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Fate of antimony and arsenic in contaminated waters at the abandoned Su Suergiu mine (Sardinia, Italy)

We investigated the fate of Sb and As downstream of the abandoned Su Suergiu mine (Sardinia, Italy) and surrounding areas. The mined area is a priority in the Sardinian remediation plan for contaminated sites due to the high concentrations of Sb and As in the mining-related wastes, which may impact the Flumendosa River that supplies water for agriculture and domestic uses. Hydrogeochemical surveys conducted from 2005 to 2015 produced time-series data and downstream profiles of water chemistry at 46 sites. Water was sampled at: springs and streams unaffected by mining; adits and streams in the mine area; drainage from the slag heaps; stream water downstream of the slag drainages; and the Flumendosa River downstream from the confluence of the contaminated waters. At specific sites, water sampling was repeated under different flow conditions, resulting in a total of 99 samples. The water samples were neutral to slightly alkaline. Elevated Sb (up to 30 mg L −1 ) and As (up to 16 mg L −1 ) concentrations were observed in water flowing from the slag materials from where the Sb ore was processed. These slag materials were the main Sb and As source at Su Suergiu. A strong base, Na-carbonate, from the foundry wastes, had a major influence on mobilizing Sb and As. Downstream contamination can be explained by considering that: (1) the predominant aqueous species, Sb(OH) 6 − and HAsO 4 −2 , are not favored in sorption processes at the observed pH conditions; (2) precipitation of Sb- and As-bearing solid phases was not observed, which is consistent with modeling results indicating undersaturation; and (3) the main decrease in dissolved Sb and As concentrations was by dilution. Dissolved As concentrations in the Flumendosa River did not generally exceed the EU limit of 10 µg L −1 , whereas dissolved Sb in the river downstream of the contamination source always exceeded the EU limit of 5 µg L −1 . Recent actions aimed at retaining runoff from the slag heaps are apparently not sufficiently mitigating contamination in the Flumendosa River.

Sardinia

Laboratory simulation of groundwater along uranium-mining-affected flow paths near the Grand Canyon, Arizona, USA

Mining of volumetrically small, but relatively enriched (average 0.6% U 3 O 8 ) breccia pipe uranium (BPU) deposits near the Grand Canyon, Arizona, USA has the potential to affect groundwater and springs in the area. Such deposits also contain base metal sulfides that can oxidize to generate acid mine drainage and release trace metals. In this study, sequential batch experiments were conducted to simulate the geochemistry of local shallow groundwater that contacts BPU ore and then moves downgradient through sedimentary strata. The experiments simulated shallow groundwater in a carbonate aquifer followed by contact with BPU ore. The experiments subsequently simulated contact with sedimentary rocks and changing oxygen availability. Concentrations of several contaminants of potential concern became substantially elevated in the waters exposed to BPU ore, including As, Co, Ni, U, and Zn, and to a lesser extent, Mo. Of these, Co, Mo, Ni, and U were minimally attenuated by downgradient processes, whereas Zn was partially attenuated. Sb and Tl concentrations were more moderately elevated but also generally minimally attenuated. Although the mixture of elements is particular to these BPU ore deposits, sulfide oxidation in the ore and carbonate buffering of pH by sedimentary rocks generates patterns of water chemistry common in acid mine drainage settings. Ultimately, downgradient concentrations of elements sourced from BPU ore will also be strongly influenced by non-geochemical factors such as the quantities of water contacting BPU materials, heterogeneity of materials along flow paths, and mixing with waters that have not contacted BPU materials.

