Viability and metal reduction of Shewanella oneidensis MR-1 under CO2 stress: implications for ecological effects of CO2 leakage from geologic CO2 sequestration

To study potential ecological impacts of CO(2) leakage to shallow groundwater and soil/sediments from geologic CO(2) sequestration (GCS) sites, this work investigated the viability and metal reduction of Shewanella oneidensis MR-1 under CO(2) stress. While MR-1 could grow under high-pressure nitrogen gas (500 psi), the mix of 1% CO(2) with N(2) at total pressures of 15 or 150 psi significantly suppressed the growth of MR-1, compared to the N(2) control. When CO(2) partial pressures were over 15 psi, the growth of MR-1 stopped. The reduced bacterial viability was consistent with the pH decrease and cellular membrane damage under high pressure CO(2). After exposure to 150 psi CO(2) for 5 h, no viable cells survived, the cellular contents were released, and microscopy images confirmed significant cell structure deformation. However, after a relatively short exposure (25 min) to 150 psi CO(2), MR-1 could fully recover their growth within 24 h after the stress was removed, and the reduction of MnO(2) by MR-1 was observed right after the stress was removed. Furthermore, MR-1 survived better if the cells were aggregated rather than suspended, or if pH buffering minerals, such as calcite, were present. To predict the cell viability under different CO(2) pressures and exposure times, a two-parameter mathematical model was developed.     

Potential restrictions for CO2 sequestration sites due to shale and tight gas production

Carbon capture and geological sequestration is the only available technology that both allows continued use of fossil fuels in the power sector and reduces significantly the associated CO(2) emissions. Geological sequestration requires a deep permeable geological formation into which captured CO(2)can be injected, and an overlying impermeable formation, called a caprock, that keeps the buoyant CO(2) within the injection formation. Shale formations typically have very low permeability and are considered to be good caprock formations. Production of natural gas from shale and other tight formations involves fracturing the shale with the explicit objective to greatly increase the permeability of the shale. As such, shale gas production is in direct conflict with the use of shale formations as a caprock barrier to CO(2) migration. We have examined the locations in the United States where deep saline aquifers, suitable for CO(2) sequestration, exist, as well as the locations of gas production from shale and other tight formations. While estimated sequestration capacity for CO(2) sequestration in deep saline aquifers is large, up to 80% of that capacity has areal overlap with potential shale-gas production regions and, therefore, could be adversely affected by shale and tight gas production. Analysis of stationary sources of CO(2) shows a similar effect: about two-thirds of the total emissions from these sources are located within 20 miles of a deep saline aquifer, but shale and tight gas production could affect up to 85% of these sources. These analyses indicate that colocation of deep saline aquifers with shale and tight gas production could significantly affect the sequestration capacity for CCS operations. This suggests that a more comprehensive management strategy for subsurface resource utilization should be developed.     

Using chemical and isotopic data to quantify ionic trapping of injected carbon dioxide in oil field brines

Injection of carbon dioxide into depleted oil fields or deep saline aquifers represents one of the most promising means of long-term storage of this greenhouse gas. While the ultimate goal of CO2 injection in the subsurface is mineral storage of CO2 as carbonates, short-term (<50 year) storage of injected CO2 is most likely to be accomplished by ionic trapping of CO2 as bicarbonate ions (HCO3-) and hydrogeological trapping of molecular CO2. