Negative PH, Efflorescent Mineralogy, and Consequences For Environmental Restoration at The Iron Mountain Superfund Site, California
Negative PH, Efflorescent Mineralogy, and Consequences For Environmental Restoration at The Iron Mountain Superfund Site, California
Negative PH, Efflorescent Mineralogy, and Consequences For Environmental Restoration at The Iron Mountain Superfund Site, California
USA
Vol. 96, pp. 3455–3462, March 1999
Colloquium Paper
This paper was presented at the National Academy of Sciences colloquium ‘‘Geology, Mineralogy, and Human Welfare,’’
held November 8–9, 1998 at the Arnold and Mabel Beckman Center in Irvine, CA.
ABSTRACT The Richmond Mine of the Iron Mountain activities in the U.S. are detailed. Government records indicate
copper deposit contains some of the most acid mine waters that many millions, perhaps billions, of fish have been killed
ever reported. Values of pH have been measured as low as from mining activities in the U.S. during this century (2).
23.6, combined metal concentrations as high as 200 gyliter, Incidents of arsenic poisoning in residents of Thailand result
and sulfate concentrations as high as 760 gyliter. Copious from arsenic contamination of the shallow groundwaters be-
quantities of soluble metal sulfate salts such as melanterite, cause of weathering of mine wastes (3). A mine flood disaster
chalcanthite, coquimbite, rhomboclase, voltaite, copiapite, in Spain occurred in April 1998 in which about 6 million m3 of
and halotrichite have been identified, and some of these are acid water and sulfide tailings escaped from a breached
forming from negative-pH mine waters. Geochemical calcu- impoundment and covered about 6,500 acres of farmland and
lations show that, under a mine-plugging remediation sce- river banks along a 70-km reach of the Guadiamar River with
nario, these salts would dissolve and the resultant 600,000-m3 fine-grained sulfides (details at www.csic.es). Numerous rivers,
mine pool would have a pH of 1 or less and contain several estuaries, and reservoirs throughout the world have been used
grams of dissolved metals per liter, much like the current as dumping grounds for the large volumes of waste produced
portal eff luent water. In the absence of plugging or other during mineral extraction and processing. Mineral processing,
at-source control, current weathering rates indicate that the
in addition to fossil fuel and metal utilization, has increased the
portal eff luent will continue for approximately 3,000 years.
concentration of selected metals and nonmetals in the atmo-
Other remedial actions have greatly reduced metal loads into
sphere. The emissions of As, Cd, Cu, Pb, Sb, and Zn from
downstream drainages and the Sacramento River, primarily
by capturing the major acidic discharges and routing them to anthropogenic sources are all greater than emissions from
a lime neutralization plant. Incorporation of geochemical natural sources, sometimes several times higher (4, 5).
modeling and mineralogical expertise into the decision- Acid mine drainage is produced primarily by the oxidation
making process for remediation can save time, save money, of the common iron disulfide mineral pyrite. Pyrite oxidation
and reduce the likelihood of deleterious consequences. is a complex process that proceeds rapidly when this mineral
and other sulfides are exposed to air. A simplified represen-
tation of this chemical process is given by the reaction of pyrite
Mining and Water Quality with air and water,
21 22 1
Mining of metallic sulfide ore deposits (primarily for Ag, Au, FeS2(s) 1 7y2O2(g) 1 H2O(1) 3 Fe(aq) 1 2SO4(aq) 1 2H(aq)
Cu, Pb, and Zn) produces acid mine waters with high concen- [1]
trations of metals that have harmful consequences for aquatic
in which the product is a solution of ferrous sulfate and sulfuric
life and the environment. Deaths of fish, rodents, livestock, and
acid. The dissolved ferrous iron continues to oxidize and
crops have resulted from mining activities and have been noted
hydrolyze when the mine water is no longer in contact with
since the days of the Greek and Roman civilizations. Mining
and mineral processing have always created health risks for pyrite surfaces,
miners and other workers. In addition, mining wastes have 21
Fe(aq) 1
1 1y4O2(g) 1 5y2H2O(l) 3 Fe(OH)3(S) 1 2H(aq) [2]
often threatened the health of nearby residents by exposure to
emissions of sulfur dioxide and oxides of As, Cd, Pb, and Zn producing additional acidity. Iron- and sulfur-oxidizing bac-
from smelter stacks and flues, metal-contaminated soils, and teria, especially Thiobacillus ferrooxidans, are known to cata-
waters and aquatic life with high concentrations of metals. As lyze these reactions at low pH, increasing reaction rates by
with most forms of resource extraction, human health risks several orders of magnitude (6). These processes occur natu-
accompany mineral exploitation. rally and, indeed, natural acidic drainage is well known from
In 1985, the U.S. Environmental Protection Agency (EPA)
many locations (7). Mining has the overall effect of dramati-
estimated that 50 billion tons (45 3 1012 kg; 1 ton 5 907 kg)
cally increasing the oxidation rates by providing greater ac-
of mining and mineral processing wastes had been generated
cessibility of air through mine workings, waste rock, and
in the United States and about 1 billion tons would continue
tailings, by creating greater surface area exposure through
to be generated each year (1). More recently, the EPA has
described 66 ‘‘damage cases’’ at their web site (www.epa.gov, blasting, grinding, and crushing, and by concentrating sulfides
search for Mining and Mineral Processing Wastes, accessed in tailings. The overall rates of sulfide oxidation and metal
Sept. 9, 1998) in which environmental injuries from mining
Abbreviation: EPA, Environmental Protection Agency.
†To whom reprint requests should be addressed. e-mail: dkn@
PNAS is available online at www.pnas.org. usgs.gov.
3455
3456 Colloquium Paper: Nordstrom and Alpers Proc. Natl. Acad. Sci. USA 96 (1999)
release in areas affected by mining are estimated to be orders Furthermore, the town of Redding (with approximately
of magnitude faster than natural rates. 100,000 residents) receives its drinking water from the Sacra-
Another process, sometimes overlooked, plays an important mento River, downstream from the Iron Mountain site. Large,
role in the environmental consequences of mining: the for- metal-rich sediment deposits containing toxic porewaters have
mation of soluble, efflorescent salts. Acid ferrous sulfate built up in Keswick Reservoir, where the Spring Creek drain-
solutions often become so enriched through rapid pyrite age from Iron Mountain empties into the Sacramento River.
oxidation and evaporation that soluble salts form. These often A brief history of mining, water management, and environ-
appear as white, blue-green, yellow to orange or red efflores- mental action at Iron Mountain is outlined in Table 1.
cent coatings on surfaces of waste rock, tailings, and in The mineral deposits are primarily massive sulfide lenses as
underground or open-pit mines. Acidity and metals, formerly much as 60 m thick containing up to 95% pyrite, variable
contained in the acid mine water, are stored in the salts, which amounts of chalcopyrite and sphalerite, and averaging about
can quickly be dissolved by a rising groundwater table or be 1% Cu and about 2% Zn. Some disseminated sulfides occur
dissolved when exposed to rain and flowing surface waters, and along the south side of the mountain. The deposits at Iron
then infiltrate to groundwaters. The Iron Mountain Mine Mountain and elsewhere in the West Shasta mining district are
Superfund site is an extreme example of how the formation of Devonian in age and have been classified as Kuroko type,
soluble efflorescent minerals can make certain remediation having been formed in an island arc setting in a marine
alternatives much more risky and potentially disastrous than environment (9). The country rock is the Balaklala Rhyolite,
might otherwise be imagined. a keratophyric rhyolite that has undergone regional metamor-
phism during episodes of accretion of oceanic crust to the
Iron Mountain continent. The brittle, fractured nature of the altered volcanic
bedrock gives rise to a hydrologic conditions dominated by
Iron Mountain is located in Shasta County, California, ap- fracture-flow at Iron Mountain. The mineral composition of
proximately 14 km northwest of the town of Redding (Fig. 1), the rhyolite is albite, sericite, quartz, kaolinite, epidote, chlo-
in the southern part of the Klamath Mountains. ‘‘Iron Moun- rite, and minor calcite; consequently it has little buffering
tain Mine’’ is really a group of mines within Iron Mountain that capacity. Kinkel and others (10), Reed (11), and South and
include Old Mine, No. 8 Mine, Confidence-Complex, Brick Taylor (12) have documented the chemical and isotopic com-
Flat Open Pit Mine, Mattie Mine, Richmond and Richmond positions of ore, gangue, and country-rock minerals in the
Extension Mines, and Hornet Mine. Ag, Au, Cu, Fe, Zn, and West Shasta mining district. Weathering of massive sulfide
pyrite (for sulfuric acid production) were recovered at various deposits at and near the surface has given rise to large gossan
times beginning in the early 1860s and ended with the termi- outcrops, enriched in Ag and Au. The 10 million tons of gossan
nation of open-pit mining in 1962. Iron Mountain was once the in place prior to mining is the residue from at least 15 million
largest producer of Cu in the state of California, and now it tons of massive sulfide that weathered naturally. A total of 7.5
produces some of the most acidic waters in the world. Prior to
Table 1. Brief chronology of Iron Mountain mining and
the late 1980s when major remediation efforts began, approx- envrionmental activities
imately 2,500 tons of pyrite weathered every year from one
mine alone (the Richmond Mine) and water containing about Year Activity
300 tons per year of dissolved Cd, Cu, and Zn drained from the 1860s Discovery of massive gossan outcropping
site into the Sacramento River. During periods of high runoff, 1879 Silver discovered in gossan and mining begins
sudden surges of acid mine waters into the Sacramento River 1897 Mountain Copper Co. acquires property and under-
have caused massive fish kills, which state and federal agencies ground mining begins
have investigated since 1939. More than 20 fish-kill events have 1902 U.S. Forest Reserve sues company for vegetation
occurred in Sacramento River receiving waters since 1963, damage from smelting activities
with at least 47,000 trout killed during a single week in 1967 (8). 1907 Smelting ends and ore is transported to Martinez,
CA, for processing
1928 California Fish and Game Commission files
complaint regarding tailings dam
1939 State initiates water quality and fish toxicity studies
1943 Shasta Dam, upstream from Iron Mountain
outflows, is completed
1950 Keswick Dam, downstream from Iron Mountain
outflows, is completed
1955–1962 Open-pit mining of pyrite at Brick Flat for sulfuric
acid production
1963 Spring Creek Debris Dam is completed, regulating
outflow of acid mine waters to the Sacramento
River
1967 Stauffer Chemical Co. acquires property
1976 Iron Mountain Mines, Inc., acquires property
1976–1982 State of California fines company for unacceptable
releases of metals
1983 Iron Mountain listed on National Priorities List
(NPL) for EPA Superfund, ranking as the
third-largest polluter in the State of California
1986–1998 Four Records of Decision by EPA have instituted
several remedial activities that include partial
capping, surface-water diversions, tailings
removal, and lime neutralization of the most
acidic, metal-rich flows, reducing copper and zinc
FIG. 1. Location of Iron Mountain Mine, California (adapted from
loads by 80–90%
ref. 15).
Colloquium Paper: Nordstrom and Alpers Proc. Natl. Acad. Sci. USA 96 (1999) 3457
million tons of sulfide ore was mined at Iron Mountain, and Table 2. Richmond Mine portal effluent
remaining reserves are estimated at approximately 15 million characteristics, 1983–1991
tons (13), so the overall size was at least 37.5 million tons prior Mean Range
to weathering. Preliminary paleomagnetic data on iron oxides
in the gossan show portions with reversed polarity, indicating Discharge, literys 4.4 0.5–50
the gossan began forming at least 780,000 years ago. Secondary pH 0.8 0.02–1.5
enrichment in the upper zones of the massive sulfides resulted Zinc, mgyliter 1,600 700–2,600
in high concentrations of Cu (5–10%) and Ag (about 1 ozyton). Copper, mgyliter 250 120–650
This enrichment took place at or near the water table during Data are from ref. 19.
gossan formation.
Three main massive sulfide ore bodies, the Brick Flat, the compilation and details of Richmond portal effluent compo-
Richmond, and the Hornet, include most of the oxidizing sition and discharge can be found in Alpers et al. (19).
sulfides causing the current water-quality problems. These ore The variability in the Richmond effluent with time can be
bodies are thought to be parts of a single massive sulfide body seen quite clearly for the 1986–1987 monitoring period. Fig. 3
about 0.8 km long, over 60 m wide, and over 60 m thick that covers the time period of late November 1986 to April 1987
was offset by two normal faults (Fig. 2). All three of these and shows the rainfall (at Shasta Dam), and the consequent
bodies have been mined, and the consequences include large changes in Richmond Mine discharge and copper and zinc
changes in the hydrogeology, resulting in highly contaminated concentrations. One explanation for the large increase in
waters from tunnels, tailings, and waste rock piles. copper concentrations is the dissolution of underground sol-
uble salts from the flushing effect of meteoric recharge (see
Acid Eff luent from the Richmond Mine below). An observed increase in temperature with increased
discharge may be the result of the dilution of concentrated
Conditions at Iron Mountain are nearly optimal for the sulfuric acid, the dissolution of soluble salts, and increased
production of acid mine waters, and this mine drainage is some pyrite oxidation.
of the most acidic and metal-rich reported anywhere in the One of the obvious options for remediation of the Richmond
world (14, 15). In the Richmond Mine, about 8 million tons of Mine was to plug it. Many mines have been plugged, but the
massive sulfide remain (13). At current weathering rates it consequences have not been consistently favorable. The EPA
would take about 3,200 years for the pyrite in the Richmond wanted to know what the consequences of plugging the
ore body to fully oxidize. The massive sulfide deposit is about Richmond Mine might be; for example, what would the
95% pyrite and is excavated by tunnels, shafts, raises, and composition of the resultant mine pool be? There was, how-
stopes which allow rapid transport of oxygen by air advection. ever, no basis on which to speculate without some idea of the
The sulfides are at or above the water table so that moisture underground conditions. Hence, one of the activities of the
and oxygen have ready access. Airflow is driven by the high Second Remedial Investigation Phase (1986–1992) under the
heat output from pyrite oxidation. About 1,500 kJ of heat is Superfund Program was an underground survey of the Rich-
released per mole (120 g) of pyrite. Air enters the main tunnel, mond tunnel and part of the mine workings. Prior to under-
heats up in the mine, then travels up through raises and shafts ground renovations in 1989–1990, the last underground tour,
to the surface. The average flux of acid mine drainage from the to the best of our knowledge, was in 1955 (Don White, U.S.
Richmond portal indicates that about 2,400 mol of pyrite is Geological Survey, personal communication, 1989). The last
oxidized every hour, producing about 1 kW of power or almost mining had occurred in the late 1940s. Other than an occa-
9,000 kW per year. Water temperatures as high as 47°C have sional inspection by a company employee, there had been no
been measured underground, and the amorphous silica geo- recorded observation of the underground workings for 35–40
thermometer (16, 17) would suggest temperatures of at least years. After underground renovations, entry was safe, and on
50°C in the subsurface. In the early days of mining at Iron September 10–12, 1990, water and mineral samples were
Mountain, fires were frequent during underground excavation,
and temperatures of 430oF (221°C) were recorded at the ore
surface (18).
A considerable amount of historical data exist for effluent
composition and discharge from the Richmond Mine because
it is the largest single source of dissolved metals (both in terms
of concentration and in terms of flux) in the Iron Mountain
district. The Richmond ore body was discovered about 1915
but it was not mined on a large scale until the late 1930s and
the war years (1940–1945). Regular monitoring of the Rich-
mond Mine effluent by the California Regional Water Quality
Control Board in cooperation with the EPA began in 1983. A
summary of the data for discharge, pH, and Cu and Zn
concentrations for 1983–1991 is shown in Table 2. Further
collected. They revealed extremely acidic seeps with pH values conditions. Several Orion Ross glass membrane electrodes and
as low as 23.6 and total dissolved solids concentration of more a Sargent–Welch glass membrane electrode all performed well
than 900 gyliter. and could be calibrated up to a sulfuric acid concentration of
The chemical compositions of five of the most acidic waters about 8 molal. Another difficulty facing the definition of pH
found underground in the Richmond Mine during 1990–1991 below 0.0 is scaling of individual ion activity coefficients. There
are shown in Table 3. These concentrations are the highest ever is no generally accepted procedure for defining individual ion
recorded for As, Cd, Fe, and SO4 and nearly the highest for Cu activity coefficients without some arbitrary assumptions. Two
and Zn in groundwater. The high subsurface temperatures common methods with the Pitzer approach include ‘‘unscaled’’
have induced considerable evaporation, which, in addition to Pitzer equations, and ‘‘MacInnes scaled,’’ using the MacInnes
pyrite oxidation, has caused the high concentrations of dis- assumption (24). The MacInnes assumption is simpler, more
solved metals and sulfate. flexible for a wide range of complex chemical compositions,
The reporting of negative pH values has been controversial, and is more consistent with conventional speciation models
and for several good reasons. The conventional definition of applied to natural waters (24). It could be argued that the
MacInnes assumption becomes less defensible at high concen-
pH based on the former National Bureau of Standards criteria
trations where the unscaled approach should be more appro-
and defined buffer systems limits the range of definable and
priate, but there is no obvious justification for using one
measurable pH values to that of 1 to 13. Outside this range, the approach over the other and the choice remains arbitrary. In
concept and measurement of pH are difficult at best. Further- the present investigations, the MacInnes scaling was used
more, a new definition of pH must be used that is consistent primarily because geochemists who have applied the Pitzer
with the conventional definition, different buffers must be method to the interpretation of brines and saline waters find
used, and electrode performance and interferences must be the MacInnes assumption more consistent with conventional
determined. The most acceptable model for activity coeffi- practice. If the unscaled approach is used, the resultant pH
cients at present for defining pH below 1.0 is the Pitzer values begin to differ significantly from MacInnes scaling for
ion-interaction approach (20, 21). Acid mine waters are solu- sulfuric acid solutions with pH values below 20.5. For exam-
tions of sulfuric acid, so the Pitzer model applied to sulfuric ple, at a sulfuric acid concentration of about 5.0 molal a scaled
acid (22, 23) could serve as a definition for pH. Standardized pH would be 22, whereas the unscaled pH would be notably
sulfuric acid solutions would then serve as buffer solutions for higher, about 21.2.