Arizona

To remediate or not? Source identification in an acid mine drainage stream, Warden Gulch, Colorado

A synoptic water quality study was implemented in Warden Gulch, a headwater stream affected by metals that are contributed by both natural and mining-impacted sources. Warden Gulch is a tributary to Peru Creek (Colorado, USA), where emplacement of a mine tunnel bulkhead and other remedial actions have improved water quality upstream of Warden Gulch. The goal of this study was to identify individual source contributions to Warden Gulch and determine if additional remedial actions were warranted. To this end, trace metal loading was quantified from various sources including an actively draining mine. Although highly concentrated waste streams from mining-impacted sites degrade water quality, natural contributions from unmined areas within the Warden Gulch watershed are the dominant sources of metal loading. Further, some mining-impacted sources are associated with diffuse groundwater inflows that may not be amenable to clean up, due to the diffuse nature of the sources and the associated cost. Mining-impacted sources that are amenable to clean up may therefore represent a small portion of the overall metal loading to Warden Gulch. Remedial measures directed at these sources may not substantially improve the water quality of Peru Creek and the larger Snake River watershed.

Colorado

Distribution of metals in water and bed sediment in a mineral-rich watershed, Montana, USA

We sampled the Blackfoot River (Montana) and its major tributaries from the headwaters of the basin to near its confluence with the Clark Fork River over the course of 5 days in August 1998. We measured streamflow, collected fine-grained (<63 μm) streambed sediment, and sampled the dissolved (operationally defined as < 0.2 μm) phase of the surface water using clean techniques. Water and sediment collected from near the historic Heddleston mining district contained the highest concentrations of most trace elements in the basin. Many solute trace metals were at their highest several kilometers downstream from the mining district, where the river flows through an unremediated marsh system that has collected mine wastes in the past. Downstream on the headwaters area, water and bed sediment metal concentrations declined sharply. Comparison of sediment samples with those collected by other workers in August 1989 and August 1995 do not show evidence of basin-scale long term changes, despite the onset of remediation efforts in 1993. The area of the proposed McDonald gold deposit near the confluence of the Landers Fork with the Blackfoot River was not contributing anomalous concentrations of naturally-occurring dissolved and bed-sediment metals into the basin.

Montana

Effect of mine drainage on the quality of streams in Colorado, 1971-72

In July 1971, a study of the effects of mine drainage on Colorado's streams was begun in cooperation with the Colorado Water Pollution Control Commission. The objectives of this study were to determine the extent and magnitude of the problem as a whole, and to gain a greater understanding of the processes and their potential ramifications by detailed definition of problems in specific areas. In order to accomplish these objectives, a three-pronged approach was devised to include: (1) a reconnaissance of the entire State to locate problem areas, (2) the detailed study of selected problem areas on a short-term basis, and (3) the monitoring of selected problem areas on a long-term basis. This report summarizes the results of the reconnaissance phase. It describes some basic physical, chemical, and biological water-quality characteristics of the streams, discusses observed effects of mine drainage on the surface-water environment, delineates problem areas, and provides a list of streams where intensive study and subsequent monitoring might provide further insight into the various problems encountered.

Colorado

Questa baseline and pre-mining ground-water quality investigation. 17. Geomorphology of the Red River Valley, Taos County, New Mexico, and influence on ground-water flow in the shallow alluvial aquifer

