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USGS2023

Contaminant risks in consuming fish from the Area of Concern in the Upper Niagara River

The lack of contemporary data on contaminants in resident fish prevents an analysis of temporal trends in contaminant concentrations and the present-day status of the “Restrictions on Fish and Wildlife Consumption” Beneficial Use Impairment (BUI) in the Niagara River Area of Concern (AOC). During 2018, concentrations of 260 contaminants in four groups of fish species from five areas in or near the upper Niagara River AOC were analyzed to determine the potential risks from fish consumption, responses to remediation in an adjacent AOC, and whether additional remedial actions were warranted in this AOC. The concentrations of most contaminants were generally undetectable or did not exceed established Federal, State, or European Union fish-consumption limits. Several contaminants without State or Federal limits exceeded European Union fish-consumption guidelines in some species and areas. High PCB residues in many bullhead from Scajaquada Creek, some bass from Hoyt Lake, and most common carp from all areas surpassed certain New York and Federal fish-consumption limits and indicate PCBs continue to restrict fish consumption at most study areas. High concentrations of several contaminants in resident fish, especially dioxins and furans in carp, from Cayuga Creek indicate that additional scrutiny of consumption advisories is warranted in this area. Because this study provides a snapshot in time of fish-contaminant data from five areas, additional data from other areas and times, and more detailed information on present-day pollutant sources may be needed before determining the status of the fish-consumption BUI in this AOC.

New York↗

USGS2012

Transport of ARS-labeled hydroxyapatite nanoparticles in saturated granular media is influenced by surface charge variability even in the presence of humic acid

Hydroxyapatite nanoparticle (nHAP) is increasingly being used to remediate soils and water polluted by metals and radionuclides. The transport and retention of Alizarin red S (ARS)-labeled nHAP were investigated in water-saturated granular media. Experiments were carried out over a range of ionic strength ( I c , 0–50 mM NaCl) conditions in the presence of 10 mg L −1 humic acid. The transport of ARS-nHAP was found to decrease with increasing suspension I c in part, because of enhanced aggregation and chemical heterogeneity. The retention profiles (RPs) of ARS-nHAP exhibited hyperexponential shapes (a decreasing rate of retention with increasing transport distance) for all test conditions, suggesting that some of the attachment was occurring under unfavorable conditions. Surface charge heterogeneities on the collector surfaces and especially within the ARS-nHAP population were contributing causes for the hyperexponential RPs. Consideration of the effect(s) of I c in the presence of HA is needed to improve the efficacy of nHAP for scavenging metals and actinides in real soils and groundwater environments.

Journal of Hazardous Materials↗

USGS2021

Seasonal movements of muskellunge in the St. Clair – Detroit River System: Implications for multi-jurisdictional fisheries management

The St. Clair-Detroit River System contains a world-class Great Lakes muskellunge ( Esox masquinongy ) fishery that has avoided the declines observed in many Great Lakes muskellunge populations. Muskellunge are an upper trophic level predator, and therefore a naturally low-density species. Limited fishery-independent data exist on which to base management decisions. To remedy this, we initiated an acoustic telemetry study in May of 2016, in collaboration with the Great Lakes Acoustic Telemetry Observation System. Our objective was to describe patterns of movement of muskellunge in this large and open system to better understand their spatial ecology. We acoustically tagged 133 muskellunge in the Detroit River and Lake St. Clair, and movements of 58 fish that passed our data quality control screens were analyzed. We utilized mixed modelling to assess the effects of sex, length, release location, and season on daily movement rates. We found that movement rates only differed among seasons, with highest movement rates occurring in the fall and lowest movement rates in the winter. Muskellunge tagged at different locations exhibited distinct residency patterns, and fish frequently crossed jurisdictional and waterbody boundaries. Ultimately our study highlights the scope and patterns of muskellunge movement in a large, unimpounded system and demonstrates that management of these fish would benefit from consideration of their full distribution covering multiple management jurisdictions.

