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Kenneth G. Stollenwerk

Publications and source records attributed to Kenneth G. Stollenwerk.

17 recordsLinked to original sources
USGS2014

Assessing the solubility controls on vanadium in groundwater, northeastern San Joaquin Valley, CA

The solubility controls on vanadium (V) in groundwater were studied due to concerns over possible harmful health effects of ingesting V in drinking water. Vanadium concentrations in the northeastern San Joaquin Valley ranged from <3 μg/L to 70 μg/L with a median of 21 μg/L. Concentrations of V were highest in samples collected from oxic groundwater (49% > 25 μg/L) and lowest in samples collected from anoxic groundwater (70% < 0.8 μg/L). In oxic groundwater, speciation modeling (SM) using PHREEQC predicted that V exists primarily as the oxyanion H 2 VO 4 − . Adsorption/desorption reactions with mineral surfaces and associated oxide coatings were indicated as the primary solubility control of V 5+ oxyanions in groundwater. Environmental data showed that V concentrations in oxic groundwater generally increased with increasing groundwater pH. However, data from adsorption isotherm experiments indicated that small variations in pH (7.4–8.2) were not likely as an important a factor as the inherent adsorption capacity of oxide assemblages coating the surface of mineral grains. In suboxic groundwater, accurate SM modeling was difficult since Eh measurements of source water were not measured in this study. Vanadium concentrations in suboxic groundwater decreased with increasing pH indicating that V may exist as an oxycationic species [e.g. V(OH) 3 + ]. Vanadium may complex with dissolved inorganic and organic ligands under suboxic conditions, which could alter the adsorption behavior of V in groundwater. Speciation modeling did not predict the existence of V-inorganic ligand complexes and organic ligands were not collected as part of this study. More work is needed to determine processes governing V solubility under suboxic groundwater conditions. Under anoxic groundwater conditions, SM predicts that aqueous V exists as the uncharged V(OH) 3 molecule. However, exceedingly low V concentrations show that V is sparingly soluble in anoxic conditions. Results indicated that V may be precipitating as V 3+ - or mixed V 3+ /Fe 3+ -oxides in anoxic groundwater, which is consistent with results of a previous study. The fact that V appears insoluble in anoxic (Fe reducing) redox conditions indicates that the behavior of V is different than arsenic (As) in aquifer systems where the reductive dissolution of Fe-oxides with As adsorbed to the surface is a well-documented mechanism for increasing As concentrations in groundwater. This hypothesis is supported by the relation of V to As concentrations in oxic versus anoxic redox conditions. Sequential extraction procedures (SEP) applied to aquifer material showed that the greatest amount of V was recovered by the nitric acid (HNO 3 ) extract (37–71%), followed by the oxalate-ascorbic acid extract (19–60%) and the oxalate extract (3–14%). These results indicate that V was not associated with the solid phase as an easily exchangeable fraction. Although the total amount of V recovered was greatest for the HNO 3 extract that targets V adsorbed to sorption sites of crystalline Al, Fe and Mn oxides, the greatest V saturation of sorption sites appeared to occur on the amorphous and poorly crystalline oxide solid phases targeted by the oxalate and oxalate-ascorbic acid extracts respectively. Adsorption isotherm experiments showed no correlation between V sorption and any of the fractions identified by the SEP. This lack of correlation indicates the application of an SEP alone is not adequate to estimate the sorption characteristics of V in an aquifer system.

California↗
USGS2010

Modeling the effects of variable groundwater chemistry on adsorption of molybdate

Laboratory experiments were used to identify and quantify processes having a significant effect on molybdate (MoO 4 2− ) adsorption in a shallow alluvial aquifer on Cape Cod, assachusetts. Aqueous chemistry in the aquifer changes as a result of treated sewage effluent mixing with groundwater. Molybdate adsorption decreased as p H, ionic strength, and the concentration of competing anions increased. A diffuse-layer surface complexation model was used to simulate adsorption of MoO 4 2− , phosphate (PO 4 3− ), and sulfate (SO 4 2− ) on aquifer sediment. Equilibrium constants for the model were calculated by calibration to data from batch experiments. The model was then used in a one-dimensional solute transport program to successfully simulate initial breakthrough of MoO 4 2− from column experiments. A shortcoming of the solute transport program was the inability to account for kinetics of physical and chemical processes. This resulted in a failure of the model to predict the slow rate of desorption of MoO 4 2− from the columns. The mobility of MoO 4 2− ncreased with ionic strength and with the formation of aqueous complexes with calcium, magnesium, and sodium. Failure to account for MoO 4 2− speciation and ionic strength in the model resulted in overpredicting MoO 4 2− adsorption. Qualitatively, the laboratory data predicted the observed behavior of MoO 4 2− in the aquifer, where retardation of MoO 4 2− was greatest in uncontaminated roundwater having low p H, low ionic strength, and low concentrations of PO 4 3− and SO 4 2− .

