the Northwest and the Ozarks provides
mine drainage water which is used in mill or concentrator tailings
transport, slag granulation, and refinery sludge disposal. This large
volume of water transports toxic waste into naturally fluvially erosive
bottom sediments, thereby contaminating the food chain.
Lead and cadmium were also found to be leaching into streams from
flyash dumps from a power plant in East Corning, New York.
Prevention of hazardous spills can include proper construction of
retaining dams and recycling of mill and smelter water with separation
of excess mine water to reduce the amount to be evaporated or recycled.
Treatment methods include alkaline precipitation with lime at pH as high
as 12 to prevent leaching of toxic metals from polluted mud already in
streams (now being achieved in Silver Bow Creek at Butte). Precipitation
with sulfide for economic recovery of metals offers potential for ultimate
control.
Procedures for determing thallium by atomic absorption in the
presence of high concentrations of chloride and other ions were developed.
The overall sensitivity achieved for thallium is approximately 0.1 ppb
in water. The detection limit for thallium in biota is typically 10 ppb
and in sediment 80 to 90 ppb because of interferences present in any
samples. Metal uptake (Tl, Cu, Zn, Cd, Pb) by algae was measured in the
laboratory. Experiments showed that dissolved thallium ions in water
can exchange with ions (probably potassium) in clay; this mechanism can
explain the relatively low concentration of thallium in fresh and sea
water compared the much higher concentration in river sediment and in
the earth's crust.
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SECTION 3
CONCLUSIONS
Based on samples and data collected in 1972 and 1973, the following
conclusions are drawn.
High levels of toxic metals were found in the particulate matter
discharged from northwestern mills, smelters, and refineries, especially
from older smelters such as those in East Helena, Montana. Levels were
lower in the New Lead Belt in Missouri and very low at White Pine,
Michigan, on Lake Superior. Fine, granulated slag and tailings have a
large surface area for leaching and are subject to catastrophic erosion.
Hazardous concentrations of over 15 ppm Tl, 17% Pb, and 0.1% Cd
have been found in stream sediments below metal sulfide processing
facilities (Table 1).
Data from the study show a definite tendency for heavy metals to
accumulate in rooted plants in greater concentrations than in algae,
fish, or other biota.
The estuarine plants and refineries, and those riparian plants and
refineries on large rivers were the most serious polluters since they
dispose of wastes directly into the water body through outfalls. Smelters
and mills (concentrators) have extensive cinder banks and tailing ponds
along the rivers. The greatest potential threat is transport of parti-
culate matter by floodwater.
In general, the volume of toxic metal in the moving sediment of the
streams is much greater than the amount in the water at any given time.
There is little observable bioconcentration through food chains as
compared to sediment concentration of the more toxic metals, especially
thallium.
Since the thallium is tied up in the sediments and very little of
the sediments from the smelters or natural thalliferous occurrences
reaches the oceans, the low concentration of thallium in the oceans as
compared with the concentration in freshwater runoff is believed to be
associated with the reduction of the thailie to the thallous ion, with
substitutions of the latter for potassium in clays.
Indium was rarely found above background but was concentrated
enough to report for Tacoma (Table 8) and Kellogg (Table 9).
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TABLE 1. THALLIUM CONCENTRATIONS (ppm)
Biota
Kellogg, Idaho, Bunker Hill copper smelter, horsetail roots under stack
Kellogg, Idaho, S. Fork of Coeur d'Alene River, cranefly in water
East Helena, Montana, Prickly Pear Creek, cattail roots in smelter pond
Tacoma, Washington, ASARCO copper smelter/refinery, horsetail leaves under stack
Kellogg, Idaho, S. Fork of Coeur d'Alene River, grass roots in water
Kellogg, Idaho, Bunker Hill copper smelter, horsetail leaves under stack
East Helena, Montana, ASARCO zinc smelter runoff, Spirogyra
Anaconda, Montana, Warm Springs Creek, stonefly larvae below old mines
Tacoma, Washington, Point Defiance, Ulva on beach at ASARCO copper smelter/refinery
Tacoma, Washington, horsetail roots on beach at ASARCO copper smelter/refinery
East Helena, Montana, Prickly Pear Creek, cattail leaves
Kellogg, Idaho, S. Fork of Coeur d'Alene River, Spirogyra
East Helena, Montana, Prickly Pear Creek, slime on diatomaceous Spirogyra
2.8
2.8
1.0
0.77
0.59
0.5
0.49
0.45
0.28
0.22
0.063
0.061
0.012
Water
Kellogg, Idaho:
Slag runoff after leaching
Mill outfall
Granulating water
0.11
0.02
0.015
Sediment
Kellogg, Idaho, mud
Butte, Montana, Silver Bow Creek, crust below Anaconda mill
Tacoma, Washington, ASARCO copper smelter/refinery, slag with live prawns
East Helena, Montana, ASARCO zinc smelter, septic ooze
Kellogg, Idaho, S. Fork Coeur d'Alene River, mud below slag and outfalls
Kellogg, Idaho, Bunker Hill zinc plant, Government Gulch
Kellogg, Idaho, Bunker Hill copper smelter, soil under stack
Butte, Montana, Silver Bow Creek, bottom soil below Anaconda mill
Butte, Montana, Silver Bow Creek, mud below Anaconda mill
Basin, Montana, mud from ruined mill
Kellogg, Idaho, Government Gulch, mud below Bunker Hill zinc plant
Selby, California, ASARCO lead smelter, soil under stack
9.1
8.6
4.9
1.7
1.1
0.61
0.52
0.44
0.42
0.32
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SECTION 4
RECOMMENDATIONS
The following recommendations are offered:
Greater care and, perhaps, closer inspection should be expended in
the proper construction and maintenance of retaining dams.
Water should be recycled wherever possible—not just where water is
scarce or expensive.
Treatment of any discharged water with hydroxide neutralization or
precipitation and sulfide precipitation can be used to reduce metal
concentrations of effluent waters. (Although the effluent may be
more alkaline than ideal, it will also be less toxic. Alkalinity
can be reduced by recarbonation.)
Close surveillance of sulfide ore-concentrating processes should be
implemented by mill owners in humid regions where floods and excess
water process occur—particularly, where dams are constructed only
of tailings.
Separation of low pH mine drainage waters from mill wastes should
be accomplished where possible to reduce the volume of mine water
in contact with tailings. Where this may not be feasible, neutrali-
zation of mine waters prior to mixing of waste streams should be
considered.
Slag granulation should be avoided, where possible, since it enhances
metal leaching due to the exposure of more surface area. However,
recycling of slag granulation water should be practiced to minimize
cooling water volume and contamination of surface or ground waters
by discharge.
Further field studies and analyses are needed to define the industrial
toxic metal threat more precisely--particularly, on more generally
polluted rivers such as the Ohio, Illinois, and Raritan.
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SECTION 5
APPROACH
SITE SELECTION
Sites to be sampled were selected from those refining and chemical
operations which produce residues and waste liquors containing toxic metal
compounds. They included smelters and metal refineries, a steel mill,
sulfuric acid plants, a pigment (lithopone) plant, and fuel-burning power
plants in close proximity to watercourses.
Selected sites were sampled in sufficient detail to provide a picture
of the course of pollution by thallium (Tl) and associated heavy metals into
and through the aquatic environment. Representative operations which
discharge into relatively clean fluvial and estuarine waters were selected.
Those streams with significant downstream human ultimate consumption were
emphasized.
Sites selected for sampling are listed in Table 2. As indicated
therein, plants operated by some or formerly operated by firms were sampled
in over 30 geographic regions. In many regions, several operations managed
by the same firm were sampled, so samples were collected (and analyzed) at
considerably more than 30 sites. In addition, several types of samples
were collected at most sites.
The locations of all sites sampled are shown on an index map (Figure 2).
The list of Table 2 does not include scrap smelters, because their
starting material contains much less heavy metals than the sites selected,
and significant concentrations of these metals should be quite rare at
such smelters. The plants listed in Table 2 are near water bodies used by
large populations. All of the significant sites drain directly into water
bodies.
Copper and lead/zinc sulfide ore milling, smelting, and refining produce
the bulk of the heavy-metals pollution problem. Although it was not possible
to test all such facilities operating in this country with the funds avail-
able, the sites selected are believed typical or worse relative to operating
procedures for waste disposal and are situated on streams of ecologic signi-
ficance.
In the processing sequence from sulfide ore to metal product, mining
creates coarse dumps which can leach slowly and be eroded by streams.
Milling produces large quantities of fine tailings which can be leached
-------
TABLE 2. SITES STUDIED
Site
Operation
Weitern U.S.
Tacoma, Washington
Kellogg, Idaho (Coeur d'Alene)
Eatt Helena, Montana
Basin, Montana
Butt e/ Anaconda, Montana
Salby, California
Hayden/Ray, Arizona
Mammoth, Arizona
Globe/Miami/Superior, Arizona
Morenci, Arizona
Fierro, New Mexico
China/Hurley. New Mexico
Tyrone, New Mexico
El Paso, Texas
Planet Mine (Parker), Arizona
Viburnum, Missouri
Bixby Region, Missouri
Bunker Region, Missouri
Flat River, Missouri
Glover. Missouri
Hereulaneum, Missouri
East St. Louis (Sauget), Illinois
White Pine, Michigan
Perth Amboy, New Jersey
Sewaren, New Jersey
Pilmerton, Pennsylvania
ASARCO, Inc. (Amer. Smelting & Refining Co.) Cu/Ag smetter*, refinery
Bunker Hill et al. Pb/Zn/Cd/Cu/Sb/Ag/Au smelter", milts, mines
ASARCO, Inc., Pb/Cu/Ag/Au smelter, Zn slag fuming
(Abandoned and ruined) smelter, mill
Defense (Zn) smelter & Berkeley (Cu/Zn/Pb/Ag/Au) mill
Anaconda (Cu) smelters', mill), mines
ASARCO, Inc., Pb/Zn smelter*
Comments
Toxic dust, salmon. On Puget Sound.
Toxic dust; drains into Coeur d'Alene River.
Toxic dust; drains into Missouri River via Prickly Pear Creek.
Open flue; dump in Boulder River.
Low pH at Butte; toxic dust at Anaconda.
Drcini into Clark Fork of Columbia River.
On San Francisco Bay; closed.
Southwestern U.S.
Kennecott Copper Corporation Cu smelter*, mill, mine
ASARCO, Inc., Cu/Ag/Mo smelter*, mills, mines
Magma Copper Co. Cu/Mo smelter, mill, mine
AMAX, Inc. (American Metal Climax, Inc.) Mo smelter
Inspiration Consol. Copper Co. Cu smetter*, mill, mine
Magma Copper Co. Cu mine, mill
Phel pi-Dodge Corporation Cu smelter*, mill, mine
U.V. Industries, Inc., Cu/Zn/Pb mills, mines
Kennecotl Copper Corp. Cu/Mo smelter*, mill, mine
ASARCO, Inc., Cu/Pb/Zn/Afl mine
Phelpi- Dodge Corporation Cu/Ag/Au mill, mine
ASARCO, Inc., Cu/Pb smelter*. Zn slag fuming
Powdered Metals Corporation Cu mine
Midwestern U.S.
St. Joe Minerals Corp. Pb/Zn/Cu mill, mines
MOLOC (Mo. Lead Operating Co.) Buick Pb/Zn smelter*, mill, mine
COMINCO American, Inc., Migmont Pb/Zn /Cu/Ag mill, mine
St. Joe Minerals Corp., Fletcher Pb/Zn/Cu mill, mine
Kennecott Copper Corp. (Ozark Lead Co.) Pb/Zn mill, mine
St. Joe Minerals Corp. Federal Division Pb/Zn mill, mine
ASARCO, Inc., Pb smeher
St. Joe Minerals Corp. Pb/Cu/Ag smelter*, refinery
AMAX, Inc., electrolytic Zn/Cd refinery*
Copper Range Co. Cu smelter, mill, mine
Eastern U.S.
ASARCO, Inc., Cu/Ag electrolytic refinery
Anaconda Co. Cu/Se/Te/Ag/Au electrolytic refinery
Copper Pigments and Chemical Works, Inc., pigment plant
The New Jersey Zinc Co. Pb/Zn/Cd smelter*, refinery
Other Known Thalliferous Surf ide Accumulations
Salt Lake City Region, Utaht
Mercury, Uuh *
Spelter, W. Virginia f
Columbus, Ohiu r
Bethlehem, Pennsylvania
Copper Basin, Tennessee
Anthracite (Scranton &
Hazleton) regions, Pennsylvania
East Corning, New York
McFarland & Hullinger Garfield Tooele Pb/Zn/Ag/Au mine
(Dump)
Matthiessen and Hegeler Zinc Co. Zn smelter
ASARCO, Inc., lithopone plant*
Bethlehem Steel Corporation steal mill*
Sulfuric acid plants & Cu/Zn/Fe smelters*, mills, mines
Pennsylvania Power & Light Co. , Antnracite.
Glen Alden Coal Co. * burning
Olyphant Premium Anthracite, Inc. \ power plants
Jenkens
Bituminous-coal -burning power plant
Being studied by G. Rathbun. Drains into Gill River.
Drains into San Pedro River.
Eventually drains into Salt River.
Drains into Gila River via tributaries.
Eventually drains into Mimbres River.
Drains into creeks used for irrigation.
Eventually drains into Mimbres River.
Drains into Rio Grande.
Closed; drain* into Colorado River.
Being studied by B.G. Wixson; clean water. Drains
into Mississippi River via Meramec River and streams.
Drain into Mississippi River (via creeks and Meramec
River) and into Black River.
Drains into Black River via creeks.
Standby; drains into Flat River.
Some drainage into Big Creek; most, recircutatad.
On Mississippi River.
On Mississippi River flood plain.
On creeks draining into Lake Superior.
Drain into Arthur Kill, Raritan River, and Raritan
Bay.
Drains into Lehigh River via creek.
Not sampled (drains into Great Salt Lake).
Not sampled (drains into (dry] Rush Lake).
Not sampled (river too polluted).
Not sampled (all effluent enters toil).
Anthracite coke no longer used; on Lehigh River.
Eventual drainage into Ocoee River.
Standby or closed. Drain Into Susquehanna, Schuylkill,
and Lehigh Riven.
Much flyash (and treatment system) washed away by
flood prior to sampling. On Chemung River.
•Alio includes acid plint. (Sulfuric acid recovered.)
tOnly thai not umplad. (Reatom for not lampling ara mora hilly deicribed in Saction 6.) Locationl of all other lital >ra ihown in Figure I.
10
-------
Viburnum, ~«ercuia
Bixby, & Bunker
-------
rapidly. Containment is now attempted for most active mills, although
removal by flood erosion still occurs rarely at some large ponds such
as at Anaconda, Montana. Smelting, by hot reduction and oxidation, releases
metals as air pollution and produces slag, which is leached and washed away.
The effluent metal concentrations are relatively low. The tank house
or final electrolytic refining step is often integrated into the smelter
complex, as at the Tacoma, Washington, and Kellogg, Idaho, sites, to
utilize acid produced from the smelter sulfur oxides. This acid is released
(or, sometimes, sold), often without recovery of unsalable byproducts such
as thallium and arsenic. The effluent is often reused at integrated plants,
so metals are recycled or concentrated at a few final outfalls.
The processing at these older plants is similar to that described in
the text of Section 6 on the White Pine, Michigan, site although the opera-
ting conditions and ore characteristics vary. In general, the western
smelters are larger and farther from byproduct markets. Their ores, formed
at higher temperatures, are richer in additional sulfides, selenides,
tellurides, and arsenides (such as those of thallium and related metals),
which are released during milling and smelting.
Site conditions and analysis results are described in Section 6 in the
order in which the sites are given in Table 2. The remainder of this
section summarizes sampling, sample preparation, and sample analysis.
SAMPLING PROCEDURES AND TECHNIQUES
Water, sediment, and biota were sampled at each site, taking into
account that leaching and other runoff may be dependent upon the action of
rain or flood water.
Samples were collected from drainage ditches, outfalls, and storm
sewers emanating from or passing through areas where heavy metals from ore
smelting or refining might be present. Additional samples were collected
from receiving bodies of water. Further sampling, for references purposes,
was conducted on upstream portions of the receiving bodies of water so that
background levels of thallium and other metal concentrations might be esta-
blished. These background levels were needed to confirm whether or not
thallium and other toxic metal concentrations in water bodies suspected of
contamination from the ore-smelting/refining operation are significantly
greater than normal background levels.
Glass bottles were used for sampling water from outfalls, ditches
and storm sewers, and shallow receiving streams. Deep bottom water was
collected using a Kemmerer bottle. Because the solubility of most metal
compounds is low, it was expected that water concentrations would often be
in the parts-per-billion range. Therefore, sufficient volumes were collected
for each sample to ensure adequate quantities for those samples which might
require repeated chemical analyses. The minimum volume of water collected
was 200 ml. Collected water samples were shipped in their glass collection
12
-------
bottles, and samples obtained using the Kenunerer bottle were placed in
glass bottles for shipment.
Sediment samples were placed in small 25 ml glass containers
with polyethylene tops which were pre-weighed and initially labeled at
the laboratory prior to each trip.
Suspended sediments were separated from water in the field and
analyzed separately. Collected bed-load sediments were elutriated to
separate silt and clay-sized particles from sand. These fractions were
analyzed separately wherever possible.
Collection and chemical analysis of receiving-water biota were
conducted to determine the extent to which thallium and associated heavy
metals accumulate in biota as a result of effluent attributable to ore
refining and chemical operations.
Specific aquatic food-web species were sampled (and analyzed) accord-
ing to the type of water body, geographical location, and degree of
pollution. Particular attention was given to sampling at various trophic
levels in food webs to ascertain whether or not bioconcentration of metals
occurs through food chains. Figure 3 is a generalized food web for a
stream community consisting of a number of interrelated food chains. The
food-web diagram suggests the degree of complexity involved among the
various food chains or building blocks of the web. The lines connect
trophic levels and represent the "upward" movement of food material through
the diagrammatic community.
Of the two most important organic-matter inputs to the food web--
namely, detritus and stream drift—the former was sampled to determine
pollutant inputs via this route. The stream producers (first trophic level)
such as algae were also sampled, as this trophic level is a major point at
which pollutants are incorporated into living tissue. Proceeding further
up the food chain, samples were collected of many primary-consumer benthic
organisms (such as insect nymphs and larvae, snails, mussels and clams, and
oligochaete worms), which feed principally from the imported organic matter
(detritus), algae, and diatoms. Toward the top of the food web, predaceous
insects and fish were sampled, as well as omnivorous organisms such as
suckers, which occupy an intermediate position between the two major
consumer trophic levels.
The food web shown in Figure 3 is a generalized composite, and genera
and families/orders have been cited for their traditionally accepted
trophic roles. The food web shown applies to a community in a relatively
unpolluted environment; however, the food webs for streams and estuaries
where some metal refineries are located do not resemble that shown. One
stream receiving refinery wastewater, the South Fork of the Coeur d'Alene
River at Kellogg, Idaho, was found to contain only pollutant-tolerant
organisms, such as sludge worms and midge larvae.
13
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Trout
(Salmon idae)
Secondary-Consumer
Trophic Level
Sucker
(Catostomidae)
Primary-Consumer
Trophic Level
Mayfly
(Ephemerellaj
Producer Trophic
Level
Imported Organic
Matter
Predaceous Stonefly
(Perlesta)
Net-Spinning Caddisfly
(Hydropsychej
Midge
(Chiron om idae)
Stream Drift
Detritus
Figure 3. Generalized food web for a stream community.
-------
Equipment used for biological sampling included dip nets, plankton
nets, drift nets, and an Eckmen dredge and Kemmerer bottles for bulk
sampling or water-dwelling organisms. Biota samples were placed in glass
containers which varied in capacity according to the size requirements of
the collected specimen. Guidance on sampling, sorting, and preservation
of biological samples was provided by appropriate EPA personnel.
Analytical controls (blanks) composed of distilled water in 200 ml
glass jars were carried into the field. Blanks showed less than 10 ppb
zinc, 20 ppb copper, 20 ppb cadmium, 10 ppb lead, 100 ppb indium, and
0.1 ppb thallium.