In April 2001, the U.S. Geological Survey (USGS) and the New Mexico Environment Department (NMED) began a cooperative study to infer the pre-mining ground-water chemistry at the Molycorp molybdenum mine site in the Red River Valley of north-central New Mexico. This report is one in a series of reports that can be used to determine pre-mining ground-water conditions at the mine site. Molycorp’s Questa molybdenum mine in the Red River Valley, northern New Mexico, is located near the margin of the Questa caldera in a highly mineralized region. The bedrock of the Taos Range surrounding the Red River is composed of Proterozoic rocks of various types, which are intruded and overlain by Oligocene volcanic rocks associated with the Questa caldera. Locally, these rocks were altered by hydrothermal activity. The alteration zones that contain sulfide minerals are particularly important because they constitute the commercial ore bodies of the region and, where exposed to weathering, form sites of rapid erosion referred to as alteration scars. Over the past thousand years, if not over the entire Holocene, erosion rates were spatially variable. Forested hillslopes eroded at about 0.04 millimeter per year, whereas alteration scars eroded at about 2.7 millimeters per year. The erosion rate of the alteration scars is unusually rapid for naturally occurring sites that have not been disturbed by humans. Watersheds containing large alteration scars delivered more sediment to the Red River Valley than the Red River could remove. Consequently, large debris fans, as much as 80 meters thick, developed within the valley. The geomorphology of the Red River Valley has had several large influences on the hydrology of the shallow alluvial aquifer, and those influences were in effect before the onset of mining within the watershed. Several reaches where alluvial ground water emerges to become Red River streamflow were observed by a tracer dilution study conducted in 2001. The aquifer narrows where erosion-resistant bedrock, which tends to form vertical cliffs, restricts the width of the valley bottom. Although the presence of a shallow bedrock sill, overlain by shallow alluvium, is a plausible cause of ground-water emergence, this cause was not demonstrated in the study area. The water-table gradient can locally decrease in the downstream direction because of changes in the hydraulic properties of the alluvium, and this may be a contributing cause of ground-water emergence. However, at one site (near Cabin Springs), ground-water emergence could not be explained by spatial changes in geometric or hydraulic properties of the aquifer. Furthermore, the available evidence demonstrates that ground water flowing through bedrock fractures or colluvium entered the north side of the alluvial aquifer, and is the cause of ground-water emergence. At that location the alluvial aquifer was already flowing full, causing the excess water to emerge into the stream. An indirect consequence of altered rock in the tributary watersheds is the rapid erosion rate of alteration scars combined with the hydraulic properties of sediments shed from those scars. Where alteration scars are large the debris fans at the mouths of the tributary watersheds substantially encroach into the Red River Valley. At such locations debris-fan materials dominate the width and thickness of the alluvium in the valley and reduce the rate of flow of ground water within the Red River alluvial aquifer. Most sites of groundwater emergence are located immediately upstream from or along the margins of debris fans. A substantial fraction of the ground water approaching a debris fan can emerge to become streamflow. This last observation has three implications. First, very little water can flow the entire length of the study area entirely within the alluvial aquifer because the ground water repeatedly contacts debris-fan sediments over that length. Second, it follows that emerging water containing unique elemental constituents must have entered the alluvial aquifer at a relatively short distance upstream. Third, a gravel aquifer downstream from a large debris fan can transmit more ground water than flows into it through the debris fan. This observation explains how the water table can be naturally, and permanently, located well beneath the level of the bed of a perennial stream.

New Mexico

Mercury mine drainage and processes that control its environmental impact

Mine drainage from mercury mines in the California Coast Range mercury mineral belt is an environmental concern because of its acidity and high sulfate, mercury, and methylmercury concentrations. Two types of mercury deposits are present in the mineral belt, silica-carbonate and hot-spring type. Mine drainage is associated with both deposit types but more commonly with the silica-carbonate type because of the extensive underground workings present at these mines. Mercury ores consisting primarily of cinnabar were processed in rotary furnaces and retorts and elemental mercury recovered from condensing systems. During the roasting process mercury phases more soluble than cinnabar are formed and concentrated in the mine tailings, commonly termed calcines. Differences in mineralogy and trace metal geochemistry between the two deposit types are reflected in mine drainage composition. Silica-carbonate type deposits have higher iron sulfide content than hot- spring type deposits and mine drainage from these deposits may have extreme acidity and very high concentrations of iron and sulfate. Mercury and methylmercury concentrations in mine drainage are relatively low at the point of discharge from mine workings. The concentration of both mercury species increases significantly in mine drainage that flows through and reacts with calcines. The soluble mercury phases in the calcines are dissolved and sulfate is added such that methylation of mercury by sulfate reducing bacteria is enhanced in calcines that are saturated with mine drainage. Where mercury mine drainage enters and first mixes with stream water, the addition of high concentrations of mercury and sulfate generates a favorable environment for methylation of mercury. Mixing of oxygenated stream water with mine drainage causes oxidation of dissolved iron(II) and precipitation of iron oxyhydroxide that accumulates in the streambed. Both mercury and methylmercury are strongly adsorbed onto iron oxyhydroxide over the pH range of 3.2-7.1 in streams impacted by mine drainage. The dissolved fraction of both mercury species is depleted and concentrated in iron oxyhydroxide such that the amount of iron oxyhydroxide in the water column reflects the concentration of mercury species. In streams impacted by mine drainage, mercury and methylmercury are transported and adsorbed onto particulate phases. During periods of low stream flow, fine-grained iron hydroxide sediment accumulates in the bed load of the stream and adsorbs mercury and methylmercury such that both forms of mercury become highly enriched in the iron oxyhydroxide sediment. During high-flow events, mercury- and methylmercury-enriched iron hydroxide sediment is transported into larger aquatic systems producing a high flux of bioavailable mercury. (C) 2000 Elsevier Science B.V.