Michigan, Ontario↗

USGS2007

Assessment of contamination from arsenical pesticide use on orchards in the great valley region, Virginia and West Virginia, USA

Lead arsenate pesticides were widely used in apple orchards from 1925 to 1955. Soils from historic orchards in four counties in Virginia and West Virginia contained elevated concentrations of As and Pb, consistent with an arsenical pesticide source. Arsenic concentrations in approximately 50% of the orchard site soils and approximately 1% of reference site soils exceed the USEPA Preliminary Remediation Goal (PRG) screening guideline of 22 mg kg-1 for As in residential soi, defined on the basis of combined chronic exposure risk. Approximately 5% of orchard site soils exceed the USEPA PRG for Pb of 400 mg kg-1 in residential soil; no reference site soils sampled exceed this value. A variety of statistical methods were used to characterize the occurrence, distribution, and dispersion of arsenical pesticide residues in soils, stream sediments, and ground waters relative to landscape features and likely background conditions. Concentrations of Zn, Pb, and Cu were most strongly associated with high developed land density and population density, whereas elevated concentrations of As were weakly correlated with high orchard density, consistent with a pesticide residue source. Arsenic concentrations in ground water wells in the region are generally <0.005 mg L-1. There was no spatial association between As concentrations in ground water and proximity to orchards. Arsenic had limited mobility into ground water from surface soils contaminated with arsenical pesticide residues at concentrations typically found in orchards.

Journal of Environmental Quality↗

USGS2017

Assessing condition of macroinvertebrate communities and bed sediment toxicity in the Rochester Embayment Area of Concern, New York, USA

The United States and Canada agreed to restore the chemical, physical, and biological integrity of the Great Lakes ecosystem under the first Great Lakes Water Quality Agreement in 1972. The lowest reach of the Genesee River and the Rochester Embayment on Lake Ontario between Bogus Point and Nine Mile Point, including Braddock Bay, were designated as an Area of Concern (AOC) due to effects of contaminated sediments and physical disturbance on several beneficial uses. Following sediment remedial efforts and with conditions improving in the AOC, the present study was conducted to reevaluate the status of the benthic macroinvertebrate (benthos) beneficial use impairment (BUI). Benthic macroinvertebrate community assessments and 10-day Chironomus dilutus bioassays were used to test the hypotheses that sediments within the AOC were no more toxic than sediments from surrounding reference areas. The study was separated into three discrete systems (Genesee River, Lake Ontario, and Braddock Bay) and non-parametric analyses determined that a multimetric index of benthic macroinvertebrate community integrity was significantly higher at AOC sites compared to reference sites on the Genesee River and in Braddock Bay while AOC and reference sites on Lake Ontario did not differ significantly. Survival and growth of C. dilutus were also similar between AOC and reference sites for each system with the exception of significantly higher growth at reference sites on Lake Ontario. Results generally indicated that the condition of benthos and toxicity of sediment of the Rochester Embayment AOC are similar to or better than that in the surrounding area.

New York↗

USGS2006

Simulation of solute transport across low-permeability barrier walls

Low-permeability, non-reactive barrier walls are often used to contain contaminants in an aquifer. Rates of solute transport through such barriers are typically many orders of magnitude slower than rates through the aquifer. Nevertheless, the success of remedial actions may be sensitive to these low rates of transport. Two numerical simulation methods for representing low-permeability barriers in a finite-difference groundwater-flow and transport model were tested. In the first method, the hydraulic properties of the barrier were represented directly on grid cells and in the second method, the intercell hydraulic-conductance values were adjusted to approximate the reduction in horizontal flow, allowing use of a coarser and computationally efficient grid. The alternative methods were tested and evaluated on the basis of hypothetical test problems and a field case involving tetrachloroethylene (PCE) contamination at a Superfund site in New Hampshire. For all cases, advective transport across the barrier was negligible, but preexisting numerical approaches to calculate dispersion yielded dispersive fluxes that were greater than expected. A transport model (MODFLOW-GWT) was modified to (1) allow different dispersive and diffusive properties to be assigned to the barrier than the adjacent aquifer and (2) more accurately calculate dispersion from concentration gradients and solute fluxes near barriers. The new approach yields reasonable and accurate concentrations for the test cases.