Water Resources Research↗
USGS2010

Groundwater transport of strontium 90 in a glacial outwash environment

As part of the investigation of groundwater contamination at a uranium-scrap recovery plant at Wood River Junction, Rhode Island, laboratory experiments led to the development of a model for predicting the transport of strontium 90 in glacial outwash sediments based on an approximate mechanism for ion exchange. The multicomponent system was simplified to two components by regarding all exchangeable cations other than strontium 90 as a single component. The binary ion-exchange parameter was a function of the variable, total ion concentration. A one-dimensional solute transport model was formulated to evaluate the time necessary for natural groundwater flow to remove the strontium 90 contamination plume from the groundwater system to the Pawcatuck River. The finite difference transport equations were solved sequentially for total ion concentrations, then strontium 90 concentrations. Clay-free quartz and feldspar sands at the study site have little potential for strontium 90 sorption, and high calcium, magnesium, and sodium concentrations compete for the few ion exchange sites. As the total ion concentration plume moves out of the system, ion exchange of strontium 90 increases, reducing the strontium 90 concentration in the groundwater. Cleanout times predicted using the binary ion exchange mechanism were about two thirds of those predicted using a constant distribution coefficient. It is suggested that this type of model can simulate solute transport more realistically in many groundwater systems where the total ion concentration is not constant.

Rhode Island↗
USGS2010

In-situ arsenic remediation in Carson Valley, Douglas County, west-central Nevada

Conventional arsenic remediation strategies primarily involve above-ground treatment that include costs involved in the disposal of sludge material. The primary advantages of in-situ remediation are that building and maintaining a large treatment facility are not necessary and that costs associated with the disposal of sludge are eliminated. A two-phase study was implemented to address the feasibility of in-situ arsenic remediation in Douglas County, Nevada. Arsenic concentrations in groundwater within Douglas County range from 1 to 85 micrograms per liter. The primary arsenic species in groundwater at greater than 250 ft from land surface is arsenite; however, in the upper 150 ft of the aquifer arsenate predominates. Where arsenite is the primary form of arsenic, the oxidation of arsenite to arsenate is necessary. The results of the first phase of this investigation indicated that arsenic concentrations can be remediated to below the drinking-water standard using aeration, chlorination, iron, and pH adjustment. Arsenic concentrations were remediated to less than 10 micrograms per liter in groundwater from the shallow and deep aquifer when iron concentrations of 3-6 milligrams per liter and pH adjustments to less than 6 were used. Because of the rapid depletion of dissolved oxygen, the secondary drinking-water standards for iron (300 micrograms per liter) and manganese (100 micrograms per liter) were exceeded during treatment. Treatment was more effective in the shallow well as indicated by a greater recovery of water meeting the arsenic standard. Laboratory and field tests were included in the second phase of this study. Laboratory column experiments using aquifer material indicated the treatment process followed during the first phase of this study will continue to work, without exceeding secondary drinking-water standards, provided that groundwater was pre-aerated and an adequate number of pore volumes treated. During the 147-day laboratory experiment, no decrease in flow through the column was observed. The primary mechanism of arsenic removal is through coprecipitation with iron oxide. Calculations based on the results of the column experiments and assuming 10 and 30 percent porosity indicated that treatment of approximately 237,000-714,000 gallons of water would be required in order to remediate arsenic concentrations to less than 10 micrograms per liter. During the first second-phase field experiment, effective injection of treated groundwater back into the aquifer was prevented due to clogging likely caused by entrained gases and the fine texture (sand, clay, and gravel) of the aquifer sediments. Because of the overflow of treated water from the injection wells, only 3,760 gallons of treated water were injected. Immediately upon terminating this first experiment, no arsenic remediation was apparent. However, approximately 24 hours after terminating the experiment arsenic concentrations in groundwater collected from one of the injection wells showed a decrease from about 30 to 15 micrograms per liter, indicating that some remediation had taken place. In agreement with the laboratory-column experiments, pre-aeration prevented the exceedence of the secondary drinking-water standards for iron and manganese. Because of complications associated with system hydraulics, no additional experiments were performed.