After completion of sampling at a particular site, preserved samples
were packed and shipped to the Calspan laboratory as part of the on-flight
baggage of the field-sampling personnel. On-site preservation of the water
samples consisted of the addition of 1.0 ml of concentrated nitric acid per
200 ml sample to stabilize metal concentrations. Biota samples were
preserved with formaldehyde solution at concentrations appropriate to the
physical size and physiological nature of the collected specimen. No
initial preservation of solid sediment samples was required or deemed
necessary.
SAMPLE PREPARATION
Water samples were analyzed by direct aspiration after settling of
any particulate matter. The majority of those samples were also extracted
with diethyldithiocarbamate (DDC) and 4-methyl-2-pentanone (MIBK) to
concentrate thallium prior to analysis.
The bulk of the sediment samples were analyzed for available metals.
Since the moisture content of the samples as collected varied widely,
2-gram portions were dried and weighed prior to extraction. Extraction
was by a 24-hour exposure of 2 grams of the sample to 2 ml of a 1:1 mixture
of Concentrated nitric and hydrochloric acids at room temperature (20°C,
68 F). The acid solution was diluted to exactly 20 ml with distilled water
prior to analysis. Metal content was reported on a dry-weight basis.
This method was chosen after preliminary investigations were conducted
to determine the most efficient method for leaching metals from sediment
samples. Further information on the study and rationale for the selection
of this method is provided in Appendix A.
Biological sample analysis was performed on a wet-weight basis, with
excess (surface) moisture removed at the sampling location. Digestion was
performed in the collection bottles to avoid loss of material and contamin-
ation of samples. Sample weight was obtained by subtracting the predeter-
mined bottle weight from the weight of bottle with sample. A 7:3 mixture
of concentrated nitric and perchloric acids was then added to the sample on
the basis of 1 ml per gram of sample. Digestion was accomplished with the
15
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bottle sealed and placed in a water bath at 50 C (122 F) for 24 hours.
The acid solution was then diluted 5:1 with distilled water for analysis.
It was found necessary to concentrate and remove potential inter-
ferences from many of the samples prior to analysis. Extremely low-level
metal samples and those with interfering ions (sodium and calcium) required
a cleanup concentration with DDC chelation, followed by MIBK extraction to
separate metals of interest prior to analysis. This was specifically
performed to improve the detection and reliability of analysis of the
extremely low-level concentrations of thallium encountered. Table 3
describes the DDC/MIBK complexation method for thallium analysis.
TABLE 3. ORGAIMIC-COMPLEXATION METHOD FOR THALLIUM
A. The following reagents are prepared:
1. Diethyldithiocarbamate (DDC) - Twenty grams (309 grains) of diethyldithiocarbamic acid sodium
salt are mixed with 380 ml of distilled water. This solution is filtered through a 0.45-micrometer
filter. The filtrate is extracted twice with 15 ml portions of MIBK.
2. MIBK - 4-methyl-2-pentanone (Eastman).
3. Phthalate buffer •• 102 grams (1,574 grains) of Baker Reagent grade potassium biphthalate are dissolved
in distilled water and diluted to 500 ml. Fourteen ml of 1M HC1 are added, and the resulting solution
is diluted to 1.0 liter.
4. Sodium hydroxide or hydrochloric acid is added to adjust pH.
B. All glassware must be rinsed with 1:1 HN03 containing a small amount of HF, followed by rinsing with
distilled water, acetone, and more distilled water.
C. Procedure
1. Dilute a sample aliquot to 100 ml with distilled water.
2. Add 2 ml of buffer and adjust pH to 3.6 + 0.1.
Add 7.0 ml of DDC solution.
Add 15.0 ml of MIBK
Shake vigorously for 30 seconds.
Withdraw MIBK layer.
Evaporate MIBK to dryness.
Add 2.5 ml of concentrated HNO3 + 2.5 ml of distilled water.
Sample is ready for analysis.
Other sample preparation procedures developed, but not used because
of inherent difficulties, are given in Appendix A.
16
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SAMPLE ANALYSIS
Atomic-Absorption Analysis
Samples were routinely analyzed for thallium, lead, zinc, copper, and
cadmium. Additional metals—namely, tellurium and indium—were analyzed
only for specifically selected samples. Arsenic and selenium, frequently
associated with the thallium-bearing ores investigated in this program,
were not routinely analyzed; because the major thrust of the program was
directed toward the detection and quantification of thallium in the environ-
ment, priority in the program was placed on this objective.
A Perkin-Elmer Model 303 atomic-absorption spectrophotometer, modified
to increase its sensitivity, was used for metal analysis. Improved
electronics provides detection limits substantially lower than those of
the unmodified instrument for some elements, and direct digital readout
in concentration is also available (and was used) to expedite the analyses.
The instrument is equipped with a deuterium-arc background corrector, and
both a sampling-boat accessory and a heated graphite atomizer (HGA) are
available and were used as required. An emission-correction circuit was
added to sense the emission resulting from the flame and automatically
subtract this signal from the photomultiplier output.
The standard detection limits for metals in aqueous solutions
analyzed on this instrument are listed below. (In this tabulation, detection
limits for lead and tellurium have been extracted from the 1968 Perkin-
Elmer atomic absorption accessories brochure; all other limits are from
the Perkin-Elmer Analytical Methods Manual, published in 1968.)
As the result of the improvements made, the sensitivities listed below
were either met or exceeded for the analyses in this program.
Element Analytical Method Detection Limit
(PPM)
Copper Direct Aspiration 0.005
Lead Sampling Boat 0.001
Zinc Direct Aspiration 0.002
Cadmium Direct Aspiration 0.004
Thallium Heated Graphite Atomizer 0.001
Tellurium Sampling Boat 0.01
Indium Direct Aspiration 0.05
The method chosen for atomic-absorption analysis of each metal was
that method which would consistently provide data with adequate sensitivity
for the metal concentration in an individual sample. Direct aspiration, the
method of greatest facility and least time consumption, was utilized in the
majority of cases. Analysis by sampling boat was used only for lead and
those selected cases where tellurium analysis was desired. The heated
graphite atomizer was used only for thallium analysis, since this method
provides the optimum sensitivity for thallium concentrations which was
necessary to provide meaningful final data.
17
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Many different approaches to obtaining thallium-concentration data
for natural samples were attempted throughout the early part of this
program. Thallium salts in distilled-water matrices posed no problem
analytically, but, in the presence of other elements, it became difficult
to perform analyses for low-level concentrations of thallium. Presence
of large quantities of alkali and alkaline-earth elements caused definite
quenching of thallium signals. The direct-aspiration method for atomic
absorption was found unsuitable for those samples where minimal thallium
levels were encountered.
Straight (nitric and hydrochloric) acid treatment of water and
sediment samples, followed by aspiration by conventional means into the
atomic-absorption spectrophotometer, produced varying results. Standard
samples containing known concentrations of thallium (as the nitrate)
could be analyzed easily, yielding interpretable results and calibration
curves. At times, levels of thallium were initially "observed" to be
present, but slight changes in burner conditions removed the thallium
signal. In each case where a response for thallium was observed, the
emissions from other elements also in the sample were extremely high.
Ordinarily, such emissions, if at moderate levels, can be compensated for
with the emission-correction device. Many of the emissions encountered
were beyond the capability of this corrector. Dilution of the sample to
reduce emissions resulted in complete removal of the previously observed
thallium signal. When a thallium response in a sample is relatively large,
a 50% dilution of that sample should produce a proportional decrease in
the thallium signal; however, n£ signal was obtained in these cases.
Since direct aspiration of acidified samples left the thallium concentra-
tions doubtful or highly questionable, other modes of sample preparation
or analysis-technique modification using atomic absorption were deemed
necessary.
A heated graphite atomizer was then used in an attempt to eliminate
flame effects and to increase sensitivity for thallium. Standard samples
of thallium were introduced into the atomizer and produced sensitivities
ten times greater than that sensitivity attainable by aspiration. A
series of samples was introduced in the same mode as standards, but no
signals were observed. Addition of a standard to a sample resulted in a
strongly decreased response, or in a complete quenching of the expected
thallium signal. It was found, through subsequent investigation, that
sodium and (primarily) chloride ions had a large quenching effect.
Chloride is very abundant in nature, and all natural samples contain it
to some degree. In addition, some of the samples of interest were
highly saline (i.e., sea water).
Additions of silver nitrate to samples, as well as to synthetic
standards containing thallium and chloride, precipitated the chloride
ion as the silver chloride. However, removal of the silver chloride
from the samples did not remove the interference in natural samples.
This indicated that other components in the sample were still inter-
fering by some mechanism.
18
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An attempt at isolating thallium from the sample matrix was attempted.
Two types of thallium removal were tried: one to precipitate the thallium
as the sulfide, and the second to complex and extract the thallium as an
organic complex. Both techniques also remove other multivalent metal ions
from solution, but ions such as potassium, sodium, chloride, and sulfate
are left behind.
If thallium levels were high, the sulfide precipitation method yielded
detectable results by aspiration. Aqueous samples could be analyzed to a
sensitivity of approximately 0.5 ppm Tl. However, to attain the greater
sensitivity which was desired, the heated graphite atomizer was used with
the sulfide precipitation preparation. This method was tested on two
water samples, which were analyzed with and without additions of 1 ppm
thallium. Thallium was not detected above 0.1 ppm in either sample, thus
indicating a quenching of the thallium signal. For this reason, sulfide
precipitation in conjunction with the atomizer was determined to be
unsuitable for use in this study. Table A-3 in Appendix A details the
sulfide precipitation procedure.
Organic complexation using diethyldithiocarbamate (DDC) and subsequent
extraction with 4-methyl-2-pentanone (MIBK) was initially performed on a
group of selected samples. Standards of thallium were extracted adequately
with an approximately 90% efficiency. These samples were analyzed by
direct aspiration of the organic solvent. Extracted samples mainly
showed minimally detectable and questionable concentrations of, or zero
response for, thallium. Thallium deliberately added to samples showed
quantitative thallium recovery.
Organic complexes of thallium were also analyzed using the heated
graphite atomizer. Strong emissions from the decomposing of the complex
prevented proper analysis by this mode. This effect was overcome by
evaporating the MIBK, which contained the complex, to dryness and redis-
solving in concentrated nitric acid, followed by dilution to 5 ml with
distilled water. Samples were then injected into the atomizer, operating
under the conditions listed below. (Oxidation of the complex with per-
chloric acid or sulfuric acid, instead of nitric acid, either completely
quenched the thallium response or added interference.)
Program: 4 @ 8 volts
Dry Time: 80 seconds at 100 C (212 F)
Ash Time: 330 seconds at 330 C (626 F)
Atomization: 15 seconds at 2200 C (3992 F)
Sample Size: 10 microliters
The type of samples collected in this study varied greatly in their
chemical and physical compositions. This necessitated at least one addition
of thallium to each sample analyzed in order to verify extraction efficiency.
This was especially important with sediment samples, where overall extraction
efficiency was shown to be about 50%. For this reason, an addition of 2.5
micrograms of thallium per 10 ml of sample was made to each water sample,
and a blank sample, consisting of 10 ml of distilled water with no thallium
addition, was also extracted and analyzed. Sediment samples were analyzed
19
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after digestion with and without addition of 1.0 raicrogram of thallium.
The extraction procedure just described was generally time-consuming,
and careful control had to be maintained to minimize losses. Under
optimized laboratory conditions, as many as 25 samples could be extracted
per day by this method.
Typical results of the thallium analyses by the organic-complexation
method are provided in Table 4; locations of those samples are given in
Table 5.
Electrochemical Analysis
A comparative analysis, for the purpose of verification, was made on
two selected water samples by the application of anodic stripping voltam-
metry. This technique has been employed for ppb-level determination of
many heavy metals, including silver, cadmium, indium, lead, thallium, and
zinc. The thallous ion gives a strong polarograhic wave at -0.475 volt
in 1M solutions of potassium nitrate, chloride, sulfate, and hydroxide.
Two water samples from the Kellogg, Idaho, site were run for Tl with
anodic stripping voltammetry through the courtesy of Dr. Eric Zink of
Environmental Science Associates, Burlington, Massachusetts, manufacturer
of the equipment. These samples were chosen because they represented the
type of sample being analyzed by atomic absorption in this program. Lead
and cadmium were measured simultaneously on 50-microliter aliquots of
each sample added to 5 ml of IN sodium acetate, adjusted to pH 5.3. Copper
and thallium were measured using 5-ml aliquots of each sample. These
aliquots were evaporated to dryness and taken up in 5 ml of IN sodium
acetate and 0.1 ml of 6M hydrochloric acid. Copper was measured by plating
at -0.5 volt, after addition of 0.2 ml ethylene diamine tetraacetic acid
of 0.1N (EDTA) solution. Typical results are shown in Table 6. With the
exception of copper in the second sample, agreement with the atomic-absorp-
tion technique is reasonably close, indicating that the atomic-absorption
determinations are fundamentally reliable.
Conclusions
The development of the organic-complexation heated-graphite-atomizer
atomic-absorption analysis method for thallium provided an analytical
method with consistent reproducibility and a reasonable degree of sensitivity.
Overall sensitivity for thallium was shown to be approximately 10 parts
per billion (ppb) for a water-sample size of 10 ml. Sediment samples
generally showed less recovery of thallium than the water samples. This
may have been due to the large amounts of other metals present also
complexing with the DDC and reducing the DDC/thallium ratio, thereby
leaving the thallium with little DDC available for complexation. The
reduced signal may also be attributed to the presence of other extracted
metals interfering with thallium in the atomizer.
20
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TABLE 4. TYPICAL RESULTS OF ATOMIC-ABSORPTION ANALYSES OF
THALLIUM USING ORGAIMIC-COMPLEXATION METHOD
Sample No.
Relative Response
of Instrument
Thallium Concentration
(ppm orxx.g/g)
Water Samples
- (Blank)
- (0.025-ppm thallium standard)
- (0.050-ppm thallium standard)
- (0.1 25-ppm thallium standard)
- (0.250-ppm thallium standard)
(0.500-ppm thallium standard)
4L-21
4L-21 + 0.25 ppm thallim
4L-26
4L-26 + 0.25 ppm thallium
6L-5
6L-5 + 0.25 ppm thallium
6L-10
6L-10 + 0.25 ppm thallium
6L-15X
6L-15X + 0.25 ppm thallium
0
9.5
14
24
36
55
4.0
33
2.0
39
1.5
36
2.0
37
3.0
22*
0
0.025
0.050
0.125
0.250
0.500
0.01
<0.01
<0.01
<0.01
<0.01
Sediment Samples
- (0.5-,ug thallium standard)
- (1 .0-yUg thallium standard)
- (2.0->ug thallium standard)
2-35 (sample weight, 0.1 348 g)
2-35 + 1.0 /ug thallium
3-47 (sample weight, 0.0470 g)
3-47 + 1.0 yug thallium
4-5 (sample weight, 0.0166 g)
4-5 + 1.0 /ug thallium
4-20 (sample weight, 0.1 343 g)
4-20 + 1.0/jig thallium
5-1 (sample weight, 0.0277 g)
5-1 + 1.0/Ag thallium
19
25
38
3.0
15
3.5
13
3.0
15
8.0
15
2.5
16
0.5
1.0
2.0
<2
<8
<15
8.6
<7
"Very broad peak
21
-------
TABLE 5. LOCATIONS OF SELECTED SAMPLES ANALYZED FOR THALLIUM
BY ORGANIC-COMPLEXATION METHOD
Sample No.
4L-21
4L-26
6L-5
6L-10
6L-15X
Location
Kellogg, Idaho
Tacoma, Washington
Bixby, Montana
Viburnum, Missouri
East St. Louis, Illinois
Operation
Water Samples
Bunker Hill Co.
ASARCO
COMINCO American
Magmont Mine/Mill
St. Joe Minerals Corp.
Fletcher Mine/Mill
American Zinc Com-
pany/AMAX
Comments
Discharge onto large slag
heap
Outfall running down
shore
Water from outfall of
tailings
Runoff from tailing ponds
Lagoon, west of elec-
trolytic refinery
Sediment Samples
2-35
3-47
4-5
4-20
5-1
Butte, Montana
East Helena, Montana
Butte, Montana
East Helena, Montana
Basin, Montana
Anaconda Co.
ASARCO
Defense Smelter
ASARCO
(Abandoned)
Fine sediment from pipe
(Silver Bow Creek)
Sediment from beneath
slag heap
Blue crust on slag
Black undersediment
from tributary
Mud near remains of
old mill and smelter
TABLE 6. RESULTS OF COMPARATIVE ANALYSES OF REPRESENTATIVE WATER
SAMPLES FROM KELLOGG, IDAHO
Sample
Slag-Pile Runoff
Smelter Weir
Metal
Thallium
Cadmium
Copper
Lead
Thallium
Cadmium
Copper
Lead
Concentration (ppm)
Atomic-Absorption
Analysis*
0.1
1.0
0.03
(Not
Available)
0.02
2.2
0.03
5.3
Anodic Stripping
Voltammetry
0.1
0.75
0.029
1.8
0.036
1.6
0.086
4.1
•Thallium was determined using the organic-complexation method.
Cadmium and copper were determined using direct aspiration, and lead
was determined using the sampling boat.
22
-------
Results of analyses for the biological samples indicated some problems
with reproducibility of results. Differences larger than expected were
found between the results of eight of 25 pairs of replicate analyses. These
differences were probably due to the plugging of the aspiration capillary,
and it was subsequently found that they could be eliminated by running samples
twice or by more frequent standardization.
The organic-complexation method as it now exists appears to have
significant potential as a reliable, consistent method for analyzing
thallium-metal concentrations in a variety of sample types. Additional
work to more accurately define the required experimental conditions may
be desirable. Variation in operating parameters (such as pH adjustment,
temperature modification, acid addition, and others) may provide increased
sensitivity as well as decreased sample preparation time. Continued work
with the analysis will undoubtedly result in an optimum level of facility
and operator accuracy.
23
-------
SECTION 6
RESULTS
SCOPE OF SECTION
The material which follows in this section is subdivided into (1)
Site Descriptions and Analyses and (2) Ecology of Thallium. The first
(and larger) subdivision includes detailed descriptions of each geographic
region sampled (selected using the criteria given under Site Selection,
Section 5) and the results of analyses of the samples for toxic heavy
metals. For each of these regions, a map is provided which shows the
locations of all sampling sites in relation to bodies of water; other
geographic features; and smelting, milling, mining, and/or other industrial
operations discussed in the accompanying text. (The reader is referred
to Figure 2, in Section 5, for the overall location of each geographic
region sampled.) In most cases, one or more tables presented for each
geographic region identify the concentrations (in parts per million =
mg/1) of all heavy metals found to be present in each type of sample
collected at each sampling site. Note that "none" in these tables
indicates that the specified type of sample (e.g., slag, mud, or biota)
was not present and, therefore, could not be collected or analyzed for
the site indicated. (It appears that, in many cases, fish or bottom-
dwelling organisms were absent due to either high toxic-metal concentra-
tions or low pH.) Where only a few metals were found present in a few
samples taken in a region, results for the region are presented in the
text rather than in tables.
The organization of Site Descriptions and Analyses precisely follows
the organization of Table 2 (Section 5). Like the table, this material
has four subsections (categories)--Western U.S., Southwestern U.S.,
Midwestern U.S., and Eastern U.S.--that reflect generally similar modes
of occurrence (geology) and processing methods for the metals involved,
plus a fifth, "other" subsection (category). Subsections are presented
in the same order as the categories of Table 2; within each subsection,
regions (general sites) are discussed in the same order as listed in
Table 2.
The ecology of the heavy metals most commonly found associated with
thallium—i.e., copper, lead, zinc, and cadmium—has been studied in
detail and is thoroughly described in the scientific literature. How-
ever, little information on thallium is available in published form.
Therefore, this section concludes with a summary of the Ecology of
Thallium which discusses the abundance and distribution of this metal,
its behavior in natural waters, results of experiments (performed under
this program) demonstrating that common clay can take up thallium to
24
-------
minimize its movement through the food chain, and the biological concen-
tration of thallium. Four graphs summarize data on bioconcentration of
thallium, cadmium, and lead based on analyses of the samples collected
in the study program.