Journal of Contaminant Hydrology↗

USGS2003

The role of microbial reductive dechlorination of TCE at a phytoremediation site

In April 1996, a phytoremediation field demonstration site at the Naval Air Station, Fort Worth, Texas, was developed to remediate shallow oxic ground water (<3.7 m deep) contaminated with chlorinated ethenes. Microbial populations were sampled in February and June 1998. The populations under the newly planted cottonwood trees had not yet matured to an anaerobic community that could dechlorinate trichloroethene (TCE) to cis -1,2-dichloroethene (DCE); however, the microbial population under a mature (∼22-year-old) cottonwood tree about 30 m southwest of the plantings had a mature anaerobic population capable of dechlorinating TCE to DCE, and DCE to vinyl chloride (VC). Oxygen-free sediment incubations with contaminated groundwater also demonstrated that resident microorganisms were capable of the dechlorination of TCE to DCE. This suggests that a sufficient amount of organic material is present for microbial dechlorination in aquifer microniches where dissolved O 2 concentrations are low. Phenol, benzoic acid, acetic acid, and a cyclic hydrocarbon, compounds consistent with the degradation of root exudates and complex aromatic compounds, were identified by gas chromatography/mass spectrometry (GC/MS) in sediment samples under the mature cottonwood tree. Elsewhere at the site, transpiration and degradation by the cottonwood trees appears to be responsible for loss of chlorinated ethenes.

Texas↗

USGS2020

Assessment of two techniques for remediation of lacustrine rocky reef spawning habitat

Rocky reef habitats in lacustrine systems constitute important areas for lithophilic‐spawning fishes. Interstitial spaces created by the structure of rocky reefs form microenvironments where incubating embryos and juvenile fish are potentially protected from predators and physical displacement. However, if interstitial spaces are filled or blocked by sediment or biofouling, the reef structure may lose these benefits. Common practices to restore reef habitat include augmentation of existing reef structures or construction of new reefs, though these practices can be costly. We explored an alternative approach for reef remediation. In 2018, we developed two benthic sled cleaning devices that used either propulsion or pressurized water jets and were towed behind a small vessel to clean reefs. We used the devices to clean two impaired natural rocky reefs in Saginaw Bay, Lake Huron. We indexed effectiveness of cleaning by measured changes in substrate relative hardness before and after cleaning. A biological response to reef cleaning was also measured by egg deposition of fall (Lake Whitefish Coregonus clupeaformis ) and spring (Walleye Sander vitreus ) lithophilic spawners. We found that our propulsion cleaning device was more effective in increasing substrate relative hardness than was the water jet device, although this was not consistent among all study locations. We also found that egg deposition on study plots was variable, but in general, egg deposition was highest on study plots that had the greatest increases in relative hardness post‐cleaning. The practicality of cleaning devices is likely related to the magnitude of site‐specific degradation. Our results indicate that the use of these or similar devices can potentially increase the quality of spawning habitat by displacing sediments that have deposited on reef structures.

North American Journal of Fisheries Management↗

USGS2012

Time series geophysical monitoring of permanganate injections and in situ chemical oxidation of PCE, OU1 area, Savage Superfund Site, Milford, NH, USA

In situ chemical oxidation (ISCO) treatment with sodium permanganate, an electrically conductive oxidant, provides a strong electrical signal for tracking of injectate transport using time series geophysical surveys including direct current (DC) resistivity and electromagnetic (EM) methods. Effective remediation is dependent upon placing the oxidant in close contact with the contaminated aquifer. Therefore, monitoring tools that provide enhanced tracking capability of the injectate offer considerable benefit to guide subsequent ISCO injections. Time-series geophysical surveys were performed at a superfund site in New Hampshire, USA over a one-year period to identify temporal changes in the bulk electrical conductivity of a tetrachloroethylene (PCE; also called tetrachloroethene) contaminated, glacially deposited aquifer due to the injection of sodium permanganate. The ISCO treatment involved a series of pulse injections of sodium permanganate from multiple injection wells within a contained area of the aquifer. After the initial injection, the permanganate was allowed to disperse under ambient groundwater velocities. Time series geophysical surveys identified the downward sinking and pooling of the sodium permanganate atop of the underlying till or bedrock surface caused by density-driven flow, and the limited horizontal spread of the sodium permanganate in the shallow parts of the aquifer during this injection period. When coupled with conventional monitoring, the surveys allowed for an assessment of ISCO treatment effectiveness in targeting the PCE plume and helped target areas for subsequent treatment.

New Hampshire↗

USGS2002

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: Groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally attenuated by a combination of active anaerobic and aerobic biotransformation processes. ?? 2002 Elsevier Science B.V. All rights reserved.