Scientific Investigations Report↗
USGS2009

Aquifer chemistry and transport processes in the zone of contribution to a public-supply well in Woodbury, Connecticut, 2002-06

A glacial aquifer system in Woodbury, Connecticut, was studied to identify factors that affect the groundwater quality in the zone of contribution to a community public-supply well. Water samples were collected during 2002-06 from the public-supply well and from 35 monitoring wells in glacial stratified deposits, glacial till, and fractured bedrock. The glacial aquifer is vulnerable to contamination from a variety of sources due to the short groundwater residence times and the urban land use in the contributing recharge area to the public-supply well. The distribution and concentrations of pH, major and trace elements, stable isotope ratios, recharge temperatures, dissolved organic carbon (DOC), and volatile organic compounds (VOCs), and the oxidation-reduction (redox) conditions, were used to identify recharge source areas, aquifer source material, anthropogenic sources, chemical processes, and groundwater-flow paths from recharge areas to the public-supply well, PSW-1. The major chemical sources to groundwater and the tracers or conditions used to identify them and their processes throughout the aquifer system include (1) bedrock and glacial stratified deposits and till, characterized by high pH and concentrations of sulfate (SO42-), bicarbonate, uranium (U), radon-222, and arsenic (As) relative to those of other wells, reducing redox conditions, enriched delta sulfur-34 (d34S) and delta carbon-13 (d13C) values, depleted delta oxygen-18 (d18O) and delta deuterium (dD) values, calcite near saturation, low recharge temperatures, and groundwater ages of more than about 9 years; (2) natural organic matter, either in sediments or in an upgradient riparian zone, characterized by high concentrations of DOC or manganese (Mn), low concentrations of dissolved oxygen (DO) and nitrate (NO3-), enriched d34S values, and depleted d18O and dD values; (3) road salt (halite), characterized by high concentrations of sodium (Na), chloride (Cl-), and calcium (Ca), and indicative chloride/bromide (Cl:Br) mass concentration ratios; (4) septic-system leachate, characterized by high concentrations of NO3-, DOC, Na, Cl-, Ca, and boron (B), delta nitrogen-15 (d15N) and d18O values, and indicative Cl:Br ratios; (5) organic solvent spills, characterized by detections of perchloroethene (PCE), trichloroethene (TCE), and 1,1-dichloroethene (1,1-DCE); (6) gasoline station spills, characterized by detections of fuel oxygenates and occasionally benzene; and (7) surface-water leakage, characterized by enriched d18O and dD values and sometimes high DOC and Mn-reducing conditions. Evaluation of Cl- concentrations and Cl:Br ratios indicates that most samples were composed of mixtures of groundwater and some component of road salt or septic-system leachate. Leachate from septic-tank drainfields can cause locally anoxic conditions with NO3- concentrations of as much as 19 milligrams per liter (mg/L as N) and may provide up to 15 percent of the nitrogen in water from well PSW-1, based on mixing calculations with d15N of NO3-. Most of the water that contributes to PSW-1 is young (less than 7 years) and derived from the glacial stratified deposits. Typically, groundwater is oxic, but localized reducing zones that result from abundances of organic matter can affect the mobilization of trace elements and the degradation of VOCs. Groundwater from fractured bedrock beneath the valley bottom, which is old (more than 50 years), and reflects a Mn-reducing to methanic redox environment, constitutes as much as 6 percent of water samples collected from monitoring wells screened at the bottom of the glacial aquifer. Dissolved As and U concentrations generally are near the minimum reporting level (MRL) (0.2 micrograms per liter or ?g/L and 0.04 ?g/L, respectively), but water from a few wells screened in glacial deposits, likely derived from underlying organic-rich Mesozoic rocks, contain As concentrations up to 7 ?g/L. At one location, concentrations of As and U were high

Scientific Investigations Report↗
USGS2008

Large-scale natural gradient tracer test in sand and gravel, Cape Cod, Massachusetts: 1. Experimental design and observed tracer movement

A large-scale natural gradient tracer experiment was conducted on Cape Cod, Massachusetts, to examine the transport and dispersion of solutes in a sand and gravel aquifer. The nonreactive tracer, bromide, and the reactive tracers, lithium and molybdate, were injected as a pulse in July 1985 and monitored in three dimensions as they moved as far as 280 m down-gradient through an array of multilevel samplers. The bromide cloud moved horizontally at a rate of 0.42 m per day. It also moved downward about 4 m because of density-induced sinking early in the test and accretion of areal recharge from precipitation. After 200 m of transport, the bromide cloud had spread more than 80 m in the direction of flow, but was only 14 m wide and 4–6 m thick. The lithium and molybdate clouds followed the same path as the bromide cloud, but their rates of movement were retarded about 50% relative to bromide movement because of sorption onto the sediments.