SITE DESCRIPTIONS AND ANALYSES
Western U.S.
Tacoma, Washington--
The ASARCO (American Smelting and Refining Company) copper smelter
and refinery is on Puget Sound at the mouth of Commencement Bay and the
adjacent Dalco Passage between Point Defiance and Vashon Island (Figure 4).
The estuary was sampled in September 1972 and resampled in May 1973.
Tables 7 and 8 contain the data on thallium and other metals from various
locations shown in Figure 4.
Much of the concentrate used is imported from the Philippines and
is predominantly enargite (3Cu2S.As2S_) with significant gold, silver,
and pyrite. In addition, arsenical materials from ASARCO operations at
Battle Mountain, Nevada, and El Paso, Texas, are processed. At present,
the blister copper produced at Tacoma has the highest concentrations of
silver and arsenic, and its lead concentration is exceeded only by the
Carteret scrap smelter among U.S. plants. The copper is refined by Q
electrolysis in hot acid. The acid at Tacoma is heated to 63 C (145 F)
in Pb tubes and purified in lead-lined cells before discharge into the
Sound. The slag is granulated in a stream of water in order to allow
it to deposit in deep water.
The plant waste banks, effluent, and waters as far out as possible
were sampled from a boat. Dredgings near the principal outfall yielded
only shell fragments of dead marine bivalves (scallops and razor clams)
in iron-rich mud to a water depth of 60 meters (200 feet) (approximately
0.8 km (0.5 mile) offshore). Green algae was collected from rocks on-
shore adjacent to the acid outfall, and also at a location at the north
end of the smelter area growing on one of the older slag deposits which
form the entire smelter site. Barnacles (Balanus) were also collected
at these same sites. In the tidal littoral zone, barnacles (as plankton
filter feeders) live closer to the outfalls than algae.
Gill nets were set adjacent to the acid outfall to the southeast
of the smelter. A number of crustacean larvae (Metanaupliae) were
pulled off the net from shallow water. In addition to the three marine
fish previously taken by gill net, a large flounder was caught off the
dock. Liver, kidney, and muscle samples were taken. Between sampling
periods, the acid outfall had been plugged, and effluent was then diverted
through a lime pit, raising the pH slightly, and allowed to seep into
the ground. Although an elaborate liquid S02 plant financed by the state
is under construction, no further work was yet underway on the apparent
arsenic or heavy-metal problems which are evident in the data presented
in Table 8 for the samples collected in May 1973.
25
-------
: J
T
Point DefianceV
TO VASHON ISLAND
Lighthous«
Boi
INDICATES
SAMPLING SITES
^LUXURIANT JP*«-STACK
HORSETAIL
FAUNA '
' SLAG BOTTOM
cht Club WITH PRAWNS ASARCO
DOCK COPPER
SMELTER/
REFINERY
COMMENCE
MENT
BAY
Figure 4. Tacoma, Washington, sampling sites.
-------
TABLE 7. CONCENTRATIONS OF THALLIUM (ppm) AT SELECTED SITES
NEAR TACOMA, WASHINGTON (ASARCO COPPER SMELTER/
REFINERY-PUGET SOUND, SEPTEMBER 1972)
Sampling
Location
Control
Smelter
Slag
Water
<0.01
Clam
Shells*
<0.46
Green Alga
(Diva)
<0.28
Horsetails
under Stack
Potential Sources of Thallium
2.4
<0.01-2
9.1
0.28
leaves 0.77
roots 0.22
*Dead, abraded carbonate fragments found in toxic mud near acid
outfall-lpreliminary determination, not reproduced) and control
at Point Defiance.
TABLE 8. CONCENTRATIONS OF HEAVY METALS (ppm) AT SITES NEAR
TACOMA, WASHINGTON (ASARCO COPPER SMELTER/REFINERY-
PUGET SOUND, MAY 1973)
Sampling Location
Control (pH 5)
Water
Mud
Algae
Invertebrates
Fish
Acid Outfall (pH 3.8)
Water
Mud
Algae
Invertebrates
Fish (Perch, 1972)
Dock Outfall (pH 4.2)
Water
Mud
Algae
Invertebrates
Fish (including Flounder)
Slag (pH 5)
Water
Mud
Algae
Invertebrates
Fish
Thallium
<0.0001
<0.1
<0.008
<0.01
—
0.0012
0.52
<0.007
<0.06
<0.06
0.00015
None
<0.02
<0.06
<0.03
0.002
0.31
None
9.1
None
Cadmium
0.003
0.11
<2
—
—
0.04
2.8
<1.8
<2.9
5.5 (shells)
0.44
0.015
None
2.8
<6.4
<4
0.004
3.5
None
None
None
Lead
0.02
0.26
<11
—
—
0.4
2400
440
140
12
0.015
None
84
<44
66
310 (spleen
0.02
1700
None
None
None
Copper
0.03
96
<5
~~
"^
0.04
2500
440
220
19
0.24
None
360
58
10
0.2
3400
None
None
None
Zinc
====
0.27
130
3.3
"™
7.2
6200
160
190
18
1.1
None
110
22
40
0.26
8000
None
None
None
Indium
0.3
—
0.4
0.4
45
3
15
21 (shells)
^~
0.1
None
2
<0.6
10
0.5
35
None
None
None
27
-------
Shells of dead clams pave the muddy bottom in front of the acid
discharge. They average 5.5 ppm Cd, 50 ppm Pb, 100 ppm Cu, and 220 ppm
Zn; Tl is undetectable.
Only Equisetum, seemingly the most tolerant terrestrial vegetation,
grows in the dust beneath the stack. The brown algae, Fucus and Lami-
naria, were taken along the beach east of Pt. Defiance, as were additional
green algae northwest of the smelter. This location, upwind in a strong
tide rip, is believed to be relatively free of smelter pollution.
Kellogg, Idaho (Coeur d'Alene District) —
This district has yielded ores worth well over a billion dollars
in lead, zinc, copper, and silver since 1879. The mines occur within
an area about 40 km (25 miles) long and 24 km (15 miles) wide. The
country rocks consist of Pre-Cambrian Pritchard black shale, 4 km (2.5
miles) thick, which has been intruded by monzonite very similar to the
Boulder granodiorite of Montana. The most productive mines (Sunshine
and Bunker Hill) are found along great faults continuing east into
Montana; the Osborn fault has a vertical displacement of 5 km (3 miles)
or more and a horizontal displacement measured in tens of miles. Be-
tween these great faults are minor faults and shear zones that have
been filled and replaced to form the lodes. They attain 2100 meters
(7000 feet) in length, average 3 meters (9 feet) in width and have been
followed downward over 1600 meters (5300 feet).
The ores consist of disseminated galena, sphalerite, pyrite, and
argentiferous tetrahedrite. Some pyrrhotite, boulangerite, magnetite,
arsenopyrite and some copper minerals occur in minor amounts. The ores
carry approximately 6% lead, 3% zinc, and 62.5 grams of silver per metric
ton (2 ounces per short ton).
The Sunshine mine produces the most silver and antimony in the U.S.
Four others in the district, including the Bunker Hill mine, are third
through sixth in lead and zinc production.
The Bunker Hill and associated smelters fill Government Gulch and
the adjacent South Fork of the Coeur d'Alene River. The situation is
potentially one of the most hazardous in the country. The entire complex
drains acidic effluent into heavily inhabited but barren gulches. The
smelter stack emissions in Government Gulch have killed nearby vegetation.
Bunker Hill has hundreds of acres of tailing ponds for over four
miles in the flood plain of the South Fork of the Coeur d'Alene River,
from Kellogg to Pine Creek. The high rainfall of the area provides
continual leaching of these huge expanses of tailings. Although now
protected by low levees, much of the toxic material has been flooded
and leached by excessive runoff from the large cutover drainage basin.
Large quantities of various sulfide-processing wastewater are dis-
charged into the river at all flows. It has received mining and raw
domestic wastes for over 80 years. In addition to present tailings
(contained since 1968), floods release significant quantities of zinc
28
-------
and other heavy metals from the old stream sediments. The zinc and
phosphate plants dump acidic effluent into a heavily inhabited area.
Human exposure to cadmium and lead is relatively high (2). Thallium
was found in Government Gulch in particulates and mud below the Bunker
Hill zinc plant; however, pipe was being laid to divert these wastes
into the main tailings pond on the valley flat.
This complex was sampled as far downstream as the level of Coeur
d'Alene Lake. Figure 5 is a topographic map of the area showing the
locations sampled. The results of this sampling are contained in Table
9.
All outfalls and the larger dumps were sampled. The main Bunker
Hill outfall on the river just below Kellogg High School was mostly acid
(pH 2.2) and contained definite indications of Tl on preliminary analysis,
as did Government Gulch below the acid plant and zinc refinery. A site
at the mouth of the South Fork (junction of the main branch and South
Fork) of the Coeur d'Alene River yielded an impoverished fauna. How-
ever, it was possible to obtain samples of beetles, a mixed sample of
mayfly nymphs and cranefly larvae, as well as a sample of algae. The
South Fork at Smelterville has an average discharge of 641 cubic meters
per minute (377 cubic feet per second (cfs)) as measured by the U.S.
Geological Survey. Its maximum flood in only 3 years of record was
4998 cubic meters per minute (2940 cfs). The North Fork of the Coeur
d'Alene, however, drains relatively unpolluted terrain. Some old mine
and placer dredge tailings in Pritchard Creek, 38 km (24 miles) above
the junction, extend up to the ghost town of Raven. A relatively clean
site was chosen three miles above the junction as control. Separate
collections of mayfly nymphs, the stonefly Perlesta, water striders,
and cranefly larvae were made. Also, a freshwater sculpin was taken
for whole-body analysis.
In samples collected in September 1972, the acidic effluent
(Figure 6) at the lead smelter was found to contain 0.02 ppm Tl and the
mud washed off the large slag pile (Figure 7) along the south fork of
the Coeur d'Alene River was found to contain more than 15 ppm Tl. Mink,
Williams, and Wallace (3) found lead, cadmium, zinc, copper, nickel,
and iron in the river as a result of sulfide extraction. In addition,
thallium has been found in Government Gulch particulates (1.5 ppm)
and mud (0.4 ppm) below the Bunker Hill zinc plant. Both of these
sources drain into the river, where the mud at the junction of the forks
is now found to contain 5 ppm of Tl.
The problem at Kellogg is still far from solved, although diversion
of Government Gulch wastes into the tailing pond will help. Until the
slag is contained and enough quick lime or alkali is added, toxic metals
will continue to enter the Coeur d'Alene River and, thereby, the Spokane
water supply (now containing concentrations of Cu and Zn higher than
allowed by Public Health Drinking Water Standards).
The data in Table 9 are believed to be a fair illustration of the
hazard.
29
-------
B/'\ POLLUTED WITH
„ SEWAGE FROM
. ETC.
Figure 5. Sampling sites in Coeur d'Alene River area near Kellogg, Idaho.
-------
TABLE 9. CONCENTRATIONS OF HEAVY METALS (ppm) AT SITES NEAR
KELLOGG, IDAHO (COEUR D'ALENE RIVER, MAY 1973)
Sampling Location and Type
Above junction of South Fork
(control -clean)
Water
Mud
Algae
Larvae and Nymphs
Fish
South Fork
Above Outfalls at High School
Water
Mud
Algae
Larvae and Nymphs
Fish
Tailings Decant Outfall
Water
Mud
Algae
Larvae and Nymphs
Fish
Slag Runoff in 1972
Water
Mud
Algae
Larvae and Nymphs
Fish
Raw Granulating Water
Water
Mud
Algae
Larvae and Nymphs
Fish
Government Gulch at School
Water
Mud
Algae
Larvae and Nymphs
Fish
South Fork at Junction
Water
Mud
Algae
Larvae and Nymphs
Fish
Thallium
15
0.28
None
None
0.029
0.64 slag
None
None
None
0.00018
0.12
None
None
None
0.0006
0.14
0.11
0.035
None
Cadmium
<0.001
<2.6
1.2
<1.6
—
0.005
30
<5 (test)
None
None
0.24
8.3
None
None
None
0.06
<2.4
254
None
None
0.75-1
0.88
270 slag
1.4
280
None
None
None
0.017
59
36
2.9
None
Lead
<0.01
26
92
25
—
0.05
4100
26 (test)
None
None
0.42
1800
None
None
None
0.04
310
111
None
None
1.8
2
7300 slag
0.45
4300
None
None
None
0.045
4500
2700
680
None
Copper
0.008
8
7.5
13
—
0.15
170
28 (test)
None
None
0.26
3200
None
None
None
0.018
420
200
None
None
0.03
0.05
620 slag
0.045
320
None
None
None
0.01
190
59
62
None
Zinc
0.1
79
140
110
—
1.1
4900
200 (test)
None
None
160
5200
None
None
None
0.072
12000
6900
None
None
5
20000 slag
72
22000
None
None
None
1.8
4700
2200
350
None
Indium
<0.1
1.5
2
0.4
3
<0.1
4.1
3
None
None
0.2
—
None
None
None
<0.1
19.5
7
None
None
<0.1
19 slag
7.8
None
None
None
<0.1
6.7
1.4
0.3
None
Control larvae are ephemerid. Mud below copper smelter slag was dry. Control algae are probably Spirogyra.
31
-------
Figure 6. Acidic effluent at zinc refinery in Government Gulch near Kellogg, Idaho.
Figure 7. Slag pile along south fork of Coeur d'Alene River near Kellogg, Idaho.
-------
East Helena, Montana--
The ASARCO zinc smelter on Prickly Pear Creek includes a recently
closed lead smelter and Anaconda slag-fuming operation. It is processing
30% sulfur ore from the Texas Gulf Sulfur mine at Timmins, Ontario.
Figure 8 shows the location of the ASARCO smelter at East Helena, Montana,
and the sites at which samples were collected. The creek is dammed by
acres of slag being poured to a height of over 30 meters (100 feet).
The hot-water stream running under the slag heap yielded only blue-green
algae (Figure 9).
To Lake Helena
and Missouri River
East Helena
ASARCO ZINC
(FORMERLY LEAD)
SMELTER STACK
N.
SCALE:
miles
kilometers
26°C(78°F) OUTFALL
ORIGINAL CONTROL POINT
NEW CONTROL POINT
INDICATES
SAMPLING SITES
FLOW
Figure 8. East Helena, Montana, sampling sites.
33
-------
Figure 9. Hot-water stream running under slag pile (Prickly Pear Creek near
East Helena, Montana).
-------
The creek was first sampled in September, 1972, and then on April
30, 1973. The 78 F water which comes from the cooling pond after washing
the arsenical speiss (Zn^s-), contained plant sewage. No improvements
were made in the arrangement of outfalls or wastes between sampling
periods.
Just above where the outfall re-entered Prickly Pear Creek, abundant
biota were found. The dragonfly nymph Gomphus occurred in small numbers.
Caddis larva of the family Hydropsychidae and the stonefly nymphs
Perlinella, Isoperla, and Pteronarcella were large and abundant. These
were all included in a collection of mixed benthos for analysis. Water
striders made a separate sample. A similar collection was made in two
locations above the smelter pond. The upstream biota are typical of a
clean Rocky Mountain trout stream, even though the stream drains the
placer gravels of Montana City. Additional upstream control samples
were obtained on Prickly Pear Creek where it runs between old placer
gravels in 2-meter (6-foot) high piles and a new paved highway. The
new sampling point was located below the new Kaiser cement plant at
Indiana, Montana, and above the East Helena smelter. However, fallout
from the smelter stacks could have influenced the sample at this point.
An additional downstream sample was taken at the first major
irrigation weir below the smelter and town to obtain more invertebrates.
Here, the raw sewage from the smelter and town has a more immediate,
apparent effect on biological productivity than does heavy-metal
pollution.
Data on cadmium and lead found in samples acquired are presented
in Table 10. Uncertainties above the detection limit are roughly 10%
of the reported value. The septic sediment in mud (oozes) from East
Helena showed 8.6 ppm thallium.
Basin, Montana--
A typical small smelter and mill ruins on the Boulder River
(Figure 10) were used to process local ore in the last century. Structural
collapse allowed collection of flue and grinding dusts from hot locations
which are inaccessible in a functioning plant. Slags have been removed
and reworked for their metal values. Samples were taken of the large
tailing dump along the river, its leachates, and the river water. The
river now has a pH of 8.7. Solid wastes contain as much as 5.1% zinc,
1.0% copper, 0.79% lead, 420 ppm cadmium, and 440 ppb thallium. No
biota were found. Only 8 ppb of copper was found in the water. Many
such small abandoned plants can be found throughout the western mining
districts. Containment of their accumulated wastes would be relatively
inexpensive in each case if necessary.
35
-------
TABLE 10. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
EAST HELENA, MONTANA (ASARCO ZINC SMELTER)
Sampling Location
Control*
Water
Mud
Leaves
Roots*
Algae (Spirogyra)
Slime**
Larvae
Water striders
Fish (Sculpin)
Potential Sources
78° F Smelter Outfall
Water
Mud
Leaves
Roots*
Algae (Cyanophyte)
Larvae (Caddis)
Fish
Downstream
Water
Mud
Leavest
Roots (Willow)
Algae
Larvae (Dragonfly)
Water Striders
Fish
Thallium
-
0.063
<0.052
0.012
—
-
<0.12
-
8.6
1.0
0.49
None
None
—
-
-
-
<0.85
<0.007
-
None
Cadmium
<0.002
3.4
0.88
10
1.5-1.8
-
26-390
(mixed)
4.2
6.3
0.047
1500
86
270
None
<0.002
170
-
-
200
10
31-74
None
Lead
0.1
50,000
22
460
6.5
40
79
76
34
0.4
180,000
1100
1500
None
0.065
8000
-
1400
40-3700
330
550
None
* Below all placer mining wastes (possibly, also contaminated by backwater and stack dust
from smelter).
Perrenial rushes and reeds.
••Diatoms on Spirogyra.
36
-------
SMELTER AND
MILL RUINS
Figure 10. Basin, Montana, sampling site.
Butte/Anaconda, Montana--
Overall description—The copper deposits of the Butte district
(Figure 11) are examples of copper mineralization in the form of a great
complex of veins. Over 6 million metric tons (7 million short tons) of
copper metal have been mined from an area only 4 km (2.5 miles) wide, 8
km (5 miles) long, and about 1.2 km (0.75 mile) deep. In addition,
considerable amounts of silver, gold, zinc, and lead, along with some
manganese, have been produced.
The host rock is a portion of the granodiorite Boulder batholith
near its western border. Porphyry dikes intrude the host rock and are,
in turn, cut by seven systems of faults. The ore deposits occur as
steeply inclined veins, deposited in these fault systems. They vary
in width from 1 to 2 meters (3 to 6 feet) to 10 to 20 meters (30 to 60
feet) and may persist as far as 2100 meters (7000 feet) in length. Each
later fault system cuts and offsets the earlier.
The oldest fissures, termed the Anaconda, trend easterly and dip
steeply south. They are long and wide, and persist at depth. These
veins are rich and rather continuously mineralized, and they have been
the great producers at Butte. The Blue system strikes northwest and
dips steeply southwest, and its members cut the Anaconda system. Their
ore is characteristically discontinous and confined to irregular bodies.
A central zone carries copper ores; an intermediate zone contains copper
and zinc ores; and an outer zone is dominated by sphalerite along with
a little galena, chalcopyrite, and silver, in a gangue of calcite,
rhodochrosite, rhodonite, and quartz. These ores yield zinc, manganese,
37
-------
and silver. They are typical hydrothermal fissure veins in granodiorite
of the Boulder batholith. The principal copper minerals are chalcocite,
enargite, bornite, chalcopyrite, tennantite, tetrahedrite, and covellite.
The gangue minerals are mostly quartz and pyrite. The zinc sulfide,
sphalerite, is abundant in certain zones, as is also the manganese
carbonate, rhodochrosite.
East of the point where the Anaconda vein becomes discontinuous,
mineralization is represented by a series of segments arranged en
echelon. Ore in this area occurs in numerous veinlets striking north-
west with a stockwork of connecting stringers, irregular lenses, and
disseminations of copper-bearing sulfides. This intensely fractured
"horsetail" area is about 600 meters (2000 feet) long, 90 to 150 meters
(300 to 500 feet) wide, and extends down below the 1020-meter (3400-
foot) level.