Journal of Contaminant Hydrology↗

USGS2017

Porosity and pore size distribution in a sedimentary rock: Implications for the distribution of chlorinated solvents

Characterizing properties of the rock matrix that control retention and release of chlorinated solvents is essential in evaluating the extent of contamination and the application of remediation technologies in fractured rock. Core samples from seven closely spaced boreholes in a mudstone subject to trichloroethene (TCE) contamination were analyzed using Mercury Intrusion Porosimetry to investigate porosity and pore size distribution as a function of mudstone characteristics, and depth and lateral extent in the aquifer; organic carbon content was also evaluated to identify the potential for adsorption. Porosity and retardation factor varied over two orders of magnitude, with the largest porosities and largest retardation factors associated with carbon-rich mudstone layers. Larger porosities were also measured in the shallow rock that has been subject to enhanced groundwater flow. Porosity also varied over more than an order of magnitude in spatially continuous mudstone layers. The analyses of the rock cores indicated that the largest pore diameters may be accessible to entry of the nonaqueous form of TCE. Although the porosity associated with the largest pore diameters is small (~ 0.1%), that volume of TCE can significantly affect the total TCE that is retained in the rock matrix. The dimensions of the largest pore diameters may also be accessible to microbes responsible for reductive dechlorination; however, the small percentage of the pore space that can accommodate microbes may limit the extent of reductive dechlorination in the rock matrix.

Journal of Contaminant Hydrology↗

USGS2025

Borehole geophysical time-series logging to monitor passive ISCO treatment of residual chlorinated-ethenes in a confining bed, NAS Pensacola, Florida

In-situ chemical oxidation (ISCO) is a common method to remediate chlorinated ethene contaminants in groundwater. Monitoring the effectiveness of ISCO can be hindered because of insufficient observations to assess oxidant delivery. Advantageously, potassium permanganate, one type of oxidant, provides the opportunity to use its strong electrical signal as a surrogate to track oxidant delivery using time-series borehole geophysical methods, like electromagnetic (EM) induction logging. Here we report a passive ISCO (P-ISCO) experiment, using potassium permanganate cylinders emplaced in boreholes, at a chlorinated ethene contamination site, Naval Air Station Pensacola, Florida. The contaminants are found primarily at the base of a shallow sandy aquifer in contact with an underlying silty-clay confining bed. We used results of the time-series borehole logging collected between 2017 and 2022 in 4 monitoring wells to track oxidant delivery. The EM-induction logs from the monitoring wells showed an increase in EM response primarily along the contact, likely from pooling of the oxidant, during P-ISCO treatment in 2021. Interestingly, concurrent natural gamma-ray (NGR) logging showed a decrease in NGR response at 3 of the 4 wells possibly from the formation of manganese precipitates coating sediments. The coupling of time-series logging and well-chemistry data allowed for an improved assessment of passive ISCO treatment effectiveness.

Florida↗

USGS2000

Phreatophyte influence on reductive dechlorination in a shallow aquifer contaminated with trichloroethene (TCE)

Phytoremediation uses the natural ability of plants to degrade contaminants in groundwater. A field demonstration designed to remediate aerobic shallow groundwater contaminated with trichloroethene began in April 1996 with the planting of cottonwood trees, a short-rotation woody crop, over an approximately 0.2-ha area at the Naval Air Station, Fort Worth, Texas. The project was developed to demonstrate capture of contaminated groundwater and degradation of contaminants by phreatophytes. Analyses from samples of groundwater collected from July 1997 to June 1998 indicate that tree roots have the potential to create anaerobic conditions in the groundwater that will facilitate degradation of trichloroethene by microbially mediated reductive dechlorination. Organic matter from root exudates and decay of tree roots probably stimulate microbial activity, consuming dissolved oxygen. Dissolved oxygen concentrations, which varied across the site, were smallest near a mature cottonwood tree (about 20 years of age and 60 meters southwest of the cottonwood plantings) where degradation products of trichloroethene were measured. Oxidation of organic matter is the primary microbially mediated reaction occurring in the groundwater beneath the planted trees whereas near the mature cottonwood tree, data indicate that methanogenesis is the most probable reaction occurring. Reductive dechlorination in groundwater either is not occurring or is not a primary process away from the mature tree. Carbon-13 isotope values for trichloroethene are nearly identical at locations away from the mature tree, further confirming that dechlorination is not occurring at the site.