Science of the Total Environment

Hydrologic modeling to examine the influence of the forestry reclamation approach and climate change on mineland hydrology

Forests in the Appalachian region of the U.S. are threatened by a variety of short- and long-term pressures, including climate change, invasive species, and resource extraction. Surface mining for coal is one of the most important drivers of land-use change in the region, reducing native forest cover, causing forest fragmentation, eliminating intact soil, and affecting water resources. The Forestry Reclamation Approach (FRA) has been demonstrated as a successful best practice for restoring forests on mine-impacted landscapes, but little information exists on how the practice will affect hydrologic processes. A study was initiated to examine soil-water movement, as in-situ saturated hydraulic conductivity (K sat ), combined with soil porosity to quantify the potential influence on streamflow of reclaimed mines relative to an unmined, forested control site in eastern Kentucky. We compared different reclamation techniques and time since reclamation to determine the extent to which hydrologic function can be restored. We also simulated evapotranspiration at the watershed scale as a function of reclamation technique for both historical and projected (2050) climate. Results indicate that conventional grassland reclamation critically changes how soil water transitions to streamflow, primarily due to K sat variability that exceeds that measured for intact and FRA soils. Sites reclaimed using FRA exhibited a soil-water environment that was more similar to the unmined control. However, all reclaimed mine soils were thinner, retained and stored less soil water, and thus could provide less plant-available water during the growing season. The plant-available water stored in reclaimed landscapes may not be sufficient to support forest health and this is exacerbated by projected climate conditions. However, soil development under a combination of FRA techniques has the potential to mitigate this limitation.

Kentucky

Questa baseline and pre-mining ground-water quality investigation 15.—Methods of phase II and III well installation and development and results of well logging, hydraulic testing, and water-level measurements in the Red River Valley, New Mexico, 2002-04