The vein systems and the "horsetail" zone contain identical ores
that apparently were all formed during the same period of mineralization.
The later systems are post-mineral faults that cut and displace the ore-
bearing veins, giving rise to disconnected segments of the latter.
The Anaconda mill (Figure 11) at the headwaters of Silver Bow Creek
processes the large volumes of ore from this pit. The new acid-leaching
plant and other modern processing facilities discharge through a series
of tanks and ponds into a reservoir in the creek valley with an elaborate
floating wastewater facility.
At Butte (Figure 11), the Tl initially found (1972) in the Berkeley
Mill effluent (headwaters of Silver Bow Creek), then acid (Table 11),
was also found in the crust and mud downstream in the abiotic creek
(iron crust-10 ppm/ mud-0.5 ppm; floodplain soil-0.6 ppm). No algae
were found. Below Anaconda, pH was restored by the confluence of alkali
smelter wastes with the acid discharge from the leaching plant in Butte.
Unlike Kellogg, the lower rainfall of Butte and Anaconda makes
water rights of value and reuse desirable. Thus, the relative effluent
volumes are small. In the first (1972) sampling period, pH values were
low. Since that time, however, new water treatment facilities serve to
reduce the heavy metal load and, hence, raise pH values.
38
-------
TO CLARK FORK OF
COLUMBIA RIVER
CONTROL
N.
INDICATES
SAMPLING SITES
ANACONDA
SMELTER
AND STACK
DEFENSE
SMELTER
Figure 11. Butte/Anaconda, Montana, sampling sites.
-------
TABLE 11. CONCENTRATIONS OF THALLIUM (ppm) AT SITES NEAR
BUTTE/ANACONDA, MONTANA (1972)
Sampling Location
Control*
(Blacktail Creek)
Potential Sources:
Berkeley Mill (2 Upstream
Sites)
Downstream in Silver Bow
Creek at Defense Smelter
Water
Not Detected
0.2
<0.01
Tailings
0.52-0.61
Crust
>10
Flora
Aquatic Moss
<0.21
Aquatic Weeds
<0.084
Lifeless
Horsetails
<0.02
Larvae
Tipulid
<0.073
Too Few
*Most upstream tributary to Silver Bow Creek
Defense smelter and Berkeley mill—The abandoned federal smelter
on Silver Bow Creek is located just below downtown Butte. In constructing
the interstate highway, the creek has been diverted through a new channel
blasted in the old slag pile (Figure 12). The pH was so low (4.3) and
metals were so concentrated that iron oxides, at least, were precipitating
on solid wastes in the channel. Those materials which are being leached
or eroded were sampled.
The Defense smelter (Figure 11) had been leased in 1973 by Anaconda
and was used as a lime kiln during rebuilding of their kiln at the smelter.
The milk of lime produced was being added at the Berkeley Mill, rather
than the old procedure of allowing mill and smelter wastes to mix in the
settling pond below Silver Bow Creek. Although some additional metal was
discharged from the smelter, much less was leaving the mill during sampling
in 1973. Table 12 lists the results of the analyses for the samples
collected in May 1973. The temporary lime kiln effluent contained 5.5
ppb Tl in waste sediment, carried in the alkaline water.
There was a total absence of benthos all along Silver Bow Creek.
However, some aquatic weeds were taken from Blacktail Creek, a tributary
draining residential and commercial areas just above the Defense smelter.
There are other abandoned plants and waste deposits in the Butte vicinity.
All drain into abiotic Silver Bow Creek.
Anaconda smelter--The company smelter complex (Figure 11), the
largest single copper source in the U.S., drains into Warm Springs
Creek. The tailing ponds extend over 9 km (6 miles) below the smelter
to the headwaters of the Clark Fork River (formed by Warm Springs and
Silver Bow Creeks), covering at least 10 square km (4 square miles).
Calspan sampling covered these wastes and waters.
40
-------
Figure 12. New stream channel through old slag pile (Silver Bow Creek in Butte, Montana).
-------
TABLE 12. CONCENTRATIONS OF HEAVY METALS (ppm) AT SITES NEAR
BUTTE/ANACONDA, MONTANA (MAY 1973)
Sampling Location
Control: Warm Springs Creek
above Anaconda (pH 5.5)
Water
Mud
Algae
Larvae and Nymphs
Fish (Sculpin)
Berkeley Mill (pH 10.3*) (3 Sites)
Water
Mud
Algae
Larvae and Nymphs
Fish (Sculpin)
Defense Lime Kiln (pH 11.5)
Water
Mud
Algae
Larvae and Nymphs
Fish (Sculpin)
Anaconda Smelter (pH 8.4)
Water
Mud
Algae
Larvae and Nymphs
Fish (Sculpin)
Clark Fork below Warm Springs Creek
Water
Mud
Algae
Larvae and Nymphs
Fish (Sculpin)
Thallium
0.00025
<0.02
<0.02
0.003
0.004
<0.0001
-------
The Anaconda smelter is the only industry in the valley since a
zinc smelter was closed in 1969. The large copper smelter reduced poly-
metal lie-sulfide concentrates from the mill in Butte. The biota within
five miles of the smelter was severly limited by heavy-metal and sulfur
toxicity. Very old, hardy shrubs, Tetrodynia and Chrysothamnus, and a
few cottonwoods and willows barely survive. Reedgrass (Calamagrostis
montanensis) exists temporarily on clean, newly eroded soil. No wild
animals or mature insects can be found (Munshower, j,t personal communi-
cation, 1972). The wastewater handling facilities resemble those at the
mill in Butte. Arsenic exposures are relatively high in Anaconda (2).
The Clark Fork site sampled receives acid wastes from the Butte
mill which are partially neutralized by alkaline (pH 12.7) smelter
effluent from the settling ponds (subject to winter overflow). This
portion of the river is also contaminated by partially treated sewage
from the town and nearby state hospital.
An uncontaminated site on Warm Springs Creek above the town of
Anaconda was sampled for control. A large species of the caddis larva
family Hydropsychidae formed one collection. A giant stonefly nymph,
Peltoperla, formed another collection. Several caddis larvae Brachycentrus
were removed from their cases and stored for analysis. In the following
spring collection, stoneflies included Arcynopteryx, Pteronarcella. and
Perlinella; mayflies included Ephemerella, Arthroplea and Potamanthus;
caddisflies were Hydropsychiad and Psychomyiid.
Warm Springs Creek upstream from Anaconda contains 0.25 ppb Tl in
the water. Although the drainage basin is now almost uninhabited grazing
land, it contains old mine workings, dumps and many prospect pits in a
locally complex volcanic terrain recently heavily glaciated.
Tl may be leaching out of both the old mining debris and glacial
till. The large mayfly larvae contain 3 ppb Tl and a small sculpin
contains 4 ppb Tl, showing a bioconcentration factor of 12-16 times the
concentration in water. Smaller, rarer mayfly larvae collected at this
site in the fall contained 200-240 ppb Tl. They have accumulated through
the open-water season a bioconcentration factor of almost 1000. This
contamination was reduced to less than 0.1 ppb above Anaconda as side
gulches diluted it. The mine-debris and glacial-till leach cannot be
the source of all the Tl still found in Clark Fork. At least 40 ppb Tl
in mud was entering from the smelter due to low pH (Table 12). The
other control stream, Blacktail Creek at Butte (Table 11), showed no Tl.
For comparison, the Tl concentrations sampled in September 1972
from the Berkeley Mill at Butte were up to 0.2 ppm in the mill effluent
water (pH 2.6), about 0.55 ppm in the mud (tailings), and over 10 ppm
in the iron crust deposited in the stream bed. It is clear that the
acid discharge from the mill carried more toxic heavy metals.
43
-------
As an additional check, Silver Bow Creek was sampled between the
mill outfall and the junction of Blacktail Creek at George and Kaw
Streets. The analysis closely confirms the data from the mill outfall
for all metals in both water and mud.
Selby, California--
A few reconnaissance samples were taken on 27 August 1973 from the
abandoned ASARCO non-ferrous smelter* at Selby, California (Figure 13).
This site, which has been used for nearly a century, has a large pile of
slag poured into the bay. Sediment, algae, water, and a representative
small fish were collected on the beach eroded into the slag pile. In
addition, bay water from across the Carquinez Strait and Pacific Ocean
water from off Monterey were sampled for comparison.
Lead at a concentration of 3 ppm, along with 240 ppb copper and 450
ppb zinc, were found in a stagnant pond draining the slag pile.
The pond and its outfall (diluted by the bay tide) showed no excess
cadmium over controls (50-100 ppb) from elsewhere in the bay. Green
algae (Ulva) near the outfall contained 5.2 ppm lead (as compared with
3.6 ppm across the straits at Neare Island) and 0.18% zinc (as compared
with 4.7 ppm). Cadmium and copper were not significantly concentrated,
nor were the other samples. Thallium was not detected except in soil
near the stack (320 ppb).
Southwestern U.S.
Synopsis--
Copper mining, milling and smelter operations in the Southwest were
sampled from the Colorado River to the Rio Grande. In this arid region,
water is expensive. Most facilities store and recycle all of the water,
including rainfall, which falls on the mine, tailings, or slag and
runoff. Results of sampling in January, 1973 from the copper processing
plants in this area are discussed below.
Porphyry District--
Overall description--The Arizona/New Mexico/West Texas porphyry
copper mining district, which supplied most of the Cu today, is in a
very dry climate with few permanent streams. The centrally located
smelters and acid plants at Hayden, however, are directly on the Gila
River, which is one of the principal sources of irrigation water for
Arizona agriculture.
* It is historically interesting that Cottrell's first precipitator was
operated in the acid plant at this facility.
44
-------
w*.-.
ighthouse M W^W v I/
Maritime Academy V'f
Slf^jE
^S^
* ( •
kilometers
CARQUINEZ STRAIT
BEACH
(SAMPLING
SITE)
ASARCO
SMELTER
(ABANDONED)
-^•"•^—^
Figure 13. Selby, California, sampling sites.
:
-------
The Ajo, Douglas, Duval, and other mines in the porphyry belt south
of Tucson have no surface runoff to ocean or irrigation.
The porphyry district is underlain by the late-pre-Cambrian sediments
found in Montana and Idaho. This thick series includes the Final schist,
a metamorphosed cupriferous blackshale which can be correlated with the
ore at White Pine, Michigan. The copper was mobilized by hot igneous
intrusions and crystallized in the partially quenched (200 -300 C)
(392°-572°F) rim of large ivory-colored oligoclase feldspar (NaAlSi-0.
with 10 to 30% CaAl2Si-08) crystals in a purple ground-mass of fine-
grained minerals. The overlying Paleozoic limestone trapped the richest
ore bodies (skarns) where they were cut by porphyry stocks, particularly
immediately below shales.
Phelps-Dodge operations at both Morenci, Arizona, and Tyrone, New
Mexico, are so combined that water is fully recycled. Location of
facilities is partially controlled by access to water.
Kennecott, at both Hayden/Ray, Arizona, and Chino/Hurley, New
Mexico, still uses a mill at the smelter rather than close to the mine.
Hayden/Ray, Arizona--Sampling locations in the Hayden/Ray vicinity,
Arizona, are shown in Figure 14.
The Kennecott Ray pit, almost 3.2 km (2 miles) across, is in a
large blanket ore deposit in the Pinal schist drained by Mineral Creek
(sampled below the acid leach plant and at Kelvin where it joins the
Gila River).* Only the Kennecott pit at Ray, Arizona, has a large runoff
problem, which will eventually be corrected by a long diversion tunnel.
All of the facilities whose runoff could enter surface irrigation or
domestic supplies were sampled. The creek ran copper-blue. It was
abiotic below the mine, as was the Gila River below its confluence.
There was no recycling, and this stream provided most of the water for
citrus and lettuce irrigation below Florence at low flow. Biota were
collected above Mineral Creek and above the mill/smelter outfall at
Hayden. The Kennecott Hayden mill/ smelter complex recycle system was
incomplete. Runoff water precipitated metal deposits in Hayden (sampled).
It drained from a tailing pond, second in size only to Anaconda. The
ASARCO smelter and acid plant recycle all water but cause heavy fumes
down the Gila Valley. Results of thallium, cadmium, and lead analyses
for water, sediments algae, and biota are given in Table 13.
Mammoth, Arizona--The large, low-grade San Manuel (Tiger) stock of
Magma Copper Co. is mined on the pediment draining into the usually dry
San Pedro River (sampled) which joins the Gila at Hayden (Winkelman).
The new Mammoth mill/smelter complex impounds tailings behind cyclone-
separator dams, as in Missouri. Water is recycled. Results of analyses
for thallium, lead, and cadmium are given in Table 14.
*Figure 15 shows a photo of Mineral Creek at the acid leach plant where
samples were taken.
46
-------
To Final Mountains
FLOW
INDICATES
SAMPLING SITES
\
ACID LEACH PLANT
TAILING
POND
SLAG
DUMP
Gila River
DISTANCE
NOT TO
SCALE
KENNECOTT
MILL & SMELTER
ASARCO SMELTER
SLAG
DUMP
^3 -t«-CHRISTMAS
MINE
inkelman
DISTANCE
NOT TO
SCALE
FLOW
*• x
X
Coolidge Dam
To
4
Tiger
Mammoth
FLOW
0
0
SCALE:
miles
1
~~i - "n - r
1 2 3
kilometers
Figure 14. Hayden/Ray/Mammoth, Arizona, sampling sites.
47
-------
TABLE 13. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
HAYDEN/RAY, ARIZONA AREA (KENNECOTT
COPPER CO. AND ASARCO)
Sampling Location
Gila River above Hayden
(below Christmas Mine)
Water
Sediment
Algae
Larvae (Caddis and Blackfly)
Fish
Kennecott Smelter
Water
Sediment
Algae
Larvae
Fish
ASARCO Smelter
Water
Sediment
Algae
Larvae
Fish
Ray Pit
Water
Sediment
Algae
Larvae
Fish
Mineral Creek
Water
Sediment
Algae
Larvae
Fish
Gila River below junction
with San Pedro River
Water
Sediment
Algae
Larvae
Fish
Thallium
<0.003
0.22
0.36
<0.003
0.12
_^
<0.003
0.16
•^
•^
-------
-
i
i
.
Figure 15. Mineral Creek at the acid leach plant near Kelvin, Arizona.
-------
TABLE 14. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
MAMMOTH, ARIZONA (MAGMA COPPER CO.)
Sampling Location
Mammoth Mill
Water
Sediment
Slime
Algae
Larvae
Mammoth Smelter
Water
Sediment
San Pedro River below mill and smelter
Water
Sediment
Slime
Algae
Larvae (Blackfly)
Thallium
^
^^
^
^*
^
'^^
< 0.003
<0.12
0.018
Cadmium
recycled
0.44
recycled
0.24
<0.0005
0.5
>0.8
Lead
recycled
2170
^
w.
w.
recycled
3800
^
^
<0.01
50
7.5
20
>160
Globe/Miami/Superior, Arizona--The layout of the Globe/Miami/Superior
area is shown in Figure 16. The middle of the mountain range is occupied
by barren, coarse Schulze granite. On the east side, the 4-km (2.5-mile)-
long Miami-Inspiration lode forms a rim around a lobe of porphyry. The
Inspiration smelter sits on a 75-meter (250-foot)-high pinnacle or ore
surrounded by windblown tailings and slag (sampled). The water from the
smelter and mill is recycled through the acid leach (sampled). The
Inspiration mill, the Ranchers Exploration and Development Corp. Bluebird
mine/mill (sampled) in Bloody Tanks Wash (control samples above Bloody
Tanks), the ruined smelter in Globe (slag sampled), and the CITGO (Cities
Service) and AMAX (American Metals Climax molybdenum) operations up
Tinhorn Wash drain into dry Final Creek, a tributary of the Salt River,
which was sampled below Radium. Analyses of water, sediments, and biota
are given in Table 15.
On the west side of the Final Mountains, the Magma Copper Co. at
Superior (discussed later) permanently transferred smelting operations to
Mammoth (discussed below) during a strike in 1970. In the original Magma
mine, still operating up the mountain above the mill and closed smelter,
the mineral relations of porphyry copper have been worked out in greatest
detail. The hot cupriferous water flowed along shear zones to deposit
massive sulfides in the thin coralline Martin limestone (Devonian Onondaga
equivalent). Analyses of water, sediment, and cattails from this old
mining area are given in Table 16.
50
-------
INDICATES
SAMPLING SITES
\
MAGMA COPPER
MINES
TAILING
PONDS
INSPIRATION
CONCENTRATOR
(CLOSED)
INSPIRATION
SMELTER
(CLOSED)
DISTANCE
NOT TO
SCALE
OLD SMELTER
(CLOSED) V
Figure 16. Globe/Miami and Superior, Arizona, sampling sites.
-------
TABLE 15. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
GLOBE/MIAMI, ARIZONA (INSPIRATION CONSOLIDATED AND AMAX)
Sampling Location
Control:
Bloody Tanks Wash Upstream of Mine
Water
Sediment
Phreatophyte Roots
Bluebird Mine Runoff into Wash
Water
Sediment
Phreatophyte Roots
Inspiration Concentrator (part of Mill)
Water
Sediment
Phreatophyte Roots
Inspiration Smelter (part of Mill)
Water
Sediment
Phreatophyte Roots
Pinal Creek below Miami Wash
Water
Sediment
Phreatophyte Roots
Cadmium
-
0.0015
<0.05
None
72 recycled
2.5
0.99
72 recycled
1.5
0.9
Flood only
<0.05
None
Lead
<0.005
114
26
0.015
365
None
190 recycled
42,000
18
190 recycled
5150
390
Flood only
310
None
TABLE 16. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
SUPERIOR, ARIZONA (MAGMA COPPER COMPANY)
Sampling Location
Queen Creek Draining Magma Mine
Water
Sediment
Cattails
Ore from Mine
Water
Sediment
Cattails
Old Mill (closed)
Water
Sediment
Cattails
Old Smelter (closed)
Water
Sediment
Cattails
Thallium
0.003
0.11
—
—
—
—
0.0033
0.089
~
—
_
—
Cadmium
<0.0005
2.6
None
None
1.9
None
0.0005
1.8
0.05
0.0045
0.62
None
Lead
<0.01
16,600
None
None
28,400
None
<0.01
1200
16.7
<0.01
1870
None
52
-------
Morenci, Arizona—The Phelps-Dodge large open-pit mine and mill/smelter
complex, shown in Figure 17, recycles water from Chase Creek. The creek is
dry below the complex. This creek drains into the San Francisco River,
which drains into the Gila below Clifton. A new company town has been
built on the old tailings. Water from the river, wastes, and mud from
these operations and a ruined smelter site on the river were sampled.
Results of these analyses are given in Table 17.
TABLE 17. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
MORENCI, ARIZONA (PHELPS-DODGE CO.)
Sampling Location
Control:
San Francisco River above Clifton
Sediment
Phelps-Dodge Morenci Open-Pit Mine
Sediment
Larvae
Phelps-Dodge Smelter
Sediment
Larvae
Phelps-Dodge Smelter
Sediment
Larvae
Chase Creek above Clifton
Sediment
Larvae
Clifton (Arizona Copper Co.) Smelter
(Ruined)
Firebrick
.' Sediment
Larvae
Slag
Sediment
Larvae
San Francisco. River (downstream at
Ward Canyon Road)
Sediment
Larvae (Caddis and Blackfly)
Thallium
-
—
-
—
• — .
0.13
—
028
Cadmium
-
4.5
None
4.9
None
0.63
None
1.2
None
270
None
<0.05
None
<0.03
2.5
Lead
.32
2860
None
13,300
None
1200-2200
None
1530
None
103,000
None
1090
None
73
28
53
-------
PHELPS-DODGE
MORENCI PITS
PHELPS-DODGE
MILL & SMELTER
WARD CANYON
ROAD
TAILING PONDS
INDICATES
SAMPLING SITES
ARIZONA COPPER CO.