Massachusetts↗
USGS2007

Chemical reactions simulated by ground-water-quality models

Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

Water Resources Bulletin↗
USGS2007

Arsenic in the environment: Biology and chemistry

Arsenic (As) distribution and toxicology in the environment is a serious issue, with millions of individuals worldwide being affected by As toxicosis. Sources of As contamination are both natural and anthropogenic and the scale of contamination ranges from local to regional. There are many areas of research that are being actively pursued to address the As contamination problem. These include new methods of screening for As in the field, determining the epidemiology of As in humans, and identifying the risk of As uptake in agriculture. Remediation of As-affected water supplies is important and research includes assessing natural remediation potential as well as phytoremediation. Another area of active research is on the microbially mediated biogeochemical interactions of As in the environment. In 2005, a conference was convened to bring together scientists involved in many of the different areas of As research. In this paper, we present a synthesis of the As issues in the light of long-standing research and with regards to the new findings presented at this conference. This contribution provides a backdrop to the issues raised at the conference together with an overview of contemporary and historical issues of As contamination and health impacts.

Science of the Total Environment↗
USGS2005

Review of the transport of selected radionuclides in the interim risk assessment for the Radioactive Waste Management Complex, Waste Area Group 7 Operable Unit 7-13/14, Idaho National Engineering and Environmental Laboratory, Idaho

The U.S. Department of Energy (DOE) requested that the U.S. Geological Survey conduct an independent technical review of the Interim Risk Assessment (IRA) and Contaminant Screening for the Waste Area Group 7 (WAG-7) Remedial Investigation, the draft Addendum to the Work Plan for Operable Unit 7-13/14 WAG-7 comprehensive Remedial Investigation and Feasibility Study (RI/FS), and supporting documents that were prepared by Lockheed Martin Idaho Technologies, Inc. The purpose of the technical review was to assess the data and geotechnical approaches that were used to estimate future risks associated with the release of the actinides americium, uranium, neptunium, and plutonium to the Snake River Plain aquifer from wastes buried in pits and trenches at the Subsurface Disposal Area (SDA). The SDA is located at the Radioactive Waste Management Complex in southeastern Idaho within the boundaries of the Idaho National Engineering and Environmental Laboratory. Radionuclides have been buried in pits and trenches at the SDA since 1957 and 1952, respectively. Burial of transuranic wastes was discontinued in 1982. The five specific tasks associated with this review were defined in a ?Proposed Scope of Work? prepared by the DOE, and a follow-up workshop held in June 1998. The specific tasks were (1) to review the radionuclide sampling data to determine how reliable and significant are the reported radionuclide detections and how reliable is the ongoing sampling program, (2) to assess the physical and chemical processes that logically can be invoked to explain true detections, (3) to determine if distribution coefficients that were used in the IRA are reliable and if they have been applied properly, (4) to determine if transport model predictions are technically sound, and (5) to identify issues needing resolution to determine technical adequacy of the risk assessment analysis, and what additional work is required to resolve those issues.

Idaho↗
USGS2003

Geochemical processes controlling transport of arsenic in groundwater: A review of adsorption

Adsorption is the predominate mechanism controlling transport of arsenic in many ground water systems. Hydrous oxides of iron, aluminum, and manganese, and clay minerals are commonly associated with aquifer solids and have been shown to be significant adsorbents of arsenic. The extent of arsenic adsorption is influenced by the chemistry of the aqueous phase including pH, arsenic speciation, and the presence and concentration of competing ions. Under moderately reducing conditions, trivalent arsenite is stable and adsorption increases with increasing pH. In an oxidizing environment, arsenate is stable and adsorption decreases with increasing pH. The presence of phosphate, sulfate, carbonate, silica, and other anions have been shown to decrease adsorption of arsenic to varying degrees. The effects of complex aqueous and solid phase chemistry on arsenic adsorption are best simulated using surface complexation models. Coupling of such models with hydrologic solute transport codes provide a powerful method for predicting the spatial and temporal distribution of arsenic in ground water.