In April 2001, the U.S. Geological Survey and the New Mexico Environment Department began a cooperative study to infer the pre-mining ground-water chemistry at the Molycorp molybdenum mine site in the Red River Valley of north- central New Mexico. This report is one in a series of reports that can be used to determine pre-mining ground-water conditions at the mine site. Weathering of hydrothermally altered bedrock in the study area has resulted in steep, highly erosive, and sparsely vegetated scar areas that are clearly visible from the ground and in aerial photographs. Runoff from intense summer rainfall over tributary drainages containing scar areas can transport large quantities of sediment and form debris fans where these tributaries join the Red River. Twenty-nine observation wells were installed in three phases as part of this study in the Red River Valley and tributary drainages. Eight Phase II observation wells were drilled using an air-rotary/hammer rig. Three Phase II and 10 phase III small-diameter wells were installed using a direct-push rig. Lithologic logs were recorded for all eight Phase II drilled wells. Borehole geophysical logging (including natural gamma, induction, and single-detector neutron) was conducted in three Phase II wells. Aquifer tests conducted during 2003 to estimate the hydraulic properties of debris-flow and Red River alluvial deposits in and near Straight Creek included a flow-meter survey, slug tests, and a pumping test. Results of a flow-meter survey in well SC-7A indicated that about 77 percent of the water entered the well from a 10-foot-thick zone near the top of the screened interval and about 23 percent of the water entered the well from a 15-foot-thick zone near the bottom of the screened interval. Slug tests, performed in 11 wells during June 3-5, 2003, indicated that the mean and median estimated hydraulic conductivities for debris-flow deposits were 15.25 and 15.35 feet per day, respectively, for bedrock were 0.12 and 0.08 feet per day, respectively, and for mixed debris flow and Red River alluvium were 73-207 (estimated range) and 80 feet per day. In general, bedrock has the smallest hydraulic conductivity, debris-flow material has the next highest hydraulic conductivity, and mixed debris flow and Red River alluvium has the largest hydraulic conductivity. A pumping test conducted December 3-4, 2003, using well AWWT-1 as the pumped well, and wells AWWT-2, SC-5A, SC-5B, SC-7A, and SC-8A as observation wells, indicated estimated transmissivity of 12,000 to 34,000 feet squared per day and estimated hydraulic conductivity of 230 to 340 feet per day. Water-level measurements in wells SC-6A, SC-7A, SC-8A, and the Hottentot, Hansen, and La Bobita wells show that water levels typically rose rapidly during melting of the winter snowpack in the springtime and then generally declined during the rest of the year. The water-level rise in response to spring snowmelt occurred earlier and was smaller at larger distances from the Red River. Differences between the stage in the Red River and water levels in wells SC-8A and SC-9A, and the absence of water in well SC-9A at the time of well completion, indicate that the Red River has a poor hydraulic connection to the underlying ground-water system and the surface-water system is perched above the ground-water system at this site. Water levels in Phase III wells indicate that the Red River and the shallow ground-water system are connected hydraulically from near wells 4-1D and 4-1S downstream to near wells 2-1 and 2-2 but are poorly connected near the La Bobita well and well 1.

New Mexico

Questa baseline and pre-mining ground-water quality investigation. 25. Summary of results and baseline and pre-mining ground-water geochemistry, Red River Valley, Taos County, New Mexico, 2001-2005

Active and inactive mine sites are challenging to remediate because of their complexity and scale. Regulations meant to achieve environmental restoration at mine sites are equally challenging to apply for the same reasons. The goal of environmental restoration should be to restore contaminated mine sites, as closely as possible, to pre-mining conditions. Metalliferous mine sites in the Western United States are commonly located in hydrothermally altered and mineralized terrain in which pre-mining concentrations of metals were already anomalously high. Typically, those pre-mining concentrations were not measured, but sometimes they can be reconstructed using scientific inference. Molycorp?s Questa molybdenum mine in the Red River Valley, northern New Mexico, is located near the margin of the Questa caldera in a highly mineralized region. The State of New Mexico requires that ground-water quality standards be met on closure unless it can be shown that potential contaminant concentrations were higher than the standards before mining. No ground water at the mine site had been chemically analyzed before mining. The aim of this investigation, in cooperation with the New Mexico Environment Department (NMED), is to infer the pre-mining ground-water quality by an examination of the geologic, hydrologic, and geochemical controls on ground-water quality in a nearby, or proximal, analog site in the Straight Creek drainage basin. Twenty-seven reports contain details of investigations on the geological, hydrological, and geochemical characteristics of the Red River Valley that are summarized in this report. These studies include mapping of surface mineralogy by Airborne Visible-Infrared Imaging Spectrometry (AVIRIS); compilations of historical surface- and ground- water quality data; synoptic/tracer studies with mass loading and temporal water-quality trends of the Red River; reaction-transport modeling of the Red River; environmental geology of the Red River Valley; lake-sediment chemistry; geomorphology and its effect on ground-water flow; geophysical studies on depth to ground-water table and depth to bedrock; bedrock fractures and their potential influence on ground-water flow; leaching studies of scars and waste-rock piles; mineralogy and mineral chemistry and their effect on ground-water quality; debris-flow hazards; hydrology and water balance for the Red River Valley; ground-water geochemistry of selected wells undisturbed by mining in the Red River Valley; and quality assurance and quality control of water analyses. Studies aimed specifically at the Straight Creek natural-analog site include electrical surveys; high-resolution seismic survey; age-dating with tritium/helium; water budget; ground-water hydrology and geochemistry; and comparison of mineralogy and lithology to that of the mine site. The highly mineralized and hydrothermally altered volcanic rocks of the Red River Valley contain several percent pyrite in the quartz-sericite-pyrite (QSP) alteration zone, which weather naturally to acid-sulfate surface and ground waters that discharge to the Red River. Weathering of waste-rock piles containing pyrite also contributes acid water that eventually discharges into the Red River. These acid discharges are neutralized by circumneutral-pH, carbonate-buffered surface and ground waters of the Red River. The buffering capacity of the Red River, however, decreases from the town of Red River to the U.S. Geological Survey (USGS) gaging station near Questa. During short, but intense, storm events, the buffering capacity is exceeded and the river becomes acid from the rapid flushing of acidic materials from natural scar areas. The lithology, mineralogy, elevation, and hydrology of the Straight Creek proximal analog site were found to closely approximate those of the mine site with the exception of the mine site?s Sulphur Gulch catchment. Sulphur Gulch contains three subcatchments?upper Sulphur Gulch, Blind Gulch, and Spring Gulc