SMELTER RUINS
To Gila River
Figure 17. Sampling sites in vicinity of Morenci, Arizona.
-------
Fierro, Chino/Hurley, and Tyrone, New Mexico—The east end of the
porphyry district shown in Figure 18 produces significant zinc as well as
copper and molybdenum. The Phelps-Dodge pit and mill at Tyrone in the
Big Burro Mountains, drains through dry washes (sampled, along with waste)
into the Mimbres River. Water from the tailings is recycled.
In the Cobre Mountains, copper occurs around Laramide (50 million
years old) porphyritic quartz monzonite stocks in a north/south trend
which is followed by Whitewater and associated creeks below the U.V.
Industries mine and mill at Fierro. The recycled U.V. Industries water
and sediment was sampled, as was the tailing runoff water and sediment
at the headwaters of Whitewater Creek. Hanover Creek, which joins White-
water Creek at Hanover Junction, flows past a closed mill (where biota
were sampled), through Hanover, and near Turnerville (mine waste and runoff
sampled). The ASARCO Groundhog mine was also sampled (no biota present).
The 1.6-km (1-mile)-wide Kennecott Chino pit (Figure 19) on a stock
east of the trend has removed everything east of Turnerville, including
the site of the former town of Santa Rita. 75% of the rock was hauled to
waste piles above the pit and leached with acid (Figure 20) (sampled in
the tributary creek below and above at the acid-leach and recycling points).
The rest was hauled to the mill and smelter downstream at Hurley (slag,
soil, tailings, and effluent sampled). Analyses of water, sediments, and
biota from this region are given in Table 18.
Below the huge Kennecott mountain of tailings, Whitewater Creek
disappears into the desert, although the peak flood waters reach the Mimbres
River and the irrigated cotton fields at Deming. Acid fumes from the
Kennecott acid plant and smelter at Hurley created serious vegetation
damage as far up as Hanover.
El Paso, Texas--The ASARCO smelter is still operating on the Rio Grande
(Figure 21). All river water used is recycled and evaporated. The smelter
originally processed ores from the entire porphyry district as well as from
Chihauhua and Sonora, Mexico. At present, old slag (sampled) is being
crushed and sold. Soil samples, mud samples from the dry wash carrying
smelter runoff, and river samples (water, muds, and biota) were collected
above and below the plant. Results of analyses are given in Table 19.
The data indicate that toxic lead, thallium, and cadmium fumes released
from smelter stacks settle in soils and sediments but are not solubilized
in water to any great extent.
55
-------
INDICATES
SAMPEINC SITES
SCALE:
miles
i :
kilometers
N
PHELPS-DODGE
X PIT & MILL
l.V. INDUSTRIES
PIT
1 LOW
DISTANCI
NOT TO
SCALH
Whitewater Creek
DISTANCE
NOT TO
SCALH
Hanover £"f ACID
Junction ^ / LEACH
ASARCO
'GROUNDHOG
MINES
FLOW
SANTA RITA
CH1NO
PIT
SLA(i
Hurley
MILL&SMLLTER
DISTANCE
NOT TO
SCALE
^^
^^
Minihre\
River
To Miinbrcs
River
Figure 18. Sampling sites near Fierro, Chino/Hurley, and Tyrone, New Mexico.
-------
Figure 19. Santa Rita-Chino pit
Figure 20. Waste pile and acid leach runoff above Santa Rita-Chino pit
.
-------
TABLE 18. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR FIERRO,
CHINO/HURLEY, AND TYRONE, NEW MEXICO
Sampling Location
U. V. Industries, Inc.,
Pit at Fierro
Water (Recycled)
Sediment
Larvae (Midge)
Old Mill Near Fierro
Water
Sediment
Larvae (Midge)
Kennecott Copper Co.
Santa Rita Pit
lA/ator
Sediment
Acid Leach
Water (Recycled)
Sediment
To Irrigation at Hanover Junction
Water
Sediment
Hurley
Below Mill
Water
Sediment
Below Smelter
Sediment
Thallium
<0.003
<0.08
<0.003
0.31
<0.08
^
0.005
1.35
0.0037
<0.14
<0.003
0.082
—*
^
0.19
Cadmium
0.0021
7.9
None
0.0005
18-98
2.6
0.5
0.16
4.3
0.15
0.5
0.0008
0.17
1
Lead
0.02
1540
None
<0.01
1100-3140
535
^
35,000
^
0.02
3500
^
0.05
645
^
0.01
216
^
^^
2190
^_
58
-------
FLOW
N.
_NEW MEXICO
MEXICO
Smeltertown'
SCALE:
miles
1
kilometers
INDICATES
SAMPLING SITES
TEXAS
CEMETERY
V ASARCO
•' SMELTER
Figure 21. Sampling sites in vicinity of El Paso, Texas.
59
-------
TABLE 19. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
EL PASO, TEXAS (ASARCO SMELTER)
Sampling Location
Rio Grande
Upstream
Water
Sediment
Algae
Smelter
Water
Sediment
Algae
Wash Draining Smelter
Water
Sediment
Algae
Cemetery Soil Under Stack
Water
Sediment
Algae
Downstream
Water
Sediment
Algae
Thallium
0.3
0.3
Cadmium
0.0008
3
4.4
Recycled
7.1
None
Flood only
19
None
None
7.5
None
13
3
Lead
0.03
415
765
Recycled
10,200
None
Flood only
11,600
None
None
3140
None
1370
48
Summary of porphyry district findings — In summary, the porphyry
copper belt wastes had high measured lead concentrations, probably as a
result of no present lead recovery from these ores. The largest source
of pollution as previously reported was Mineral Creek (Table 13, Figure 14)
draining the Kennecott-Ray pit into the Gila River. The next largest
operations were at the Kennecott-Santa Rita Pit on Whitewater Creek (Table
18, Figure 18). Although most of the flood flow of Whitewater Creek was
used to irrigate cotton around Deming, New Mexico, some alfalfa was grown
and fed to beef cattle. The low flow went to ground water recharge, where
ion exchange capacity was sufficient to remove most toxic metals. Some
of the mine wastes found at Santa Rita had as high as 3.5% lead (but is
essentially cadmium-free). It was eroding and leaching rapidly.
Magma Copper Co. operations at Mammoth (Table 14) and Superior
(Table 16, Figure 16) are well dammed off from permanent surface streams
although these, like all tailing dams, are subject to rainwash. Thallifer-
ous slime in the San Pedro River was probably related to sewage treatment
of domestic wastes from the town site.
The only thallium found in Globe/Miami (Table 15, Figure 16) was
5 ppb in the acid leach water which was recycled through the mine wastes.
No cadmium was found at the control site upstream (less than 0.5 ppb in
water and 50 ppb in sediment and biota). At Globe, the ruined Miami
Copper Company (now Cities Service) smelter site had over 20 hectares
(50 acres) of old slag containing 98 ppb of thallium which was eroding
into Final Creek.
60
-------
No toxic metals were observed in the Phelps-Dodge operations or on
the San Francisco River below Clifton, Arizona (Table 17, Figure 17),
although flood erosion and leaching were a potential hazard. At Tyrone,
New Mexico, a sample of exposed mine wastes contained 73 ppb thallium,
43 ppm cadmium, and 0.52% lead.
Planet Mine (Parker), Arizona--
The Planet Mine, now closed, was sampled in January 1973. It produced
the representative, high-temperature ores that are close to the active
rhyolite volcanism and copper mineralization of the Salton Sea. The mine
is on the Bill Williams River, which drains into the Colorado above Parker,
Arizona (across from Earp, California) (see Figure 22). During operations
from 1966 to 1970, a coarse, poorly controlled acid leach was used to
extract copper from the hematite-magnetite (Fe~0_-Fe_0.) ore sampled.
Wastes sampled could be carried down the dry Planet Wash to the river
during floods (Figure 23).
The highest concentration of thallium found in the Southwest—5 ppm--
was found at the closed Planet Mine (Table 20). The Colorado River below
the Bill Williams River and Planet Mine had the highest regional back-
ground, with 21 ppb of thallium. It is an area of natural metal concen-
tration.
N.
INDICATES
SAMPLING SITES
PLANET
RANCH
0
SCALE:
miles
1234
Parker
I l I I | I
0123456
kilometers
Figure 22. Planet Mine (Parker), Arizona, sampling sites.
61
-------
,
Figure 23. Planet Mine acid leach.
-------
TABLE 20. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR PLANET MINE,
PARKER, ARIZONA (POWDERED METALS CORP., JANUARY 1973)
Sampling Location
Planet Mine Acid Leach (Closed)
Water
Sediment
Algae
Grass Roots
Larvae (Blackfly)
Clams
Fish
Bill Williams River at Planet Ranch
below Mine Wash
Water
Sediment
Algae
Grass Roots
Larvae (Blackfly)
Clams
Fish
Colorado River at Parker below
Bill Williams River
Water
Sediment
Algae
Grass Roots
Larvae (Blackfly)
Clams
Fish
Thallium
5.1
None
_
—
_
—
—
<0.11
0.031
_
—
—
—
...
0.021
<0.07
—
—
—
Cadmium
125
—
None
None
None
-
1
0.23
0.4
None
-
_
0.05
—
^^
None
12
—
Lead
Dry
34.200
None
None
None
None
None
0.01
37
16
35
42
None
9300
<0.01
32
110
_
None
170
-
Midwestern U.S.
Mid-continent Lead/Zinc Region--
Thallium is not significant in the extensive low-temperature lead/zinc
ores of the mid-continent: Wisconsin, Illinois, Missouri, Kansas, Oklahoma,
and Arkansas. Only those smelters in the midwest which have used or are
using significant amounts of Cordilleran or foreign ores and which meet
the established criteria (Section 5) were included in the study locations.
With the exception of the single refinery located in East St. Louis,
Illinois, all of these smelters are located in southeastern Missouri
surrounding the so-called New and Old Lead Belts of that state. The limits
of the Missouri study area, the approximate limits of the Missouri Lead
Belts, and East St. Louis are shown in the locator map of Figure 24. The
Missouri study area is depicted in detail in Figure 25.
Missouri New Lead Belt (Viburnum Trend)—
Overall description—A field sampling program was conducted in the
Missouri New Lead Belt, or Viburnum trend, and associated processing
facilities.
63
-------
NEBRASKA
IOWA
MISSOURI
Kansas City
AREA DETAILED
IN FIGURE 25
I I I I I FT
0 20 40 60 80
kilometers
•'••• •vTX/ «JLL» L
W///////,
NEW LEAD BELT '//
Y///////////,
N.
E. St. Louis
ILLINOIS
ARKANSAS
KENTUCKY
TENNESSEE
Figure 24. Missouri New and Old Lead Belts in relation to area of Missouri sampled (shaded area).
-------
*OPERAT10NS SAMPLED
Hcrculaneum
Minerals Corp
Smeller * - ».^
Festus
Siintc Gtncvieve 4
Bonne Terre . *
9
MISSOURI
Sluw Branch
\
^Farrnington
West t-'ork llit::ali Creek
/•.'as/ Fort llu::uli Creek
* MOLOC Smeliei
ASARCOlGlovei
"^ Smelter
* Fletcher Mine/Mill
Bunker
0/.ark Lead Co. Mine/Mi
SCALE:
miles
5 10
Ellington
Clear\\vi
Clearu^ter Dam
0 5 10 15 20
"(•"•I i ' i I1 I 'l I
5 0 5 10 15 20 25 30
kilometers
Figure 25. Southeastern Missouri showing operations sampled
and associated features discussed in text.
65
-------
The New Lead Belt runs over 56 km (35 miles) north-south through the
virtually uninhabited Ozark Plateau in Clark National Forest. A regional
fracture trend in the Cambrian Bonneterre dolomite bedrock controls the
occurrence of narrow caverns. These caverns extend 360 meters (1200 feet)
below the surface down to the underlying insoluble pre-Cambrian granite
basement and have been gradually filled by reductive precipitation from
circulating groundwater with up to 270 meters (900 feet) of sulfide ore.
The sulfide ores are of massive galena (PbS) with a thin rim of sphalerite
(ZnS) and chalcopyrite (CuFeS ) containing a small amount of argentite
(Ag2S). The first chalcopyrite (CuFeS~) containing a small amount of
argentite (Ag2S). The first mines at viburnum, geophysically discovered,
were opened in 1967 and the trend has become the largest lead-producing
district in the world. The production required by the terms of Forest
Service leases, coupled with recent restrictions on pigment and gasoline
use, have cut the price of lead drastically.
A mine must pump 315 to 440 liters/second (5000 to 7000 gallons/
minute) of groundwater to operate. Conventional operations run most of
this relatively clear water through the mill and flotation concentrators
to wash away waste rock flour. The high grade of the more massive galena
ore often overloads the flotation system, and, with the decline of lead
prices, it is not economical to recover the last percent or more of the
lead mined.
The muddy water, organic flotation agents, and wastes are discharged
into any convenient nearby valley which could be provided by a series of
dams made of the coarser mill tailings (by a cruder version of the cyclone
separation process described for the White Pine facility). The final
effluent thus varies with the pond size and mine water volume discharged.
The dark lead-bearing dolomite mud coats the stream bottoms with a
gray algal-bacterial slime. The benthic fauna appeared to be intolerant
of this lead-rich diet. The entire region is drained by various tribu-
taries of the Mississippi River.
The air and water pollution by Pb, Zn, Cu, and Mn are being studied
on a continuing basis by B.C. Wixson and colleagues in Environmental
Engineering at the University of Missouri-Rolla, with support furnished
by the National Science Foundation RANN Program.
Viburnum--The most extensive producer in the area is the St. Joe
Minerals Corp. This Corporation was the largest producer from the Old
Lead Belt 48 km (30 miles) to the east. Conventional mines and mills
were in operation at Virburnum and at the Fletcher Mine/Mill, and under
construction on the intervening Brushy Creek. Their ponds were minimal
in size, the dams were eroding rapidly, and the effluent from their
plants was virtually abiotic, apparently due to excess organic flotation
agents discharged. The milled ore was shipped to the old company smelter
on the Mississippi at Herculaneum. All of their active facilities were
sampled.
66
-------
Two mines at Viburnum were in operation along Indian Creek, a tributary
of Huzzah Creek, which is a tributary of the Meramec River. The ore from
the downstream mine was trucked up to the mill at the upstream mine. The
truck route, paralleled by a large-diameter pipe which conveyed the mine
water to the upper pond, was built along the creek. Samples were taken
from the relatively clear uppermost pond (which has a thick mat of the
algae Chara); from the lower pond; from mill tailing discharge; and from
the creek below the lowermost dam, which contained mill wastes. Analyses
of lead and cadmium in water, mud, and biota are given in Table 21.
Bixby Region—The largest facilities center around the Homestake
Mining Co./American Metals Climax, Inc. (Missouri Lead Operating Co.,
or MOLOC smelter, 1.2 km (0.75 mile) southwest of the Magmont Mine, midway
between Bixby and Buick). Its slag is presently being stockpiled, although
it was used on roads until recently. The effluent is combined with tail-
ings from their Buick mill and the Magmont mine/mill of COMINCO American
(Kennecott Copper and partners), settled, recirculated, and discharged
into Strother Creek. The large volume of mine water from this huge
operation fills Strother Creek over capacity. (Much larger pond capacity
would be required to allow evaporation of this flow. Separation of the
tailings, however, and recirculation of the mill water required could be
achieved readily, as suggested to MOLOC by Wixson).
TABLE 21. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
VIBURNUM, MISSOURI
Sampling Location
Mine/Mill Tailing Discharge
Water
Mud
Algae
Minnows
Pondt
Water
Mud
Algae (Chara)
Minnows
Pond 2
Water
Mud
Algae
Minnows
Waste Discharge into Indian Creek
Water
Mud
Algae
Minnows
Cadmium
^ Pumped f
2.5
None
0.008
<1.3
3
0.001
2.5
None
0.001-0.002
None
Lead
rom Mine-^-
1250
None
4.3
500
63
0.55
None
0.04-0.9
300
None
2
67
-------
Samples were taken of slag and tailings at the MOLOC/Magmont complex.
Effluent, sediment, and biota samples were taken below the final serpentine
spillway (designed by Wixson to promote algal growth) above Asher Cemetery.
Results of chemical analyses are given in Table 22. The analysis shows
0.27 +_0.03 ppm Pb in this water. Wixson found up to 0.83 ppm Pb in the
water~at this point and approximately 60 ppm Pb, 7-14 ppm Zn, 0.25-0.7 ppm
Cd, and 3-7 ppm Cu in Strother Creek mud. Control samples were taken along
Neals Creek, which joins Strother Creek below the last MOLOC dam.
Significant Tl was not found in the plant effluent or river samples.
Tl levels determined by plant laboratory personnel from emission spectros-
copy were clearly below 1 ppm in any waste stream. Serious Pb pollution
occurred due to the slag-granulating cooling water, which must be recir-
culated to meet current effluent standards.
TABLE 22. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
BIXBY, MISSOURI (MOLOC/MAGMONT COMPLEX)
Sampling Location
Clean Control Streams
Water
Sediment
Algae
Larvae (Caddis)
Crayfish
Minnows
Magmont Mill
Water
Sediment
Algae
Larvae (Caddis)
Crayfish
Minnows
MOLOC Smelter
Water
Sediment
Algae
Larvae (Caddis)
Crayfish
Minnows
Strother Creek
Water
Sediment
Algae
Larvae (Caddis)
Crayfish
Minnows
Cadmium
£0.002
0.5
0.14
1.7
0.29
—
0.002
13
None
None
None
—
None
8.2
None
None
None
—
0.001
0.5-1.3
0.13-0.21
3.4
2.5
—
Lead
10.013
50
20
44
5.7
2.9-8.4
5
1550
None
None
None
None
None
10,500
None
None
None
None
0.27
850-2050
None
320 (Blackfly)
48
5.6
68
-------
Bunker Region--A mine and mill operated by the Ozark Lead Co. (a
subsidiary of Kennecott Copper) in the most isolated location (southeast
of Bunker) has the most nearly complete recirculation system yet in the
trend. A small, nearly abiotic effluent discharged into Sweetwater Creek
was sampled, and 1 ppb Cd and 44 ppb Cu were found.
The most serious waste problem is the effluent from the Fletcher
mine/mill close to Bee Fork. The settling ponds are narrow and already
full of tailings, except for the small, shallow lagoons in the floodplain.
The virtually abiotic effluent into Bee Fork was sampled along with the
upstream control biota. The effluent was sampled where mixing first occurs
(Figure 26) and 3.2 km (2 miles) further downstream. The effluent contained
0.12 +_ 0.003 ppm of lead by atomic absorption analysis. Recent severe local
flooding had reduced the benthos all along Bee Fork, which receives flash
runoff from a cleared area upstream (south) around the small town of Bunker-.
Analyses of lead and cadmium in water, sediments, and biota are given in
Table 23.
TABLE 23. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
FLETCHER MINE/MILL, MISSOURI (ST. JOE
MINERALS CORP.)
Sampling Location
Bee Fork
Above Outfall*
Water
Sediment
Algae (Myriophyllum)
Larvae (Caddis)
Crayfish
Minnows
Mill Tailing Pond
Water
Sediment
Algae (Myriophyllum)
Larvae (Caddis)
Crayfish
Minnows
Below Outfall
Water
Sediment
Algae (Myriophyllum)
Larvae (Caddis)
, Crayfish
Minnows
Cadmium
0.001
0.5
None
2.2
0.17
0.25
0.001-0.002
_
0.28
2.6
None
None
0.001
1
0.1
1.8
0.22
0.08
Lead
<0.01
350
None
11
10
32
0.12-0.13
^
112
71
None
None
0.003
38
19
97
19
3.9*
'Below Highways, Lily Farm, and Bunker
69
-------
Figure 26. Tailings effluent at Bee Fork Creek.
-------
In summary, the lead levels in waters from the New Missouri lead belt
were high, as shown in Tables 21 and 23. The low levels of lead discharge
which can be achieved were shown below the Viburnum mine/mill, which
recirculates its water through two tailing ponds. In the final effluents,
lead was below 10 ppb, zinc below 100 ppb, and cadmium below 1 ppb. Only
copper (44 ppb) was above the levels in uncontaminated control streams.