calibration and the remaining question is the performance of Some of these negative-pH mine waters were in apparent
standard glass membrane electrodes under these extreme equilibrium with prominent soluble salts. For example, a
Table 3. Compositions of five extremely acid mine water samples from the Richmond Mine
Concentration of element in sample, mgyliter
90WA103 90WA109 90WA110A 90WA110C 91WA111
34.8°C 38°C 42°C 46°C 28°C
Element pH 0.48 pH 20.7 pH 22.5 pH 23.6 —
Aluminum 2,210 6,680 1,420 — 6,470
Antimony 4.0 16 29 — 15
Arsenic(III) 8.14 38 32 — 74
Arsenic (total) 56.4 154 340 — 850
Barium 0.068 0.1 0.2 — ,0.1
Beryllium 0.026 0.1 0.2 — ,0.1
Boron 1.5 2.5 17 — —
Cadmium 15.9 48.3 211 — 370
Calcium 183 330 279 — 443
Chromium 0.12 0.75 0.6 — 2.6
Cobalt 1.3 15.5 5.3 — 3.6
Copper 290 2,340 4,760 — 9,800
Iron(II) 18,100 79,700 34,500 9,790 —
Iron (total) 20,300 86,200 111,000 16,300 68,100
Lead 3.6 3.8 11.9 — 8.3
Magnesium 821 1,450 437 — 2,560
Manganese 17.1 42 23 — 119
Molybdenum 0.59 1.0 4.2 — 2.3
Nickel 0.66 2.9 3.7 — 6.3
Potassium 261 1,170 194 — 11.1
Selenium 0.42 2.1 4.2 — ,2.8
Silicon (as SiO2) 170 34 35 — —
Silver 0.16 0.65 2.4 — 0.70
Sodium 251 939 416 — 44
Strontium 0.25 0.49 0.90 — —
Sulfur (as SO4) 118,000 360,000 760,000 — —
Thallium 0.44 0.15 0.39 — 1.6
Tin 1.6 15 41 — —
Titanium 5.9 125 1.0 — —
Vanadium 2.9 11 15 — 28
Zinc 2,010 7,650 23,500 49,300
FIG. 4. Growth of cuprian melanterite in a manway of the Rich- FIG. 5. Stalagmite of rhomboclase (white) and coquimbite (pur-
mond Mine with stalactite dripping pH 5 20.7 water into plastic ple) in the Richmond Mine. (Photo by C.N.A. and D.K.N.)
beaker. (Photo by D.K.N. and C.N.A.)
flow rate of the water. Consistent with this expectation, the
stalactite of zincian-cuprian melanterite had water dripping only iron sulfate salts containing exclusively ferrous iron,
from the tip that had a pH of 20.7 (Table 3 and Fig. 4). melanterite, rozenite, and szomolnokite, are found close to
Enormous quantities of highly soluble iron sulfate salts were pyrite sources and associated with more rapidly flowing wa-
found as efflorescences and precipitates, coating walls, ceil- ters. Ferric-bearing minerals are found to form in more
ings, and floors of the mine and growing out of muck piles in stagnant conditions and can be considered to be hydrologic
colorful assemblages. Identification of these soluble salts made ‘‘dead-ends,’’ where much of the FeII has had time to oxidize
it possible to estimate what the composition of a mine pool to FeIII. Additional evidence for this mineralogical evolution is
formed by mine plugging might be. the observation that melanterite is the first-formed mineral
when typical acid mine water is allowed to evaporate under
Soluble Salts and Consequences of the Mine-Plugging
ambient conditions and rhomboclase and voltaite are the last
Scenario
formed (25).
Ten soluble iron sulfate salts plus gypsum and chalcanthite A copper–zinc partitioning study of melanterite demon-
were identified in the Richmond Mine. These minerals and strates that melanterite prefers copper over zinc (15). The
their idealized formulae are listed in Table 4, with the iron salts consequences of this partitioning are that portal effluents will
in approximate sequence downward from the early formed to tend to have higher ratios of ZnyCu during the dry season
the later formed. Rhomboclase was found as stalactites and when melanterite is forming underground and lower ZnyCu
stalagmites (Fig. 5), and clusters of coquimbite, römerite, ratios in the wet season when these salts are dissolved and
copiapite, and voltaite crystals were common throughout the flushed from the mine workings. This trend is seen in the
mine (Fig. 6). Rhomboclase was rarely found without voltaite historical data on the Richmond Mine effluent (15).
crystals. Dissolution of these soluble, iron sulfate salts (with variable
As long as an acid mine water is in contact with pyrite, the amounts of copper, zinc, cadmium, and aluminum substituting
dissolved iron will remain in the ferrous state because of the
strong reducing capacity of the pyrite. Rapidly flowing mine
water will still maintain a high proportion of ferrous iron
because the oxidation rate is often slow enough relative to the
Gypsum CaSO4z2H2O FIG. 6. Cluster of coquimbite, voltaite, and copiapite from the
Richmond Mine. (Photo by G. Robinson, Canadian Museum of
Chalcanthite CuSO4z5H2O
Nature, Ottawa.)
3460 Colloquium Paper: Nordstrom and Alpers Proc. Natl. Acad. Sci. USA 96 (1999)
for the iron) can generate acidic solutions with high concen- sites, plugging may ultimately prove to be successful, but more
trations of dissolved metals. During the rising limb of a stream careful planning and peer review are essential to lessen the
discharge in central Virginia after the onset of rain, Dagenhart probability of disastrous results.
(26) showed that rapid increases in the concentrations of Cu,
Zn, Fe, and Al resulted from the dissolution of efflorescent Regulatory Investigations and Remediation
salts found on upstream tailings and waste rock piles. This
phenomenon must be common at mine waste sites and is likely Several investigations and regulatory actions at Iron Mountain
to be an important cause of fish kills associated with periods have been initiated by California State agencies over the last
of high runoff, especially after prolonged dry periods. Now we few decades. These are too lengthy to summarize here. Since
consider the consequences of dissolution of the enormous the original listing of Iron Mountain on the National Priorities
quantity of salts in the Richmond Mine in a mine-plugging List in 1983, the EPA has authorized four Records of Decision
scenario. (RODs) and has considered numerous options for remedia-
The chemical composition of the mine pool created by tion. A condensed version of the main remedial alternatives is
plugging the Richmond Mine can be estimated by allowing as follows:
these salts to dissolve in a volume of water equivalent to the
void space created by the underground workings. The exact
Y No action
proportion of the different type of salts is not known, but the
Y Surface-water diversion
results of the calculations are not particularly sensitive to this
Y Lime neutralization
factor. The amount of salts stored underground is a more
Y Capping (partial or complete capping of the mountain to
critical factor, and so that was considered a variable. Compu- prevent infiltration)
tations were made by inputting the mineral compositions to the
Y Enlargement of Spring Creek Debris Dam (acid water
PHREEQE program (ref. 27, now superseded by PHREEQC, ref.
storage and release structure)
28) for a range of salt volumes. PHREEQE can calculate the
Y Ground-water interception
speciation and chemical equilibrium for mass transfer pro-
Y Air sealing
cesses such as precipitation, dissolution, oxidation–reduction
Y Mine plugging
reactions, ion exchange, and gas addition or removal (29). The
Y On-site leaching and solution extraction
results are shown in Fig. 7, where the resultant pH in the mine
Y Continued mining under environmentally safe conditions
pool is plotted against the volume of added salts under two Y Combined alternatives
scenarios: active infiltration (actively injecting clean water) Surface-water diversions have been installed to divert clean
and passive infiltration (letting the groundwater naturally fill headwater streams around contaminated areas. The waters
the void spaces). The latter scenario gives a worse picture that are the largest sources of metal loadings have been
because passive infiltration would allow more pyrite oxidation captured and diverted to a lime neutralization plant. In the late
and the buildup of more acid waters. The salts probably occupy 1980s, an emergency lime neutralization plant with a capacity
about 1% of the volume of the mine workings based on visual of about 60 gallons per minute (gpm; 1 gallon 5 3.8 3 1023 m3)
inspection from the limited subsurface survey. As can be seen was installed to handle the worst flows from the Richmond and
in Fig. 7, however, an error in this value makes little difference. Hornet portals. By December of 1992, this plant had been
The consequences are that a mine pool of about 600,000 m3 expanded to handle 140 gpm, but was operated only 4 months
with a pH at or below 1, with many grams of dissolved metals per year during highest flows. In July of 1994 a new plant with
per liter (much like the current portal effluent), would likely a capacity of about 1,400 gpm began operation at the Minne-
form at or near the top of the groundwater table, in a rock with sota Flats tailings site. In 1996 it was upgraded to 2,000 gpm,
almost no neutralization capacity, and in which the hydrologic and high-density sludge treatment was added. Now it accepts
flow is governed by fractures, excavations, and drill-holes. drainage from Slickrock Creek (pumped from Old Mine and
Thus, plugging presents a remediation scenario that has a high No. 8 Mine workings) as well as the Richmond and Hornet
degree of risk with potentially dangerous results. Mine portal effluents.
It has been common engineering practice to plug abandoned The decision to build the larger treatment plant and to treat
or inactive mines without monitoring, modeling, or even discharges from the Lawson tunnel (Hornet Mine) was also
considering the physical and chemical consequences. Major influenced by geochemical modeling. Opinion was divided as
leaks or failures at plugs, widespread and disseminated seeps to whether the flow of acid mine water from the Lawson tunnel
of enriched acid mine waters, and increases in subsurface head originates from the Richmond Mine by spillage or leakage or
pressures of more than 100 m have occurred. For some mine whether the Hornet ore body produces its own contaminant
effluent. An ore chute and a raise that connected the two
mines were identified from the old mine maps (Fig. 2). Because
of its proximity to the surface and the collapsed nature of the
mine workings, it was generally agreed that the Hornet Mine
itself could not be effectively plugged. However, consultants
proposed that plugging the Richmond Mine would stop or
greatly reduce the flow from the Lawson tunnel. There was
also reason to believe that during the intervening years since
mining ceased, cave-ins and other ground failures had largely
cut off direct connections from the Richmond to the Hornet.
Alpers and others (19) studied the historical data on rain-
fall–discharge relationships between the two mines, ZnyCu
ratios as a signature of reactions within each mine site, and
mass balance calculations for the two portal effluents. The
most definitive method of determining the possible influence
of the Richmond Mine water on the Lawson tunnel effluent
was a mass balance approach. Using the known water com-
FIG. 7. PHREEQE simulation of water composition for mine pool positions discharging from each mine and knowing the com-
after plugging the Richmond Mine. position of the minerals that are reacting to form the effluent
Colloquium Paper: Nordstrom and Alpers Proc. Natl. Acad. Sci. USA 96 (1999) 3461
waters, it is possible to calculate the mass amounts of minerals effect the best and most appropriate remediation available at
dissolved or precipitated to produce these waters by using the a given time for a given site. Both long-term and short-term
BALANCE program (30). Mineral reaction signatures were remediations are needed. For the short term, we need to fill in
developed for each mine effluent separately, and then Rich- the knowledge gaps, especially as they pertain to a particular
mond effluent was mixed with clean ground water and allowed site. For the long term, we need to continue to develop better
to precipitate and dissolve additional minerals to determine if remediation techniques and mining and processing techniques
it was possible to derive the Lawson effluent from the Rich- that can utilize mine wastes and mineral deposits of lower
mond. No version of this mass balance model produced a water grade. Mineralogical and geochemical knowledge make it
that matched the Lawson effluent. Next, Richmond effluent possible to foresee the potential consequences of a remedial
was also mixed with Lawson effluent, and geochemical reac- option and to plan a remediation strategy. The results of
tion was allowed, to see how much effluent each mine could long-term research by the U.S. Geological Survey provided
be contributing to the Lawson. The model results indicated technical tools (computer programs for geochemical modeling
that not more than about 2% of the Richmond effluent could and procedures for measuring pH) that could be used to
be present in the Lawson effluent. Therefore, the Hornet Mine answer important questions regarding remediation scenarios.
is producing its own effluent independently of the Richmond Third, it would seem prudent to proceed on mine waste
Mine. Even if the Richmond Mine were successfully plugged, cleanup in a phased, iterative approach. Our natural inclina-
water from the Hornet would continue to be a significant tion is to identify the worst part of a hazardous waste site and
problem and it would have to be treated. attempt to clean it up. For Iron Mountain, there is no single
The fourth Record of Decision, issued in September of 1997,
remedial solution that would clean up 90% of the problem on
selected the construction of a dam on Slickrock Creek. This
a permanent and maintenance-free basis (with the exception
structure will capture the largest remaining loads of Cu and Zn
of completely mining the mountain). There are, however,
and divert them to the neutralization plant for treatment. The
several options (most of which have been exercised) that are
remaining remediation is now focused on Boulder Creek,
low risk and low cost and should reduce the discharge of acid
lower Spring Creek, Spring Creek Reservoir, and the metal-
enriched sediments that formed in Keswick Reservoir from the mine waters. These options can be instituted while delibera-
neutralization of acid mine waters for nearly 50 years. tions and research continue to find the long-term solution.
The EPA and the potentially responsible parties remain in Fourth, mine waste sites commonly contain low-grade re-
legal contention over the appropriate final remediation ap- sources that are potentially mineable—it requires the right
proaches to be used at Iron Mountain and the costs. Both the technology to make resource recovery economic. In an age of
U.S. Government and the potentially responsible parties have increasing recycling, recycling strategies should be applied to
funded a considerable number of investigations, remediation mine sites. Many mine wastes have already undergone further
efforts, legal fees, and oversight management. The loads of metals extraction and others could be stockpiled or tested for
copper, zinc, and cadmium into the Sacramento River have new uses. Additional research into metal recovery from acidic
been reduced by 80–90%, and further remediation is in solutions could also provide economic incentive to recycling
progress or being planned. The main challenge that remains is metals from mine drainage waste streams.
how to find a permanent (and passive) treatment solution in Finally, Iron Mountain has been an extraordinary and
light of the fact that the mine drainage will continue for extreme environment in which to study and document the
approximately 3,000 years unless the sulfide ore is mined out. processes of acid mine water production and efflorescent
mineral formation, the value of which goes far beyond just the
Conclusion immediate remediation needs. The processes and properties
found at Iron Mountain are probably commonplace at metal
Prevention and control of contamination at mine sites is a sulfide mine and mineral processing sites, but usually on a
challenging task, and remediation of large inactive mine sites smaller scale. We now have some direct observations of the
such as Iron Mountain has proven to be extraordinarily composition of water that produces efflorescent minerals. We
difficult, complex, and expensive, not to mention litigious. The have some idea of the consequences of efflorescent mineral
physical and chemical nature of the site makes it difficult to dissolution when a mine is plugged. We can estimate the
assess the effectiveness of remediation and the relative risks geochemical consequences of various remediation scenarios
and costs of various alternatives and their contingencies. There for mine sites with better confidence. Unraveling the dynamic
are no easy solutions to these types of environmental problems, processes that affect water–mineral interactions is often crit-
but several important points can be made about cleanup of ical to solving hazardous waste problems in the hydrogeologic
mine waste sites on the basis of our experiences at Iron environment.
Mountain.
First, there is tremendous value to having a technical We are grateful to personnel of Region 9 of the U.S. EPA, especially
advisory team of multidisciplinary professionals, without an Rick Sugarek, for their continued support of our investigations on this
obvious conflict of interest, to advise the regulatory agencies, project and to personnel of CH2M Hill for their help and assistance in
to review data, and to make recommendations. Mine sites and our efforts to answer technically challenging questions. We thank the
their contaminants are complex functions of the geology, California Regional Water Quality Control Board in Redding and all
hydrology, geochemistry, pedology, meteorology, microbiol- the state agencies that have worked on Iron Mountain for their
ogy, and mining and mineral processing history, and their cooperation and support. Roger Ashley and Katie Walton-Day (U.S.
remediation is subject to considerations of economic limita- Geological Survey) and James Hanley and Carol Russell (EPA)
tions, available technology, and potential land use. Further- provided helpful reviews. We also acknowledge Rick Sugarek for
making helpful suggestions on the manuscript.
more, the risks of failed remediation or no action are often
poorly known. Assessing such risks involves toxicology, epi-
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tion. To ignore professionals in these areas, who can contribute Rock, Asbestos, Overburden from Uranium Mining, and Oil Shale:
both to the wisest choice of remediation strategies and to Report to Congress EPAy530-SW-85–033.
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