New Mexico

Advances in the hydrogeochemistry and microbiology of acid mine waters

The last decade has witnessed a plethora of research related to the hydrogeochemistry and microbiology of acid mine waters and associated tailings and waste-rock waters. Numerous books, reviews, technical papers, and proceedings have been published that examine the complex bio-geochemical process of sulfide mineral oxidation, develop and apply geochemical models to site characterization, and characterize the microbial ecology of these environments. This review summarizes many of these recent works, and provides references for those investigating this field. Comparisons of measured versus calculated Eh and measured versus calculated pH for water samples from several field sites demonstrate the reliability of some current geochemical models for aqueous speciation and mass balances. Geochemical models are not, however, used to predict accurately time-dependent processes but to improve our understanding of these systems and to constrain possible processes that contribute to actual or potential water quality issues. Microbiological studies are demonstrating that there is much we have yet to learn about the types of different microorganisms and their function and ecology in mine-waste environments. A broad diversity of green algae, bacteria, archaea, yeasts, and fungi are encountered in acid mine waters, and a better understanding of their ecology and function may potentially enhance remediation possibilities as well as our understanding of the evolution of life.

International Geology Review

Radioactivity in the environment; a case study of the Puerco and Little Colorado River basins, Arizona and New Mexico

This report, written for the nontechnical reader, summarizes the results of a study from 1988-91 of the occurrence and transport of selected radionuclides and other chemical constituents in the Puerco and Little Colorado River basins, Arizona and New Mexico. More than two decades of uranium mining and the 1979 failure of an earthen dam containing mine tailings released high levels of radionuclides and other chemical constituents to the Puerco River, a tributary of the Little Colorado River. Releases caused public concern that ground water and streamflow downstream from mining were contaminated. Study findings show which radioactive elements are present, how these elements are distributed between water and sediment in the environment, how concentrations of radioactive elements vary naturally within basins, and how levels of radioactivity have changed since the end of mining. Although levels of radioactive elements and other trace elements measured in streamflow commonly exceed drinking-water standards, no evidence was found to indicate that the high concentrations were still related to uraniurn mining. Sediment radioactivity was higher at sample sites on streams that drain the eastern part of the Little Colorado River basin than that of samples from the western part. Radioactivity of suspended sediment measured in this study, therefore, represents natural conditions for the streams sampled rather than an effect of mining. Because ground water beneath the Puerco River channel is shallow, the aquifer is vulnerable to contamination. A narrow zone of ground water beneath the Puerco River containing elevated uranium concentrations was identified during the study. The highest concentrations were nearest the mines and in samples collected in the first few feet beneath the streambed. Natuxal radiation levels in a few areas of the underlying sedimentary aquifer not connected to the Puerco River also exceeded water quality standards. Water testing would enable those residents not using public water supplies to determine if their water is safe to use.