Cadmium values were all low.
Missouri Old Lead Belt (St. Francois Mountains Trend) —
Summary--St. Joe Minerals Corp. and ASARCO have extensive facilities
in the Old Lead Belt on the Bonneterre outcrop in the St. Francois Mountains,
where lead has been known to exist since the 18th century.
Flat River—Near the confluence of Shaw Branch with the Flat River,
at the towns of Flat River and Esther, there are extensive mining wastes.
In the river, there is a mountain of coarse, gravel-size tailings which is
over 92 meters (300 feet) high and contains visible galena. On the branch,
the closed St. Joe Federal mine and mill are surrounded by extensive waste
piles and tailing ponds. To determine the effects of both waste sources,
samples were collected at the confluence. Analyses of water, slag, sedi-
ment, and biota for lead and cadmium are given in Table 24.
Glover--The ASARCO Custom smelter on Big Creek near Glover, Missouri,
has been recently rebuilt. It serves Ozark Lead Co. and some of the
remaining minor production from the Old Lead Belt. Water is recirculated
at this smelter. The slag effluent and sediment were sampled, and water
from Big Creek was sampled above and below the small effluent discharge,
which contained 53 ppb Cd, 220 ppb Pb, 212 ppm Zn, and 3 ppb Tl. (Refer
to Table 24).
Herculaneum, Missouri—
The St. Joe smelter was built in 1864 on a narrow terrace between high
cliffs and the Mississippi River. Its capacity is being increased by high-
rise construction. The hot effluent, including sanitary sewage and acid-
plant leakage, is discharged directly into the main deepwater channel of
the river from a new tall structure. A water recirculating system has
been "under construction" for years. The slag and river above the smelter
were sampled, but access to the present effluent could not be obtained
The St. Joe Minerals Corp. slag piled along the bank of the Mississippi
River at Herculaneum, contains from 1 to 3.3% lead, 1 to 9.2% zinc, 300 to
3800 ppm copper, and 14 to 250 pp« cadmium. The most toxic of this material
was being bulldozed into the river in large quantities in the process of
building a sanitary sewage treatment plant next to the smelter
71
-------
TABLE 24. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR
FLAT RIVER (ST. JOE MINERALS CORP.) AND
GLOVER(ASARCO)
Sampling Location
North of Flat River, 300-ft high Tailing Pile
Water
Slag
Sediment
Algae
Larvae
St. Joe Federal Mill Near Flat River
Water
Slag
Sediment
Algae
Larvae
Drainage into Shaw Branch at Flat River
Water
Slag
Sediment
Algae
Larvae (Caddis)
ASARCO Glover Smelter
Water
Slag
Sediment
Algae
Larvae
Drainage into Big Creek
Water
Slag
Sediment
Algae
Larvae
Cadmium
None
None
1.3
None
None
Closed
None
7.5
None
None
0.001
None
1.3
0.96
2.1
0.053
12
300
1330
None
< 0.001
None
—
—
—
Lead
None
None
12,000
None
None
Closed
None
1500
None
None
0.23
None
6500
2800
2200
0.22
9500
25
2230
None
0.013
None
—
—
^
72
-------
East St. Louis, Illinois—
The American Zinc (now owned by AMAX) electrolytic refinery, sampled
in November 1972, is located in the floodplain of the Mississippi River.
Spent acid and water were discharged into a serpentine lagoon discharging
into a slough. This waste and two tank-bottom sludges (one being rich in
Cu) dumped on its banks were sampled. The cupriferous waste was 12% zinc,
15% copper, 0.18% lead, and 0.62% cadmium. The black sludge covering a
large area west of the plant was 8.7% zinc, 0.75% copper, 0.45% lead, and
0.1% cadmium. No thallium was detectable at the 90-280 ppb level.
White Pine, Michigan—
The Copper Range Co., White Pine, Michigan, mine and smelter, with a
large tailing area, is on the Mineral River draining into Lake Superior,
cleanest and coldest of the Great Lakes (Figure 27). These waters still
support commercial fisheries and provide the public supply for tens of
millions of people. The wastes and waters from the smelter and mill were
sampled down to the lake on August 24-26, 1972.
In the copper processing at White Pine, pit-run shale is milled to a
mud and most of the CuS concentrate floated off with surfactants. The fine
tailings from the mill are neutralized with lime and piped to storage behind
earthen dams. The storage area is gradually covering the large region
between the mine and Lake Superior. Some of the coarser tailings are used
to build the dam and fill the mine. Mill water, rain, and snowmelt are
decanted with minimal mud (restricted by state standards) and collected in
Native Creek (Figure 28), a deep stream 1 to 2 meters (3 to 6 feet) wide,
which joins the Mineral River where it is 15 meters (50 feet) wide and
0.3 meter (1 foot) deep, just above Lake Superior.
The wet concentrate from the mill is melted in reverberatory furnaces.
Up until now, pyrite has been added to enhance sulfur concentration and
reduce smelting costs. This pyrite has been acquired from Bethlehem Steel's
Cornwall, Pennsylvania, mine, which also supplies the Sparrows Point,
Maryland acid plant. Because the pyrite deposits are nearly exhausted,
and in an effort to reduce sulfur emissions from the stack, the concentra-
tion of pyrite used in the White Pine processing is currently being minimized
and, presumably, will be eliminated.
For this reason, the nature of the slag and the water effluents is
now in a state of transition. In any case, slag from the furnaces is
dumped, crushed, washed, and (as much as possible) sold for road and other
use. Wash water and other smelter runoff settles in a small new pond and
flows through the woods and Bannister Creek (1 to 2 meters (3 to 5 feet)
wide), into the Mineral River (Figure 29), where it is 4 meters (12 feet)
wide and 1 meter (3 feet) deep, just below the Carp Lake Township Dump.
The survey of the Mineral River (Figure 27) started above the smelter
and company town, where it is 0.3 to 0.6 meter (1 to 2 feet) wide and
has a complete normal boreal biota consisting of algae, aquatic moss,
caddisfly larvae, water striders, and minnows. The river was then follo<
past the facilities, including a sewage treatment plant and uncontrolled
erosion from the slag pile, down to the junctions with the muddy influents.
73
-------
Lake Superior
INDICATES
SAMPLING SITES
SLAG; SMALL
PILE / DAM
COPPER RANGE CO.
SMELTER
SCALE:
miles
kilometers
Figure 27. White Pine, Michigan, sampling sites.
74
-------
Figure 28. Native Creek (White Pine, Michigan).
Figure 29. Turbidity of Bannister Creek near junction of
Mineral River (White Pine, Michigan).
.
-------
With the assistance of plant environmental-control personnel, we
sampled soil, tailings, pond waters, and effluent into both Native and
Bannister Creeks. Results of these analyses are given in Table 25. The
mud in the Mineral River below Bannister Creek continues out into Lake
Superior to such an extent as to reduce the biota to a few algae and
water striders. The latter probably feed primarily on terrestrial insects
which fall in from the forest.
No thallium was detected, even in recycled flue dusts.
levels of lead, copper, and zinc are present.
Significant
TABLE 25. CONCENTRATIONS OF HEAVY METALS (ppm) NEAR WHITE PINE, MICHIGAN
(COPPER RANGE CO., AUGUST 1972)
Sampling Location
Control (Mineral River below [North of] Sewage Plant)
Sediment
Algae
Larvae (Caddis)
Fish (Stickleback)
Mill Tailings (Native Creek) at Tailing-Pond Outfall
Sediment
Algae
Larvae (Caddis)
Fish (Stickleback)
Mill Tailings (Native Creek) at Junction of Mineral River
Sediment
Algae
Larvae (Caddis)
Fish (Stickleback)
Slag Runoff (Bannister Creek) at Dam Outfall
Sediment
Algae
Larvae (Caddis)
Fish (Stickleback)
Slag Runoff (Bannister Creek) at Junction of Mineral River
Sediment
Algae
Larvae (Caddis)
Fish (Stickleback)
Cadmium
0.057
0.72
—
1.0
0.14
3.5
— _
11
0.008
0.88
11
None
0.12
None
None
None
0.011
None
None
None
Lead
1.1
45
—
36
0.29
128
73
0.08
24
190
None
0.33
None
None
None
0.13
None
None
None
Copper
240
360
—
55
4600
5000
—
360
1400
52
230
None
1300
None
None
None
1300
None
None
None
Zinc
22
81
—
55
Not analyzed
1300
—
190
13
—
300
None
180
None
None
None
67
None
None
None
76
-------
Eastern U.S.
Perth Amboy and Sewaren, New Jersey--
A visit was made to Perth Amboy, New Jersey, to examine plants typical
of those situated on estuaries and tidal basins. It was found that the
ASARCO and Anaconda copper refining plants on the Raritan River estuary
discharge into an area containing 4 hectares (10 acres) of waste (Figure 30)
Next to ASARCO along Arthur Kill, National Lead reclaims battery plates
along with other operations, with over 10 hectares (25 acres) of waste
placed directly in the tidal marsh of the estuary. While none of its own
operations may contribute Tl to the aquatic ecosystem, the dump was also
used by surrounding industry and is believed to be a serious source of
pollution, possibly including Tl. Waste-material samples were obtained
for the Anaconda refinery. Samples were also taken at the Copper Pigments
and Chemical Works, Inc., located at Sewaren, New Jersey.
Analyses of the collected samples were made using the Perkin Elmer
Model 303 atomic absorption spectrometer. The results of these analyses
are listed in Table 26. They are consistent with the amounts of thallium
present in primary blister copper and the sludge-handling techniques of
electrolytic refining. However, the Cottrell-precipitator dusts, which
contained more hazardous concentrations, were only intermittently dis-
charged to the aquatic environment.
The high thallium concentrations found in New Jersey were from small
dumps of sludge and other highly toxic material, which may not be repre-
sentative. They were not resampled, however, because of the high level of
background contamination throughout the entire industrial area, including
the Raritan River and Arthur Kill, which drain these sites.
TABLE 26. RESULTS OF THALLIUM ANALYSES FOR NEW JERSEY SAMPLES
Plant
Anaconda Co.
Anaconda Co.
Anaconda Co.
Copper Pigments and
Chemical Works
Location
Perth Amboy
Perth Amboy
Perth Amboy
Sewaren
Sample
Sludge Dump, near
tailing pond
Sludge Dump, fresh
Sludge Dump, gley
horizon
Sludge Dump
Thallium
Concentration (ppm)
20
21
26
17
77
-------
SCALE:
miles
COPPER PIGMENTS
AND CHEMICAL WORKS
ASARCO
REFINERY
NATIONAL LEAD CO.
Perth Amboy
SLUDGE
DUMP
Staten Island
ANACONDA CO
REFINERY
SAMPLING SITES
Figure 30. Perth Amboy/Sewaren, New Jersey, sampling sites.
78
-------
Palmerton, Pennsylvania--
The old smelter and refinery complex of the New Jersey Zinc Co. is at
Palmerton, Carbon County, Pennsylvania, on the Lehigh River just above the
watergap through Blue Mountain where the river emerges from the Appalachian
Mountains (Figure 31). Metal fumes from the low stacks at Hazard (West
Palmerton) have killed almost all of the trees in the valley. Hot 30 C
(87°F) effluent (pH 4.5) from the smelter was sampled where it enters the
Lehigh River along with slag and the resistant flora: algal slimes, mosses,
and horsetails. Mud in the river bed contained 13% zinc, 590 ppm copper,
0.13% lead, and 5.4 ppm cadmium. The river was heavily polluted by sewage
from Lehighton, Jim Thorpe, and other communities above the smelter.
The acid plant and refinery in East Palmerton are on Aquashicola
Creek, which joins the Lehigh at the watergap. Cold effluent and sediment
were sampled from the outfall at the creek, where acid recovery appears to
be satisfactory. The water contained only 90 ppb zinc. The sediment in
the creek, however, contained 6.1% zinc, 0.7% copper, 290 ppm lead, and
93 ppm cadmium.
Other Known Thalliferous Sulfide Accumulations
Sites Not Requiring Sampling or Impossible to Sample--
The high-capacity plant in the Salt Lake City, Utah, area (Garfield
and Tooele) drains directly into Great Salt Lake, which is essentially
a lifeless, saturated brine.
The known Tl reserves in the dump at Mercury, Utah (4), are not
near any permanent water and drain through ephemeral channels into dry
Rush Lake. Inactive and secondary plants were not sampled, although the
locations of a number of such waste concentrations are known.
The zinc smelter operated by the Matthiessen and Hegeler Zinc Company
in the village of Spelter (0.4 km (0.25 mile) south-southwest of the town
of Meadowbrook), West Virginia, 7.2 km (4.5 miles) north-northeast of the
city of Clarksburg, has apparently filled an entire bend in the West Fork
River up to 6 meters (20 feet), over 0.8 km (0.5 mile) long, of what was
floodplain. High rainfall of the region tends to promote leaching. The
river, like most of those in the Coal Measures, is entrenched without a
wide floodplain, so catastrophically high water levels may occur. However,
the river is too polluted to provide significant data on bioconcentration.
Lithopone production has become negligible. A small amount has
recently been exported to South Vietnam. Lead-free ZnO has replaced it
domestically. The largest plant (American Zinc Company) at Columbus, Ohio
(which also produces sulfuric acid), is not situated on a surface stream.
Any surface runoff apparently runs into a nearby cemetery and percolates
into the soil.
79
-------
oo
o
INDICATES
SAMPLING SITES
NEW JERSEY ZINC CO.
SMELTER & REFINERY
Figure 31. Palmerton, Pennsylvania, sampling sites.
-------
Steel Mills in Bethlehem, Pennsylvania, and Elsewhere--
Blast furnaces formerly using anthracite coke at the main Bethlehem
Steel Co. plant in Bethlehem, Pennsylvania, are closed. Current metallur-
gical operations use electrical furnaces to produce high-grade specialty
steels. The slag dump and Lehigh River water at this plant were sampled.
Analysis of these and other steel slags previously sampled indicates that
ferrous metallurgy produces little serious heavy-metal hazard. No thallium
was detected. The gross observable biological effects are negligible
compared with those of copper, lead, and zinc operations.
Sulfuric Acid Plant in Copper Basin, Tennessee--
Up to 3-1/2% Tl has been reported in sulfuric acid made from thalli-
ferous pyrite (5). Sulfuric acid made from pyrite (FeS-) may concentrate
Tl in the exit stack gas. The original Cottrell precipitator was installed
to remove sulfuric acid mist at the ASARCO copper smelter in Selby,
California, in 1909. A decision was made to sample from the Copperhill
smelter and acid plant within the large Copper Basin region of Tennessee.
The Copper Basin (Figure 32) is an eroding, devegetated wasteland,
9.6 km (6 miles) across, centered near Ducktown, Polk County, and covering
the southeast corner of Tennessee. Chalcopyrite, pyrite, and other sulfides
similar to the rocks mined at Kellogg, Idaho, and White Pine, Michigan, are
found in black schists of the Ocoee series. Mines are scattered throughout
the basin, with an active mill and abandoned smelter at Isabella (Ducktown)
on North Potato Creek and an active smelter with a large acid and chemical
plant at Copperhill on the Ocoee River.
The control sampling stations for this region were the headwaters of
Burra-Burra Creek above the tailing pond and the Ocoee River at the
Tennessee-Georgia border (Figure 32). A number of areas suspected of
heavy metal concentration were sampled. These included ore from an abandoned
mine pit near the tailing pond, the tailing pond itself, drainage from the
tailing pond into North Potato Creek, the Copperhill smelter wasteweir on
Davis Mill Creek and a ditch (West Newton) draining through the vicinity
of the smelter to the Ocoee River. The Ocoee River was further sampled
below the Rogers Bridge and 8 miles downstream at the Ocoee No. 3 power-
house. Results of analyses are given in Table 27.
The tailing pond was found to contain 1.4 ppm phenol, apparently from
chemical wastes in the mill water. Relatively large amounts of thallium
are stored in the tailing pond as a byproduct of pyrite mining and sulfuric
acid production. The tailing pond is subject to flood overflow. Cd could
not be detected anywhere in the Ocoee River water or uncontaminated control
stream waters but was found in all the outfalls and creeks leading from
the mill and smelter. Copper, zinc, lead, and cadmium showed a tendency
to accumulate in aquatic roots and mosses but not in algae and fish. This
probably results from direct exchange between sediments and root hairs.
81
-------
00
K)
JARNIGAN MOUNTAIN
OCOEE NO. 3
POWERHOUSE
DISTANCE
NOT TO
SCALE
ISABELLA
MILL (ACTIVE)
AND SMELTER
(ABANDONED)
INDICATES
SAMPLING SITES
CITIES
SERVICE CO
SMELTER
ROGERS
BRIDGE
TENNESSEE
GEORGIA
Figure 32. Copper Basin, Tennessee, sampling sites.
-------
TABLE 27. CONCENTRATIONS OF HEAVY METALS (ppm)
IN COPPER BASIN, TENNESSEE REGION
Sampling Location
Controls
Headwaters of Burra-Burra Creek
at Jarnigan Mountain (pH 4.4)
Water
Sediment
Aquatic Roots
Algae
Minnows
Upstream Ocoee River at Georgia
State Line (pH 5.0)
Water
Sediment
Aquatic Roots
Algae
Minnows
Contaminated Materials
Mine Waste Near Tailing Pond
Water
Sediment
Aquatic Roots
Algae
Minnows
Tailing Pond
Water
Sediment
Aquatic Roots
Algae
Minnows
Pond Drainage into N. Potato Creek
IpH 3.5)
Water
Sediment
Aquatic Roots
Algae
Minnows
Copperhill Smelter Waste Weir on
Davis Mill Creek (pH 3.9)
Water
Sediment
Aquatic Roots
Algae
Minnows
W. Newton Ditch (at gate) (pH 3.9)
Water
Sediment
Aquatic Roots
Algae
Minnows
Ocoee River below Rogers Bridge
(pH 4.7)
Water
Sediment
Aquatic Roots
Algae
Minnows
8 Miles Downstream at Ocoee No. '.
Powerhouse (pH 4.5)
Water
Sediment
Aquatic Roots
Algae (Aquatic Moss)
Minnows
Thallium
_
0.1
—
—
—
—
—
—
—
—
_
0.25
—
—
—
_
1.4
—
—
—
_
—
—
—
—
_
—
—
—
—
_
—
—
—
—
-
0.5
—
—
-
_
_
—
—
-
Cadmium
<0.003
0.1
0.25
None
None
<0.003
0.4
6.4
0.4
0.5
None
1
None
None
None
0.007
7.5
0.15
None
None
0.003
—
None
Norn
None
0.002
2
None
None
None
0.006
10
None
Nona
None
< 0.003
10
1.9
None
None
<0.003
2
0.25
0.6
None
Lead
<0.05
<12
<5
None
-
<0.05
75
<110
25
—
None
200
None
None
—
<0.05
250
4.2
None
—
0.3
—
None
None
—
1.0
170
None
Norn
—
0.1
150
Norm
None
-
0.2
2550
245
None
-
<0.05
150
<1.6
60
Copper
<0.01
40
5
None
-
<0.01
30
430
75
-
None
2100
Nona
None
—
0.01
2100
4.2
None
—
<
0.28
—
None
None
—
4.2
900
None
None
—
0.31
280
None
None
-
0.52
3800
450
None
-
0.06
500
25
240
Zinc
0.15
25
8.6
None
None
0.1
550
540
50
35
None
900
None
None
None
0.15
10,000
15
None
None
1.5
—
None
None
None
9.8
900
None
None
None
4.5
120
None
None
None
0.8
8800
450
None
None
0.25
1500
41
224
None
83
-------
Ore from an abandoned mine pit near the tailing pond contained 11%
copper, along with 900 ppm zinc, 300 ppm lead, and 1.8 ppm cadmium. The
slags at Isabella and Copperhill vary from 500 to 1400 ppm copper, 350 to
4800 ppm zinc, 75 to 200 ppm lead, and 0.5 to 1 ppm cadmium. Thallium was
not detectable at the 100 ppb level in any of these samples. Thallium was
not detected (at a sensitivity of 1 ppb) in any water or biota samples
collected from this region.