Book chapter↗
USGS2003

Arsenic in ground water: Geochemistry and occurrence

Interest in arsenic in ground water has greatly increased in the past decade because of the increased awareness of human health effects and the costs of avoidance or treatment of ground water supplies used for consumption. The goal of this book is to provide a description of the basic processes that affect arsenic occurrence and transport by providing sufficient background information on arsenic geochemistry and descriptions of hi- arsenic ground water, both affected and unaffected by human activity. An understanding of thermodynamics, adsorption, and the speciation of arsenic in solid phases, which are described in first three chapters, is needed to predict the fate of arsenic in ground water systems. Large-scale and deep movement of ground water can and has redistributed arsenic in the near surface environment, as described in the next two chapters. These large-scale systems can affect large volumes of both ground water and surface water, such as in the Yellowstone system, and can produce mineralised zones that subsequently release arsenic to ground water supplies. Regional identification of high-arsenic ground water and its consumption as described in the next three chapters clearly demonstrates a need for increased wat- quality monitoring, particularly in south and southeast Asia. Chapters 9-11 provide examples of high arsenic ground water associated with sulfide mineral oxidation and alkaline conditions. Finally, smaller scale studies of the effects of human activities that have produced high-arsenic ground water and methods for attenuation of ground water are presented

Book↗
USGS2003

Reactive-transport simulation of phosphorus in the sewage plume at the Massachusetts Military Reservation, Cape Cod, Massachusetts

The subsurface transport of phosphorus introduced by the disposal of treated sewage effluent to ground-infiltration disposal beds at the Massachusetts Military Reservation on western Cape Cod was simulated with a three-dimensional reactive-transport model. The simulations were used to estimate the load of phosphorus transported to Ashumet Pond during operation of the sewage-treatment plant from 1936 to 1995 and for 60 years following cessation of sewage disposal. The model accounted for spatial and temporal changes in water discharge from the sewage-treatment plant, ground-water flow, transport of associated chemical constituents, and a set of chemical reactions, including phosphorus sorption on aquifer materials, dissolution and precipitation of iron- and manganese-oxyhydroxide and iron phosphate minerals, organic carbon sorption and decomposition, cation sorption, and irreversible denitrification. The flow and transport in the aquifer were simulated by using parameters consistent with those used in previous flow models of this area of Cape Cod, except that numerical dispersion was much larger than the physical dispersion estimated in previous studies. Sorption parameters were fit to data derived from phosphorus sorption and desorption laboratory column experiments. Rates of organic carbon decomposition were adjusted to match the location of iron concentrations in an anoxic iron zone within the sewage plume. The sensitivity of the simulated load of phosphorus transported to Ashumet Pond was calculated for a variety of processes and input parameters. Model limitations included large uncertainties associated with the loading of the sewage beds, the flow system, and the chemistry and sorption characteristics in the aquifer. The results of current model simulations indicate a small load of phosphorus transported to Ashumet Pond during 1965-85, but this small load was particularly sensitive to model parameters that specify flow conditions and the chemical process by which non-desorbable phosphorus is incorporated in the sediments. The uncertainties were large enough to make it difficult to determine whether loads of phosphorus transported to Ashumet Pond in the 1990s were greater or less than loads during the previous two decades. The model simulations indicate substantial discharge of phosphorus to Ashumet Pond after about 1965. After the period 2000-10 the simulations indicate that the load of phosphorus transported to Ashumet Pond decreases continuously, but the load of phosphorus remains substantial for many decades. The current simulations indicate a peak in phosphorus discharge to Ashumet Pond of about 1,000 kilograms per year during the 1990s; however, comparisons of simulated phosphorus concentrations with measured concentrations in 1993 indicate that the peak in phosphorus load transported to Ashumet Pond may be larger and moving more quickly in the model simulations than in the aquifer. The results of the three-dimensional reactive-transport simulations are consistent with the loading history, experimental laboratory data, and field measurements. The results of the simulations adequately reproduce the spatial distribution of phosphorus concentrations measured in 1993, the magnitude of changes in phosphorus concentration with time in a profile near the disposal beds following cessation of sewage disposal, the observed iron zone in the sewage plume, the approximate flow of treated sewage effluent into Ashumet Valley, and laboratory-column data for phosphorus sorption and desorption.