Water-Resources Investigations Report

Removal of phosphorus from agricultural wastewaters using adsorption media prepared from acid mine drainage sludge

Excess phosphorus in wastewaters promotes eutrophication in receiving waterways. A??cost-effective method for the removal of phosphorus from water would significantly reduce the impact of such wastewaters on the environment. Acid mine drainage sludge is a waste product produced by the neutralization of acid mine drainage, and consists mainly of the same metal hydroxides used in traditional wastewater treatment for the removal of phosphorus. In this paper, we describe a method for the drying and pelletization of acid mine drainage sludge that results in a particulate media, which we have termed Ferroxysorb, for the removal of phosphorus from wastewater in an efficient packed bed contactor. Adsorption capacities are high, and kinetics rapid, such that a contact time of less than 5 min is sufficient for removal of 60-90% of the phosphorus, depending on the feed concentration and time in service. In addition, the adsorption capacity of the Ferroxysorb media was increased dramatically by using two columns in an alternating sequence so that each sludge bed receives alternating rest and adsorption cycles. A stripping procedure based on treatment with dilute sodium hydroxide was also developed that allows for recovery of the P from the media, with the possibility of generating a marketable fertilizer product. These results indicate that acid mine drainage sludges - hitherto thought of as undesirable wastes - can be used to remove phosphorus from wastewater, thus offsetting a portion of acid mine drainage treatment costs while at the same time improving water quality in sensitive watersheds.

Water Research

Stable isotope geochemistry of acid mine drainage: Experimental oxidation of pyrite

Sulfate and water from experiments in which pyrite was oxidized at a pH of 2.0 were analyzed for sulfur and oxygen stable isotopes. Experiments were conducted under both aerobic and anaerobic sterile conditions, as well as under aerobic conditions in the presence of Thiobacillus ferrooxidans, to elucidate the pathways of oxidation. Oxygen isotope fractionation between SO2-4 and H2O varied from +4.0 %. (anaerobic, sterile) to + 18.0 %. (aerobic, with T. ferrooxidans.). The oxygen isotope composition of dissolved oxygen utilized in both chemical and microbially-mediated oxidation was also determined (+11.4 %., by T. ferrooxidans; +18.4 %., chemical). Contributions of water-derived oxygen and dissolved oxygen to the sulfate produced in the oxidation of pyrite could thus be estimated. Water-derived oxygen constituted from 23 to ~ 100 percent of the oxygen in the sulfate produced in the experiments, and this closely approximates the range of contribution in natural acid mine drainage. Oxidation of sulfides in anaerobic, water-saturated environments occurs primarily by chemical oxidation pathways, whereas oxidation of sulfides in well-aerated, unsaturated zone environments occurs dominantly by microbially mediated pathways.

Geochimica et Cosmochimica Acta

Fixed bed sorption of phosphorus from wastewater using iron oxide-based media derived from acid mine drainage

Phosphorus (P) releases to the environment have been implicated in the eutrophication of important water bodies worldwide. Current technology for the removal of P from wastewaters consists of treatment with aluminum (Al) or iron (Fe) salts, but is expensive. The neutralization of acid mine drainage (AMD) generates sludge rich in Fe and Al oxides that has hitherto been considered a waste product, but these sludges could serve as an economical adsorption media for the removal of P from wastewaters. Therefore, we have evaluated an AMD-derived media as a sorbent for P in fixed bed sorption systems. The homogenous surface diffusion model (HSDM) was used to analyze fixed bed test data and to determine the value of related sorption parameters. The surface diffusion modulus Ed was found to be a useful predictor of sorption kinetics. Values of Ed < 0.2 were associated with early breakthrough of P, while more desirable S-shaped breakthrough curves resulted when 0.2 < Ed < 0.5. Computer simulations of the fixed bed process with the HSDM confirmed that if Ed was known, the shape of the breakthrough curve could be calculated. The surface diffusion coefficient D s was a critical factor in the calculation of Ed and could be estimated based on the sorption test conditions such as media characteristics, and influent flow rate and concentration. Optimal test results were obtained with a relatively small media particle size (average particle radius 0.028 cm) and resulted in 96 % removal of P from the influent over 46 days of continuous operation. These results indicate that fixed bed sorption of P would be a feasible option for the utilization of AMD residues, thus helping to decrease AMD treatment costs while at the same time ameliorating the impacts of P contamination.