Texas↗

USGS2017

Understanding and finding solutions to the problem of sedimentation in the National Wildlife Refuge System

The National Wildlife Refuge System (Refuge System) is a collection of public lands maintained by the U.S. Fish and Wildlife Service for migratory birds and other wildlife. Wetlands on individual National Wildlife Refuges (Refuges) may be at risk of increased sedimentation because of land use and water management practices. Increased sedimentation can reduce wetland habitat quality by altering hydrologic function, degrading water quality, and inhibiting growth of vegetation and invertebrates. On Refuges negatively affected by increased sedimentation, managers have to address complex questions about how to best remediate and mitigate the negative effects. The best way to account for these complexities is often not clear. On other Refuges, managers may not know whether sedimentation is a problem. Decision makers in the Refuge System may need to allocate resources to studying which Refuges could be at risk. Such analyses would help them understand where to direct support for managing increased sedimentation. In this paper, we summarize a case study demonstrating the use of decision-analytic tools in the development of a sedimentation management plan for Agassiz National Wildlife Refuge, Minnesota. Using what we learned from that process, we surveyed other Refuges in U.S. Fish and Wildlife Service Region 3 (an area encompassing the states of Illinois, Indiana, Iowa, Ohio, Michigan, Minnesota, Missouri, and Wisconsin) and Region 6 (an area encompassing the states of Colorado, Kansas, Montana, Nebraska, North Dakota, South Dakota, Utah, and Wyoming) about whether they experience sediment-related impacts to management. Our results show that cases of management being negatively affected by increased sedimentation are not isolated. We suggest that the Refuge System conduct a comprehensive and systematic assessment of increased sedimentation among Refuges to understand the importance of sedimentation in context with other management problems that Refuges face. The results of such an assessment could guide how the Refuge System allocates resources to studying and managing widespread stressors.

Minnesota↗

USGS2025

anadrofish: Anadromous fish population responses to dams

Diadromous fishes world-wide experienced precipitous declines during the 19th and 20th centuries due to a combination of overfishing, pollution, and freshwater habitat loss through construction of dams (Limburg & Waldman, 2009). Following wide-spread fishing closures and large-scale remediation of many historical pollution sources, dams in coastal rivers remain as the largest tractable impediment to population recovery for many of these species (Waldman & Quinn, 2022). In some cases, dams reduce access to as much as 95% of freshwater and rearing habitat (Hall et al., 2011). These effects are especially pronounced for species that rely on long-distance migrations to spawning and rearing habitat upstream of barriers such as various alosines (herrings; e.g., American shad Alosa sapidissima , alewife A. pseudoharengus , and blueback herring A. aestivalis (Noonan et al., 2012)) and salmonines (trout and salmon; e.g., Salmo spp. (Parrish et al., 1998) and Oncorhynchus spp. (Quiñones et al., 2015). Traditional stock assessment tools such as per-recruit analyses often fail to capture management complexities related to diadromous life histories such as fish passage at dams, and integrated assessment models can be difficult to parameterize for data-poor species such as herrings (Atlantic States Marine Fisheries Commission, 2024). This has resulted in the development of species- and system-specific approaches to fisheries stock assessment and management strategy evaluation (Barber et al., 2018; Nieland et al., 2015; Roy et al., 2018; Stich et al., 2019). We created the anadrofish package (Stich, Hardesty, et al., 2025) for R (R Core Team, 2025) to provide a generalized approach that also allows broader application to novel species, systems, and scenarios.

Journal of Open Source Software↗

USGS2011

A distribution-based parameterization for improved tomographic imaging of solute plumes

Difference geophysical tomography (e.g. radar, resistivity and seismic) is used increasingly for imaging fluid flow and mass transport associated with natural and engineered hydrologic phenomena, including tracer experiments, in situ remediation and aquifer storage and recovery. Tomographic data are collected over time, inverted and differenced against a background image to produce ‘snapshots’ revealing changes to the system; these snapshots readily provide qualitative information on the location and morphology of plumes of injected tracer, remedial amendment or stored water. In principle, geometric moments (i.e. total mass, centres of mass, spread, etc.) calculated from difference tomograms can provide further quantitative insight into the rates of advection, dispersion and mass transfer; however, recent work has shown that moments calculated from tomograms are commonly biased, as they are strongly affected by the subjective choice of regularization criteria. Conventional approaches to regularization (Tikhonov) and parametrization (image pixels) result in tomograms which are subject to artefacts such as smearing or pixel estimates taking on the sign opposite to that expected for the plume under study. Here, we demonstrate a novel parametrization for imaging plumes associated with hydrologic phenomena. Capitalizing on the mathematical analogy between moment-based descriptors of plumes and the moment-based parameters of probability distributions, we design an inverse problem that (1) is overdetermined and computationally efficient because the image is described by only a few parameters, (2) produces tomograms consistent with expected plume behaviour (e.g. changes of one sign relative to the background image), (3) yields parameter estimates that are readily interpreted for plume morphology and offer direct insight into hydrologic processes and (4) requires comparatively few data to achieve reasonable model estimates. We demonstrate the approach in a series of numerical examples based on straight-ray difference-attenuation radar monitoring of the transport of an ionic tracer, and show that the methodology outlined here is particularly effective when limited data are available.