Massachusetts↗
USGS2003

Natural remediation potential of arsenic-contaminated ground water

Migration of leachate from a municipal landfill in Saco, Maine has resulted in arsenic concentrations in ground water as high as 647 μg/L . Laboratory experimental data indicate the primary source of arsenic to be reductive dissolution of arsenic-enriched iron oxyhydroxides in the aquifer by organic carbon in landfill leachate. A core from an uncontaminated part of the aquifer yielded no dissolved iron or arsenic when leached with oxic ground water. Eluent ground water spiked with organic carbon in order to create reducing conditions mobilized both ferrous iron and arsenite from this core. The landfill was capped in early 1998 to eliminate the source of leachate. Cores from the contaminated portion of the aquifer were collected and leached with uncontaminated ground water in the laboratory to simulate natural remediation conditions. Data from these experiments show that significant concentrations of labile organic carbon have accumulated on aquifer solids, causing significant biological oxygen demand. In laboratory leaching experiments of the most contaminated core, the organic carbon caused complete consumption of the influent dissolved oxygen (6 mg/L) for 220 pore volumes. Arsenic leaching from contaminated cores rapidly decreased in concentration initially in response to flushing with uncontaminated ground water. Subsequent leaching produced more gradual decreases in dissolved arsenic concentrations, controlled by a combination of reductive dissolution of arsenic-enriched iron oxyhydroxides and adsorption/desorption. In leachate from the most contaminatedcore, arsenic concentrations exceeded the new United States Environmental Protection Agency drinking-water standard of 10 μg/L for more than 200 pore volumes. A geochemical model simulated the concentration of selected constituents as uncontaminated ground water eluted through contaminated aquifer solids. Concentrations of dissolved oxygen, arsenic, and iron, in leachate from one core were used to calibrate the model. This model was validated by successfully simulating constituent concentrations in leachate from cores collected from other contaminated areas of this aquifer.

Saco↗
USGS1996

Geochemical and hydrologic controls on phosphorus transport in a sewage-contaminated sand and gravel aquifer near Ashumet Pond, Cape Cod, Massachusetts

Currently (1993), about 170 kg/yr of phosphorus discharges into Ashumet Pond on Cape Cod from a plume of sewage-contaminated ground water. Phosphorus in the plume is mobile in two distinct geochemical environments--an anoxic zone containing dissolved iron and a suboxic zone containing dissolved oxygen. Phosphorus mobility in the suboxic zone is due to saturation of available sorption sites. Phosphorus loading to Ashumet Pond may increase significantly after sewage disposal is stopped due to phosphorus desorption from sediment surfaces.

Massachusetts↗
USGS1994

Geochemical interactions between constituents in acidic groundwater and alluvium in an aquifer near Globe, Arizona

Acidic water from a copper-mining area has contaminated an alluvial aquifer and stream near Globe, Arizona. The most contaminated groundwater has a pH of 3.3, and contains about 100 mmol/1 SO 4 , 50 mmol/1 Fe, 11 mmol/1 Al and 3 mmol/1 Cu. Reactions between alluvium and acidic groundwater were first evaluated in laboratory column experiments. A geochemical model was developed and used in the equilibrium speciation program, MINTEQA2, to simulate breakthrough curves for different constituents from the column. The geochemical model was then used to simulate the measured changes in concentration of aqueous constituents along a flow path in the aquifer. The pH was predominantly controlled by reaction with carbonate minerals. Where carbonates had been dissolved, adsorption of H + by iron oxides was used to simulate pH. Acidic groundwater contained little or no dissolved oxygen, and most aqueous Fe was present as Fe(II). In the anoxic core of the plume, Fe(II) was oxidized by MnO 2 to Fe(III), which then precipitated as Fe(OH) 3 . Attenuation of aqueous Cu, Co, Mn, Ni and Zn was a function of pH and could be quantitatively modeled with the diffuse-layer, surface complexation model in MINTEQA2. Aluminum precipitated as amorphous Al(OH) 3 at pH < 4.7 and as AlOHSO 4 at pH < 4.7. Aqueous Ca and SO 4 were close to equilibrium with gypsum. After the alluvium in the column had reached equilibrium with acidic groundwater, uncontaminated groundwater was eluted through the column to evaluate the effect of reactants on groundwater remediation. The concentration of Fe, Mn, Cu, Co, Ni and Zn rapidly decreased to the detection limits within a few pore volumes. All of the gypsum that had precipitated initially redissolved, resulting in elevated Ca and SO 4 concentrations for about 5 pore volumes. Aluminum and pH exhibited the most potential for continued adverse effects on groundwater quality. As H + desorbed from Fe(OH) 3 , pH remained below 4.5 for more than 20 pore volumes, resulting in dissolution of AlOHSO 4 and elevated aqueous Al.

Applied Geochemistry↗