Anthracite-Burning Powerplants Near Scranton and Hazleton, Pennsylvania--
Some coal deposits, notably anthracite of high-temperature diagenetic
origin, contain considerable amounts of thallium associated with pyrite.
In addition to any small amount of heavy metals in the original biomass'
of the coal swamp, as groundwater slowly circulates through the sediment
mass, the reducing effect of the coal traps metal ions as sulfides. The
more deeply buried the coal, the more pyrite (FeS ) and other sulfides
crystallize within the fossil biomass and the greater the trapping potential
for heavy metals. The sequence of burial changes that occur in coal can
be expressed in the fixed-to-volatile carbon ratio, essentially the
graphite present relative to the amount of hydrocarbons (organic precursors
decay relatively rapidly to stable hydrocarbons and CCL) . These
metamorphic changes are the result of increased temperature at depth.
Therefore, anthracites are most likely to contain significant metal con-
centrations. When this coal is burned at power plants, any Tl present can
become concentrated in electrically precipitated fly ash. Power plants
using this type of coal are now restricted to the original mining district
from the Lehigh River to Scranton (centered on Wilkes-Barre), Pennsylvania.
Up to 76 ppm of thallium has been reported in flyash (6).
On the basis of these arguments, the anthracite region of Pennsylvania
was selected for study of the heavy metal hazard in fuel burning. Unfort-
unately, earlier low coal prices has caused closing of most mines, and
consequently, almost all anthracite-burning operations. Electric power-
plants sampled are identified in Table 28, and their locations are shown
in Figure 33. All but the standby plant at Harding were sampled. No
other large anthracite-consuming processes were found in use locally.
TABLE 28. ANTHRACITE-BURNING POWER PLANTS (PENNSYLVANIA)
Status
Stand by
Closed
Ruined
Burial Under
Waste
Plant/Owner
Pennsylvania Power & Light Co.
Pennsylvania Power & Light Co.
Glen Alden Coal Co.
Olyphant
Jenkins
Location
At Harding on
Susquehanna River
At Hauto Dam on
Nesquehoning Creek
At Nanticoke on
Sesquehanna River
At Dickson City on
Lackawanna River
At Port Blanchard on
Susquehanna River
84
-------
oo
en
North Anthracite Field
East-Middle Anthracite Field
West-Middle Anthracite Field
4 South Anthracite Field
SCALE:
miles
10 5 0 JO
......
'l''l'
16 0 8 16
kilometers
PENNSYLVANIA
INDICATES SITE
SAMPLED
Figure 33. Coal-burning sites sampled in Eastern Pennsylvania.
-------
Ash from the closed power plant at Hauto Dam contained 47 ppm zinc,
37 ppm copper, 0.51 ppm lead, 21 ppb cadmium, but no measurable thallium.
Strip-mine tailings in the immediate vicinity contained comparable amounts
of heavy metals. Flyash from the abandoned Glen Alden power plant on the
Susquehanna River at Nanticoke contained 64 ppm zinc, 123 ppm copper, 2 ppm
lead, 0.26 ppm cadmium, and no measurable thallium.
Mine-run coal contains larger amounts of waste each year, and the
convenient surface area available for disposal becomes less. Huge mountain-
ous piles of waste fill the coal-bearing valleys. In the narrow southern
valleys, conveyors pour the waste over the rimrock and down into the
surrounding unpolluted wooded plateau. The fine tailings of silt or "slush"
have also been deposited in huge unstable piles to avoid the final cost of
returning it underground or to fill strip-mine pits. The mud eroded from
the mound of waste at Port Blanchard contained 170 ppm zinc, 40 ppm copper,
0.41 ppm lead, and 77 ppb cadmium.
As much as 36 metric tons (40 short tons) of water were dumped from
the mines into streams to recover each ton of coal. The streams draining
waste and strip areas were acid and dead. Particularly dirty stream water
from Taylor, southwest of Scranton, was sampled, as well as sediment from
several waste ponds and streams. The water contained 71 ppb copper and
80 ppb zinc. No cadmium, lead, or thallium were detected.
All of the data indicate that coal mining and burning could contribute
significant quantities of toxic lead and cadmium to the environment by
tlood erosion. However, no measurable thallium quantities would be con-
tributed.
Bituminous-Coal-Burning Powerplant at East Corning, New York--
For comparative purposes, a bituminous-coal-fired powerplant in East
Corning, New York (Figure 34), was sampled. The plant is on the Chemung
River, a large, swift Appalachian stream with a steep gradient and a coarse
alluvial bed.
The river water and bed were sampled immediately above and below the
plant. Fine sediment and benthos (algae, mayfly larvae, and miscellaneous
forms) were obtained from beneath many boulders. Fish, including minnows,
foot-long suckers, and giant shiners, were netted by hand from swift
shallow riffles.
A flyash pond, approximately 92 meters (100 yards) from the river bank
and backwater, was sampled to determine the variability of the fine
metalliferous waste. This material erodes into the Chemung River as a
result of rainfall and washwater leaching. Smartweed (Equisitum), and
poplar (Populus) seedlings were found growing close to the flyash pond.
The recent flood, which did even more serious damage in the Anthracite
Coal District, washed out the Corning city sewage treatment plant just
above our sample sites. In addition to the increasing upstream pollution
the flood washed away everything around the powerplant, including much
flyash and its treatment system.
86
-------
N.
SCALE:
miles
1
kilometers
SAMPLING SITE
Susquehanna
River
Figure 34. East Corning, New York, sampling site.
Results of heavy metal analyses for water, sediment, and biota samples
are tabulated in Tables 29 and 30. Although significant thallium was
found in sediments and biota, none was detected in water samples. The data
suggest that bituminous-coal pyrite does not contain enough Tl to provide
an environmental threat. Cadmium, copper, lead, and zinc were found in
sediments, biota, and water. Levels of cadmium and lead in river water both
upstream and downstream of the flyash pond exceeded recommended EPA drinking
water standards (EPA lead limit-0.05 mg/1; cadmium limit-0.10 mg/1). The
data indicate that the flyash pond could be a source of cadmium and lead
discharges to the river.
87
-------
TABLE 29. RESULTS OF EAST CORNING, NEW YORK, WATER SAMPLE ANALYSES (ppm)
Downstream river water
Upstream river water
Upstream river water
Upstream river water
Fly ash pond
Fly ash pond (duplicate)
Fly ash pond (triplicate)
Cadmium
0.01740.002
0.015+0.002
0.018+0.002
0.022+0.002
0.018+0.002
0.10+0.01
0.017+0.002
<0.002
Copper
0.009+0.002
0.007+0.002
0.005+0.002
0.006+0.002
0.11+0.01
0.031+0.003
0.002+0.002
Lead
0.13+0.01
0.084+0.008
0.10+0.01
0.12+0.01
0.23+0.02
0.27+0.03
0.14+0.1
<0.002
No thallium was detectable in water samples
Zinc
0.035+0.004
0.015+0.002
0.010+0.001
0.018+0.002
0.14+0.01
0.14+0.01
0.048+0.005
<0.002
Variations shown are estimated analytical errors from variations in standard signal levels.
TABLE 30. RESULTS OF EAST CORNING, NEW YORK, SEDIMENT
VEGETATION, AND BIOTA SAMPLE ANALYSES (ppm)
Fly Ash Pond:
Horsetails
Poplar
Grass-leaves
Grass-roots
Grass-leaves & Roots
Helianthus
Fine Sediment
Fine Sediment (duplicate)
Coal
Septic Sediment
Cladophora
Coarse Sediment
Copper
27 ±3
29 ±3
22 ±2
16±2
29 ±3
18±2
20 ±2
14 ±1
28 ±3
29 ±3
8.2 ±0.8
13±1
Lead
23 ±2
20 ±2
18±2
40 ±5
11±1
2.1 ±0.8
21 ±2
1.
12±1
2.2 ±0.4
Thallium
<2
1±1
<1.2
1.6 ±0.9
<1.3
1.5 ±0.8
1
1.9 ±0.9
6.2 ±1
Zinc
39 ±4
67 ±7
32 ±3
11±1
28 ±4
26 ±3
120 ±10
22 ±2
63 ±6
30 ±3
26 ±3
88
-------
ECOLOGY OF THALLIUM
Purpose of This Subsection
The ecology of most of the trace metals measured in this study (copper,
zinc, lead, and cadmium) has been discussed in detail previously in the
scientific literature. Their known biological and geochemical balances
are reasonably well supported by the data in this report. Thallium (along
with some data on indium), however, has rarely been studied and is con-
sidered in more detail.
Abundance and Distribution of Thallium
There is approximately 1 gram of thallium (Tl) per ton of the earth's
crust. This is one-tenth the abundance of lead and 1/300 that of copper
and zinc. Thallium is strongly concentrated in igneous and volcanic
rocks (4).
Significant amounts of Tl are concentrated in the high-temperature
sulfide metal deposits of volcanic terrains. In the United States, these
are bodies that are restricted to Alaska, the western Cordilleran mountain
states, and the Appalachians. Although the distribution of Tl within such
ores is variable (depending on the composition of the mineralizing solutions,
country rock, and geothermal gradient), it has been possible to indicate
which industrial plants present the greatest Tl hazard as long as volcanic-
origin ores are processed.
Tl is usually associated with sulfide concentrations of zinc (Zn),
lead (Pb), copper (Cu), iron (Fe), cadmium (Cd), arsenic (As), indium (In),
selenium (Se), and tellurium (Te). The overt mineralization of Tl is
summarized in Table 31. The solutions, minerals, and equilibrium of Tl
deposition with Cd, Zn, Cu, and Fe can be visualized by means of the Eh-pH
diagram, a plot of reduction-oxidation potential (Eh) versus acity (pH)
(see Figure 35). The appropriate Eh versus pH field depicts the equilibrium
thermodynamic conditions under which Tl can exist in solutions and solids.
TABLE 31. THALLIUM MINERALS
Name
Chemical
Composition
Occurrence
Crookesite
Lorandite
Hutchinsonite
Vrbaite
(Cu,TI,Ag)2Se
TI2S • As2S3
(TI,Ag)2S • PbS • 2As2S3
TI(As,Sb)3S5
A Variety of Argentite (Silver Glance, A928)
With Realgar, AsS
In Dolomite, MgCa(CO3)2
With AsS, As2S3. and HgS
89
-------
vo
o
Eh
-0.8 —
12
Figure 35. Chemical environments of metal deposition.
-------
The Eh-pH ranges of Tl deposition are shown as the shaded area in
Figure 35. Depositions from hot brine (H_0) occur in the field including
Tl and chalcopyrite (CuFeS2), pyrite (FeS-), and galena (PbS), but not
magnetite (Fe,0.) or chalcocite (C^S). Eh-pH diagrams are available for
the systems Cu-Fe-S-0-H and Pb-S-CCL-0-H, shown superposed in Figure 35.
The deposition of Tl is confined to the FeS2 field. Zn and Cd are similar
to Pb.
Thus, the most important occurrence of the Tl is in pyrite, or "fool's
gold," which is almost universally present in base-metal ores, coal, and
other chemically reduced rocks.
Copper is, by far, the most important sulfide metal commercially. Its
most important ore, chalcopyrite (CuFeSO, like FeS™, can contain relatively
large quantities of Tl.
The western copper mines occur in a trend from Arizona through Utah
and Nevada to Butte, Montana, paralleling the Pacific Coast. Up to 5% Tl
is found in cupriferous pyrites (5).
Lead and zinc are found associated with or to the east of the
Cordilleran copper belt. The more easterly occurrences are of colder
origin and tend to contain less Tl. The zonation of commercial major
metal from west to east (from high- to low-temperature deposition)
is roughly Fe-Cu-Au-Ag-W-Mo-Zn-Pb (7).
The forms of the trace metals found in mining and smelting wastes
are indicated below.
Tailings, which contain most of the pollution from metal mining,
are mineralogically the same (primarily sulfide) as the ore which has
been concentrated. Smelter slag, however, is fayalite (Fe^SiO.) with
other unrecovered heavy metals substituted for iron in the lattice.
The major precipitant for toxic metals in natural waters is carbonate.
The beneficial effect of carbonate alkalinity for removing soluble metals
from water is particularly we11-demonstrated in the Missouri New Lead Belt,
particularly Strother Creek, which receives large quantities of mill and
smelter lead discharges (5 ppm in mill water, 1550 ppm in mill sediments,
and 10,500 ppm in smelter sediments). The high carbonate bedrock in
Strother Creek precipitates lead effectively from the water to 0.27 ppm.
The tie up of lead and cadmium in sediments does not prevent uptake by
biota in this case, however, as evidenced by high concentrations of lead
in larvae and crayfish, which feed on the metal-laden detritus.
As discussed under analytic methods, chloride ions form a significant
control to the solution transport of thallium. A particular halogen
complex (ligand) is formed with the thallous ion, which is readily adsorped
or precipitated. The loss of this ligand is similar to the precipitation
of thallium with bromine outlined in Appendix B.
91
-------
Sulfate ions have a slight solubilizing effect on thallium as compared
to+nitrate ions at constant pH, probably due to the oxidation of some
Tl to more soluble Tl
Chelation by dissolved organic substances may be an important mechanism
in addition to the thallous chloride complex and adsorption on particulate '
matter, particularly in suspended clays with their enormous surface area
This is especially true in streams like the South Fork of the Coeur d'Alene
River, which is saturated by untreated sewage. The organic ligands generally
tend to increase metal solubility, in contrast to the chloride precipitation
CIi6CL•
Behavior of Thallium in Natural Waters
The chemistry of thallium in natural waters has some puzzling features
The most obvious is the discrepancy between the relative abundance in soils'
(typically up to 10 ppm in those derived from granite crust) and the rarity
r^Sear!!ater t™™*1^ less t!?an 0.01 ppb as reported by Rex and Goldberg
(8). The atomic radius of Tl is 0.144 nanometers, making the density
relatively low so that Tl is carried into stack gas where it is easily
precipitated electrically. Up to 9% Tl has been found in flue dusts (4)
soil thallium is derived from orjhoclase, the common potash feldspar where
Tl may readily substitute for K in the lattice because of comparable
atomic size (0.144 vs. 0.133 nanometers, respectively).
Thallium Exchange with a Montmorillonite Clay
Need for the Experiments--
It was hypothesized that the substitution of thallium for other
metallic cations may take place in the montmorillonitic clays, which
if true, could be a significant factor in minimizing thallium movement
in the environment. To check this hypothesis, a series of experiments
was designed in which a montmorillonitic clay (hectorite) was chosen to
determine the extent of preference of exchange of the thallous ion compared
to the potassium ion and to other ions such as copper and zinc.
Montmorillonite is the principal clay mineral of bentonite beds, which
originate from altered volcanic ash. Montmorillonite minerals are common
as alteration products of igneous and metamorphic rock minerals in an
alkaline environment with little leaching (e.g., arid climates). The
western U.S. Rocky Mountain region has an abundance of montmoriilonite
in its soils. There are different species in the montmoriilonite group
and they vary in the type and degree of isomorphous lattice substitution
rather than in structure. In this study, the montmoriilonite called
hectorite (hectorite #34 - API reference standard) was used. This
mineral is one in which the principal substitutions are octahedral and
has a general structural formula of:
01 Li.30%.67> CSV °10
92
-------
In the presence of water, the cations in the interlayer positions
may be easily exchanged with other cations when available in solution.
Isomorphous substitution results in charge deficiency, which may occur
in the octahedral or tetrahedral layer. The charge deficiencies can be
neutralized by exchangeable cations so that the mineral becomes electri-
cally neutral. Therefore, exchange may occur not only by cations in the
interlayer position, but in layers of the lattice as well.
Approach--
Ten- and one-gram samples of hectorite per liter distilled water
were prepared containing 1000, 100, and 10 micrograms per liter of
thallium (I), copper (II) and zinc (II). The pH of the solution of
hectorite and water was adjusted to 4 and approximately 8 with dilute
sulfuric acid prior to the addition of metals. The clay slurry was
continually agitated for 24 hours to achieve good contact between the
clay and metal ions in solution. After the contact period, clay was
removed by settling and centrifuging to obtain a clear liquid prior to
extraction and atomic absorption analysis.
The liquid, free of clay, was extracted with DDC (diethyldithio-
carbamate) to concentrate the metal ions. Thallium analysis was per-
formed using a heated graphite atomizer, whereas copper and zinc were
aspirated directly.
Blank samples without hectorite and hectorite solutions without
metals were prepared to assure no interferences or metal losses.
Results--
Three separate experiments were carried out using hectorite, potassium-
treated hectorite, thallium, copper, and zinc in various concentrations.
Ten grams of hectorite per liter of water with different concentrations
of thallium, copper, and zinc at two pH levels (4.0 and 8.2) revealed
more efficient takeup of metal ions in basic solution. (Refer to Table
32). At pH 8.2, the thallium concentration was reduced from 1000 micro-
grams per liter to 25 micrograms per liter. Copper and zinc were reduced
from 1000 micrograms per liter to less than 10 micrograms per liter.
Other concentrations of Tl, Cu, and Zn were reduced to below their
detectability limit.
In acidic solution (pH 4.0), metal reduction in solution was not as
pronounced as in basic solution. Initial 1,000-microgram levels of Tl,
Cu, and Zn were reduced to 900, 562, and 619 micrograms per liter, res-
pectively. Concentration of metals at 100 micrograms per liter also did
not reduce as dramatically as in basic solution but did adsorb in greater
proportion than the 1000-microgram-per-liter metal sample at the same pH
value.
An experiment was performed in which the concentration of clay was
changed from 10 grams of hectorite per liter to 1 gram of hectorite per
liter of solution at a pH of 8.1 (Table 33). Initial concentrations of
1000-micrograms-per-liter levels of Tl, Cu, and Zn were reduced to 115,
270, and 511 micrograms per liter, respectively. Other concentrations
93
-------
TABLE 32. EXCHANGE CAPACITY OF HECTORITE WITH
THALLIUM, COPPER, AND ZINC (10 g/liter HECTORITE)
pH
8.2
8.2
8.2
8.2
4.0
4.0
4.0
4.0
Initial (fjig/l)
Thallium
1000
700
10
0
1000
100
10
0
Copper
1000
100
10
0
1000
100
10
0
Zinc
1000
100
10
0
1000
100
10
0
Final (^g/l)
Thallium
25
<3
<1
<1
900
3
<1
<1
Copper
CIO
<10
CIO
<[10
562
10
cio
<10
Zinc
CIO
-------
Conclusions—
The experimental results show that thallium ions can be removed
effectively from solution by a montmorillonite clay. Greater removal of
thallium is achieved in slightly basic waters versus slightly acidic
waters. This may be due to the increased solubility of the metallic ion
in acidic media. Other metal ions—specifically, copper and zinc—also
follow the same trend. Clays, saturated with potassium ions, show only
slight differences to clay that had not been treated with potassium
ions.
The disappearance of thulium from less-ajid waters may be related
to reduction of unstable Tl (thallic) to Tl (thallous) ions and
subsequent ion-exchange with suspended clay. This mechanism is quite
efficient, and there is little biological uptake of thallium. However,
organic complexes such as those formed with MIBK are known on analysis
and may persist through the food chain despite their toxicity. The
general path of thallium from water through biota is shown in Figure 36.
A good example is the South Fork of the Coeur d'Alene River, mentioned
above (Table 9).
The metal fractionation between water and sediment can be understood
in terms of the solubility of the available salts of the metal ions
found (Table 35). Tl, like Pb, accumulates from acid water in neutral
or alkaline sediments, especially fine muds.
TABLE 35. SOLUBILITIES OF SELECTED HEAVY-METAL SALTS IN WATER
Heavy Metal
(Ion)
Thallium"1"1"1"
Thallium"1"
Cadmium++
Lead++
Copper"1"1"
Copper"1"
Zinc++
Solubility of Salt in Neutral (pH 7.0) water at 20°C (68° F)* (ppm [mg/J ] )
Carbonate
Does not exist
42,000 (15.5°C)
Insoluble
1.1
(Basic) Insoluble
Insoluble
10(15°C)
Chloride
862.000 (17°C)
2.900 (15.5°C)
1,400,000
9,900
707,000 (0°C)
62
4,320,000 (25°C)
Sulfate
Decomposes
48,700
760.000 (0°C)
42.5 (25°C)
143,000 (0°C)
Decomposes
965,000
Sulfide
Insoluble
220
1.3 (18°C)
0.86 (18°C)
0.33 (18°C)
5.0 (18°C)
6.9 (18°C)
"Unless temperature is otherwise indicated. 0°C = 32°F; 15°C = 59°F; 15.5°C = 60°F; 17°C = 63°F-
:64°F;250C = 77°F.