Pennsylvania

Titanium

Titanium is a mineral commodity that is essential to the smooth functioning of modern industrial economies. Most of the titanium produced is refined into titanium dioxide, which has a high refractive index and is thus able to impart a durable white color to paint, paper, plastic, rubber, and wallboard. Because of their high strength-to-weight ratio and corrosion resistance, titanium metal and titanium metal alloys are used in the aerospace industry as well as for welding rod coatings, biological implants, and consumer goods. Ilmenite and rutile are currently the principal titanium-bearing ore minerals, although other minerals, including anatase, perovskite, and titanomagnetite, could have economic importance in the future. Ilmenite is currently being mined from two large magmatic deposits hosted in rocks of Proterozoic-age anorthosite plutonic suites. Most rutile and nearly one-half of the ilmenite produced are from heavy-mineral alluvial, fluvial, and eolian deposits. Titanium-bearing minerals occur in diverse geologic settings, but many of the known deposits are currently subeconomic for titanium because of complications related to the mineralogy or because of the presence of trace contaminants that can compromise the pigment production process. Global production of titanium minerals is currently dominated by Australia, Canada, Norway, and South Africa; additional amounts are produced in Brazil, India, Madagascar, Mozambique, Sierra Leone, and Sri Lanka. The United States accounts for about 4 percent of the total world production of titanium minerals and is heavily dependent on imports of titanium mineral concentrates to meet its domestic needs. Titanium occurs only in silicate or oxide minerals and never in sulfide minerals. Environmental considerations for titanium mining are related to waste rock disposal and the impact of trace constituents on water quality. Because titanium is generally inert in the environment, human health risks from titanium and titanium mining are minimal; however, the processes required to extract titanium from titanium feedstock can produce industrial waste.

Professional Paper

Hydrologic investigations concerning lead mining issues in southeastern Missouri

Good stewardship of our Nation's natural resources demands that the extraction of exploitable, minable ore deposits be conducted in harmony with the protection of the environment, a dilemma faced by many land and water management agencies in the Nation's mining areas. As ore is mined, milled, and sent to the smelter, it leaves footprints where it has been in the form of residual trace metals. Often these footprints become remnants that can be detrimental to other natural resources. This emphasizes the importance of understanding the earth's complex physical and biological processes and their interactions at increasingly smaller scales because subtle changes in one component can substantially affect others. Understanding these changes and resulting effects requires an integrated, multidisciplinary scientific approach. As ore reserves are depleted in one area, additional exploitable deposits are required to replace them, and at times these new deposits are discovered in previously unmined areas. Informed decisions concerning resource management in these new, proposed mining areas require an understanding of the potential consequences of the planned mining actions. This understanding is usually based on knowledge that has been accumulated from studying previously mined areas with similar geohydrologic and biologic conditions. If the two areas experience similar mining practices, the information should be transferable. Lead and zinc mining along the Viburnum Trend Subdistrict of southeastern Missouri has occurred for more than 40 years. Additional potentially exploitable deposits have been discovered 30 miles to the south, within the Mark Twain National Forest. It is anticipated that the observation of current (2008) geohydrologic conditions in the Viburnum Trend can provide insight to land managers that will help reasonably anticipate the potential mining effects should additional mining occur in the exploration area. The purpose of this report is to present a compilation of previously unpublished information that was collected as part of a larger multidisciplinary study of lead mining issues in southeastern Missouri. The report resulted from the application of a multidisciplinary approach to investigate current hydrologic and biologic conditions in streams of the Viburnum Trend and the exploration area in the Mark Twain National Forest.

Missouri

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.

Applied Geochemistry