Geophysical Journal International↗

USGS2021

Evaluation of a modified rapid viability-polymerase chain reaction method for Bacillus atrophaeus spores in water matrices

A rapid method that provides information on the viability of organisms is needed to protect public health and ensure that remediation efforts following a release of a biological agent are effective. The rapid viability-polymerase chain reaction (RV-PCR) method combines broth culture and molecular methods to provide results on whether viable organisms are present in less than 15 h. In this study, a modified RV-PCR (mRV-PCR) method was compared to a membrane-filtration culture method for the detection of viable Bacillus spores in water matrices. Samples included small and large volumes of chlorine and non‑chlorine treated tap water. Large volume water samples (up to 100 L), were processed by ultrafiltration using a semi-automated waterborne pathogen concentrator, followed by centrifugation as a secondary concentration technique. The concentrated samples were analyzed by mRV-PCR and culture methods. The overall agreement between the mRV-PCR and culture methods when seed concentrations were greater than 10 spores per sample volume analyzed was 96%. The total time from the start of sample processing to the final sample result for the mRV-PCR method was decreased by approximately 2 h, in comparison to the previously published RV-PCR method because of the incorporation of shorter, more efficient primary and secondary concentration steps and a shorter DNA extraction technique. Overall, this study confirmed that RV-PCR is a promising approach for identifying viable Bacillus spores in small- and large-volume water samples and for producing results in less time than traditional culture methods.

Journal of Microbiological Methods↗

USGS1998

Analysis and simulation of reactive transport of metal contaminants in ground water in Pinal Creek Basin, Arizona

Large-scale mining activities have generated a plume of acidic ground water more than 15 km long in the regional aquifer of the Pinal Creek Basin. A one-dimensional reactive-transport model was developed using PHREEQC to aid in the analysis of transport and chemical processes in the plume and to determine the uses and limitations of this type of modeling approach. In 1984, the acidic part of the plume had a pH as low as 3.4 and contained milligram-per-liter concentrations of iron, copper, aluminum and other metals. From 1984 to 1994, concentrations of contaminants in the alluvial aquifer in Pinal Creek Basin, Arizona, decreased as a result of mixing, recharge, remedial pumping and chemical reactions. For reactions involving gypsum and rhodochrosite, the equilibrium modeling assumption of a local geochemical equilibrium was generally valid. From 1984 to 1990, water along the simulated flow path was at equilibrium or slightly supersaturated with gypsum, and gypsum equilibria controlled dissolved concentrations of calcium and sulfate. Beginning in 1991, water in the acidic part of the plume became increasingly undersaturated with respect to gypsum, indicating that the gypsum available for dissolution in the aquifer may have been completely consumed by about 1991. Rhodochrosite precipitation was thought responsible for the measured attenuation in dissolved manganese in the neutralized zone. For reactions involving calcite, the assumption of a local geochemical equilibrium was generally not valid. Dissolution of calcite in the transition zone was not sufficient to establish equilibrium although, following neutralization, the calcite saturation index decreased to −1.2 in 1986. Calcite undersaturation decreased along the flow path in the neutralized zone, and equilibrium was attained about 7 km downgradient of the transition zone. The assumption of a local geochemical equilibrium was not valid for oxidation–reduction reactions that involved iron oxides and manganese oxides. Kinetically controlled oxidation–reduction reactions continued in the acidic part of the flow path for years following the passage of the transition zone. Although the equilibrium approach helped to provide an increased understanding of contaminant transport at Pinal Creek, future work will require a kinetic modeling approach to more accurately simulate selected reactions between the plume and aquifer materials.

Arizona↗