Data based on information given in Weast, Robert C. (ed.), Handbook of Chemistry and Physics, 53rd
Edition (1972-1973), The Chemical Rubber Company (Cleveland, Ohio) and Lange, Norbert A. (ed.).
Handbook of Chemistry, Revised Tenth Edition (1967), McGraw-Hill Book Company (New York).
95
-------
HIGH
TOXICITY DUE TO THALLIUM
MODERATE
LOW
THALLIUM-RICH
MONTMORILLONITE
CLAY
ACIDIC EFFLUENT
WITH HIGH
CONCENTRATION
OFTHALLIC
(Tl+++) IONS
REDUCING
ENVIRON-
MENT
(E.G., ONE
RICH IN
SULFIDES)
bNVIRON-
I MENT —
|^ (E.G., ONE —
ACIDIC EFFLUENT
WITH MODERATE
CONCENTRATION
OFTHALLOUS
(Tl+) IONS*
MONTMORILLONITE
CLAY
(E.G., HECTORITE)
NEUTRAL OR
NEAR-NEUTRAL
EFFLUENT
CONTAINING "
LITTLE
THALLIUM
INITIAL
DISCHARGE
DISCHARGE
AFTER REACTION
WITH BYPRODUCTS
OF MINING/MILLING
ION EXCHANGE WITH
EVER-PRESENT CLAY
CAUSES TI+ IN SOLUTION
TO BE REPLACED BY K*
FROM CLAY. ALKALINITY
OF THE CLAY NEUTRALIZES
THE ACIDIC EFFLUENT
TO
BIOTA
DISCHARGE
ENCOUNTERED
BY MOST
BIOTA
•THALLOUS FORM IS LESS SOLUBLE THAN THALLIC FORM.
Figure 36. Generalized flow of solubilized thallium in the environment.
-------
Biological Concentration of Thallium
The relations of the more toxic metal (Tl, Cd, Pb) concentrations in
each trophic level of the biota to its sediment and water concentrations
are plotted in Figures 37 through 40. Data from all sampled sites
are included. The concentration of metal in the biota was found to be
more closely related to the concentration in its bottom sediment than to
its concentration in water except for a few floating algal slimes surviving
above lead-rich mud, particularly at East Helena. Toxic water discharges
can occur sporadically, leaving a record in the sediment. Generally,
benthic organisms were found to accumulate more than fish.
In the following discussion, prior observations (9) for each metal
are summarized for comparison with the data collected in this study.
The average concentration of cadmium found in rivers by Hager was 0.24
ppb, but only 0.11 ppb in seawater. In rivers, the average concentration
of lead is now 4.2 ppb, and in surface seawater, 0.3 ppb, primarily due
to leaded gasoline. Deeper seawater contains only 0.03 ppb. Toxicity
is cumulative and varies from 100 ppb for oysters to 4 ppm for fish.
The average concentration of copper in rivers is 10 ppb, about as much
as in nearshore seawater. Copper is toxic to algae at approximately 25
ppb, although fish can tolerate 30 ppm. The average concentration of
zinc is 10 ppb in rivers and up to 15 to 20 ppb in seawater. Aquatic
toxicity of zinc requires 5 to 10 ppm. Marine plankton can concentrate
heavy metals at factors which can vary from 910 for cadmium, 4100 for
lead, and 20,000 for zinc (9).
The higher trophic levels sampled in this study, especially larvae
and fish, were found to have lower concentrations of toxic metals than
lower trophic levels (algae). We believe this is due to a combination
of factors including feeding on uncontaminated detritus, mobility and
biochemical rejection mechanisms.
This agrees with Merlini et_ al^. (10), who showed copper concentra-
tions of 2.2 ppm in Lake Maggiore algae (MyriophyIlium), but only 0.9
ppm in small fish (Alburius) and 0.5 ppm in large fish (Coregorus.
Scardinius ). Zinc decreased from 20 ppm in algae to 4 to 8 ppm in
large fish.
Unlike methyl mercury, thallium and other toxic heavy metals showed
little increase in concentration up the food chain. Sulfide precipitation
removes these readily reduced cations, concentrating them in black
organic oozes.
The graphs (Figures 37 through 40) summarize the research in showing
that there was little bioconcentration from water.
97
-------
100,000 r
10,000 -
1,000 -
Q
LU
V)
cc
g
00
z
I
o
cc
I-
z
111
o
o
o
LU
5
100 -
0.0001
• SEDIMENT
+ ALGAE
X LARVAE
X FISH
O THALLIUM
O CADMIUM
(NONE) LEAD
0.01 -
0.001 -
0.0001 0.001 0.01 0.1 1 10 100 1,000 10,000 100,000
METAL CONCENTRATION (ppm) IN WATER
Figure 37. Concentration of the toxic metals thallium, cadmium, and lead in biota,
sediment, and water.
98
-------
100,000
o
0
8
2
o
5 1,000
z
o
<
DC
Ul
o
§
o
2
UJ
_
8
3
_
5
0
2
0.01
+
X
*
D
0
(NONE)
ALGAE
LARVAE
FISH
THALLIUM
CADMIUM
LEAD
x>
>P
0.1 1 10 100 1,000 10.000 100,000
METAL CONCENTRATION (ppm) IN SEDIMENT
Figure 38. Concentration of the toxic metals thallium,
cadmium, and lead in biota and sediment.
99
-------
<
10,000 i-
1,000 -
100 -
z
o
kl m
3 r-
VH1N30NOO 1\
! 0.1
0.01
<^
CB ®/
-*/
/ , 1 , 1 . 1
w
»
X
*
a
o
(NONE)
1
LARVAE
FISH
THALLIUM
CADMIUM
LEAD
1 , 1
0.01 0.1 1 10 100 1,000 10,000
METAL CONCENTRATION (ppm) IN ALGAE
Figure 39. Concentration of the toxic metals thallium,
cadmium, and lead in fauna and algae.
100
-------
I
CO
a
cc
UJ
LU
10,000 r-
1,000
100
10
0.1
0.01
D THALLIUM
O CADMIUM
(NONE) LEAD
0.01 0.1 1 10 100 1,000 10.000
METAL CONCENTRATION (ppm) IN LARVAE
Figure 40. Concentration of the toxic metals thallium,
cadmium, and lead in fish and larvae.
101
-------
REFERENCES
1. Pinta, M. Detection and Determination of Trace Elements. Ann Arbor
Science Publishers, 1971.
2. Hammer, D.I., £t al_. Trace-Metal Concentrations in Human Hair. In:
Helena Valley, Montana, Area Environmental Pollution Study. U.S.
Environmental Protection Agency, Office of Air Programs, Research
Triangle Park, N.C., 1972. pp. 125-134.
3. Mink, L.L., R.E. Williams, and A.T. Wallace. Effect of Industrial and
Domestic Effluents on the Water Quality of the Coeur d'Alene River
Basin. Idaho Bureau of Mines and Geology, Pamphlet 149, Moscow, 1971.
4. Sargent, J.D. Thallium. In: Mineral Facts and Problems. U.S..Bureau
of Mines Bulletin 556, 1952.
5. Gmelins. Handbuch der Chemie (Handbook of Chemistry): Anorganischen
Chemie (Inorganic Chemistry), System 38. Section I: History, Occurrence
and the Element, 1939 (revised 1962); Section II: Alloys and Compounds
up to Thallium and Iodine, 1940 (revised 1962); and Section III:
Concluding Compounds and Natural Isotopes, 1940 (revised 1962). Verlag
Chemie GmbH, Leipzig (Germany).
6. Natusch, D.F.S., J.R. Wallace, and C.A. Evans. Toxic Trace Elements:
Preferential Concentration in Respirable Particles. In: Science, 183,
1974. pp. 202-204.
7. Brown, A.S. Mineralization in British Columbia and the Copper and
Molybdenum Deposits. In: Canadian Inst. Mining Trans., 72, 1969.
pp. 1-15.
8. Rex, R.W. and E.D. Goldberg. Insolubles. In: The Sea, Vol. 1, Physical
Oceanography, M.N. Hill, ed. Interscience Publishers, 1962.
9. Hager, S.W. Trace Metals in Oceanography of Nearshore Coastal Waters
of the Northwest Pacific Relating to Possible Pollution. EPA WQO Grant
16070 EOK, 1971.
10. Merlini, M., C. Bigliocca, A. Berg, and G. Pozzi. Trends in Concentra-
tion of Heavy Metals in Organisms of a Mesotrophic Lake as Determined by
Activation Analysis. In: Nuclear Techniques in Environmental Pollution.
International Atomic Energy Agency, Vienna, 1971.
102
-------
11. Feigl, F. Spot Tests. Vol. 1, Elsevier Publishing Co., 1954.
12. Stumm, W. and J.J. Morgan. Aquatic Chemistry. Wiley-Interscience
New York, 1970.
13. Rolf, G.L., J.W. Melin, and B.B. Ewing. Lead Pollution in a Watershed
Ecosystem. Paper No. 931, 23rd AIBS Meeting at the University of
Minnesota, 1972.
103
-------
APPENDIX A
STUDY OF ALTERNATIVE SOLID-SAMPLE-PREPARATION METHODS
Sediment samples must be solubilized before analysis by atomic-
absorption spectrophotometry, the analytical method used in this project.
Sediments can be digested by utilizing a variety of acids (such as
perchloric, hydrochloric, phosphoric, and sulfuric) but care must be taken
not to volatilize the elements of interest (including thallium, lead,
cadmium, zinc, and copper). Table A-l gives data on volatilization losses
of various heavy metals using the aforementioned acids.
Five methods for achieving the solution of metals from representative
sediment and sludge samples were originally investigated. It was expected
that an extraction technique which would provide reliable analysis of both
of these.sample types would also be applicable to those soils which would
be collected throughout the program. The five sample-preparation procedures
studied are:
(1) Pressure digestion--5 grams of sample were digested with 1.5
grams of perchloric acid (HC10 ) +3.5 grams of nitric acid (HNO_)
in a closed bottle; stored overnight; and then cooled, diluted,
and analyzed.
(2) Room-temperature extraction by mixed acids—5 grams of sample
were extracted with 10 ml of nitric acid and 15 ml of hydrochloric
acid (HC1) at room temperature, with a contact time of approxi-
mately 72 hours with occasional mixing.
Boiling-acid extraction with resolubilization—0.2 gram of
sample, 15 ml of hydrochloric acid, and 10 ml of nitric acid
were heated and evaporated to dryness. The soluble residue was
dissolved in 5 ml of hot hydrochloric acid and then diluted with
water.
(4) Boiling-acid extraction--0.2 gram of sample, 15 ml of hydrochloric
acid, and 5 ml of nitric acid were boiled 10 to 15 minutes,
cooled, and diluted with water.
(5) Room-temperature extraction by nitric acid--5 grams of sample
were extracted with 10 ml of nitric acid at room temperature
for approximately 72 hours with occasional mixing.
104
-------
TABLE A-1. SAMPLE DIGESTION WITH VARIOUS ACIDS
Volatilization of some metal compounds during digestion with perchloric, hydrochloric, sulfuric and
phosphoric acids at 200-220°C (392-428°F).
Procedure 1. (HCIO4-HCI): 20 to 100 mg (0.3 to 1.5 grains) of the chloride are treated with 15 ml of 60%
HCIO4;the temperature is raised to 200°C (392°F); 15 ml of HCI are slowly added (during 15 minutes)
while the temperature is kept at 200-220°C (392-428° F).
Procedure 2. (HCIO4-H3PO4-HCI): same as procedure 1 except that 15 ml of HCIO4, 5 ml of 85% H3PO4,
and HCI are used.
Procedure 3. (H2SO4-HCI): same as Procedure 1, HCIO4 being replaced by H2SO4 (d = 1.84).
The following elements are not volatilized by any of these procedures: Ag, alkali metals (Na, K, Rb, Cs). Al Ba,
Be, Ca, Cd, Co, Cu, Fe, Ga, Hf, In. Ir, Mg, Ni, Pb, Pd, Pt, rare earths, Rh, Si, Ta, Th. Ti, U, W, Zn, and Zr.
Element
As
-------
One or two samples of each soil type were extracted by each technique
to provide a measure of the reproducibility of the analytical results.
Results of the analysis are summarized in Table A-2, where an average
for each of the two soil types and for each of the five sample-preparation
procedures is also presented. The number of samples analyzed and the
number used in determining the average values differ in several cases
because those samples which were known to have significant experimental
error were not included in the calculations of the averages or in deter-
minations of the root-mean-square (rms) variations.
After evaluating the results of the five proposed preparation
techniques, a general method for solid-sample preparation was developed
which most closely allied those two methods which seemed to yield the
highest concentration of metals (i.e., Procedure (2) and Procedure (5)
above). The final sediment-preparation method, discussed in the text of
Section 5 under Sample Preparation, consisted of a mixed-acid digestion
at room temperature for 24 hours.
As discussed in Section 5, sulfide precipitation was not utilized as
a method for sample preparation because of its failure to yield detectable
thallium concentrations below 0.5 ppm. Apparently, there are interferences
remaining in solution after precipitation which completely quench the
thallium signal when the heated graphite atomizer is used for analysis.
Table A-3 gives the details of the sulfide preparation procedure. Although
this method remains a viable choice for preparation of those samples with
high metal concentrations, it was not applicable for this study because
of the high level of sensitivity for thallium which was desired.
The organic-complexation method for thallium (Section 5) resulted
from an intense effort throughout the program to develop a sample-
preparation procedure which would consistently yield reliable thallium
levels in a variety of sample types—especially, at low concentrations.
The organic-complexation method fulfilled this requirement. Analytical
results of tests run on selected water and sediment samples are shown in
Table 4 (Section 5). Of particular interest in this table is the high
rate of recovery of the thallium spike—notably, in the water samples.
The rate of spike recovery in the sediment samples is somewhat less, as
can be seen from the table. This may be due to the large amounts of
other metals present that also complex with the DDC and reduce the DDC-to-
thallium ratio, thereby leaving the thallium with little DDC available
for complexation. The reduced signal may also be due to the large amounts
of other extracted metals interfering with thallium.
As previously mentioned, this method yielded the most consistent
results and was, therefore, utilized throughout the program for analyzing
samples for the presence of thallium.
106
-------
TABLE A-2. ANALYTIC RESULTS (in ppm) OF SAMPLE-PREPARATION TRIALS
Cd
1
Average (Mean)
Procedure 1 (2 samples)
Procedure 2 (2 samples)
Procedure 3 (2 samples)
Procedure 4 (2 samples)
Procedure 5 (2 samples)
No. of Samples
No. of Samples in Average
No. of Measurements in Average
Rms Deviation of Measurements
Rms Deviations of Sample Averages
Cu
— ^s^_,
Pb
Tl
Zn
SOIL TYPE A
184
180
200
163
163
200
10
7
7
18.4
18.4
22,000
23,000
21,000
22,000
23,000
20,000
10
7
14
1,900
1,500
SOIL TYPE B
Average (Mean)
Procedure 1 (2 samples)
Procedure 2 (2 samples)
Procedure 3 (1 sample)
Procedure 4 (1 sample)
Procedure 5 (2 samples)
No. of Samples
No. of Samples in Average
No. of Measurements in Average
Rms Deviation of Measurements
Rms Deviation of Sample Averages
65
67
60
67
69
65
8
8
8
4.3
4.3
50,000
50,000
51,000
48,000
53,000
48,000
8
8
15
3,800
2,500
2,897
1,170
2,933
3,016
3,140
2,580
10
7
12
256
219
1,400
1,300
1,480
1,450
1,390
1,410
8
8
16
102
74
3.1
1.7
3.6
ND
ND
2.8
6
4
5
0.74
0.75
7.0
8.2
5.2
ND
ND
7.4
6
6
9
1.8
1.4
1,720
2,080
1,900
1 650
1 608
1,800
10
7
10
130
125
416
405
410
479
405
380
g
g
10
39
32
ND = Not determinable (<0.001 ppm)
107
-------
TABLE A-3. SULFIDE PRECIPITATION PROCEDURE
1. Exactly 10.0 ml of sample is acidified with 1 ml of HNOg and 1 ml of HCI.
2. The pH is then adjusted to 12 with 2.5 M sodium hydroxide.
3. 0.5 g of Na2S, dissolved in 1 ml of water, is added.
4. When no observable precipitate forms, 1 ml of 1000 ppm Zn and 1 ml of 1000 ppm Pb are added.
5. The resulting solution is filtered through a millipore HWAG 0.45-micrometer filter.
6. The precipitate is redissolved in 5 ml of concentrated nitric acid and made up to 10 ml in a volumetric
flask with distilled water.
7. Sample is then ready for subsequent analysis.
108
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing/
1 REPORT NO. 2-
EPA-600/2-77-171
4. TITLE AND SUBTITLE
HEAVY METAL POLLUTION FROM SPILLAGE AT ORE SMELTERS
AND MILLS
7. AUTHOR(S)
Staff, Environmental Systems Department
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Calspan Corporation
P.O. Box 235
Buffalo, N.Y. 14221
12. SPONSORING AGENCY NAME AND ADDRESS
Industrial Environmental Research Laboratory-Cin. , OH
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
3. RECIPIENT'S ACCESSION>NO.
5. REPORT DATE
August 1977 issuing date
6. PERFORMING ORGANIZATION CODE
8, PERFORMING ORGANIZATION REPORT NO.
ND-5189-M-1 (Rev.)
10. PROGRAM ELEMENT NO.
1BB610 03-01-06A-03
11. CONTRACT/GRANT NO.
68-01-0726
13. TYPE OF REPORT AND PERIOD COVERED
Final 6/72 - 10/74
14. SPONSORING AGENCY CODE
EPA/600/12
15. SUPPLEMENTARY NOTES
EPA Project Officer: Dr. John Brugger
16. ABSTRACT
Smelter and mill wastewater outfalls, receiving water, biota, slag heaps, tailings
ponds, streams, and coal-burning fly ash dumps were sampled as part of this effort to
determine the effect of effluent or residual spillage on aquatic systems. Since con-
centration of heavy metals in sediment was found to be greater at any given time than
that dissolved in water, flood water erosion of particulate matter presents a hazard.
Up to 17% lead, 0.1% cadmium and 5 ppm thallium were found in sediments of streams
used for irrigation and drinking water below copper and zinc extractive industries in
high runoff regions.
Groundwater infiltration in the Northwest and Ozarks provides mine drainage water
which is used as process water in mills. This water transports potentially toxic
wastes into naturally erosive bottom sediments thereby contaminating the food chain.
Heavy metal concentrations in water and biota tend to be higher in the fall at low
water following benthic accumulations during the growing season.
Prevention techniques recommended here include separation of waste streams, pro-
tection of tailings dams from flood erosion, and recycle of mill and smelter waste-
water. Excess water discharged can be treated with lime at elevated pH to precipitate
heavy metals and to prevent leaching of sediment already in streams.
The overall sensitivity achieved for thallium by a method developed and reported
here is 0.1 ppb in water. The detection limit for thallium in biota was determined to
be approximately 10 ppb and 80 to 90 ppb in sediment. This was due primarily to the
presence of high concentrations of chloride and other interfering ions in the collec-
ted samples.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
Thallium, Beneficiation, Hazardous
Materials, Water Quality, Surface Waters,
Cadmium, Lead, Copper, Zinc, Indium,
Toxicity
Ore Milling
Metal Smelting
Heavy Metals
Bioconcentration
Toxic Metals
COSATI Field/Group
08G
08H
081
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
UNCLASSIFIED
21. NO. OF PAGES
123
20. SECURITY CLASS (Thispage)
UNCLASSIFIED
22. PRICE
EPA Form 2220-1 (9-73)
6U.S.GOVERNMENTPRINTING OFFICE: 1977-241-037:80
109
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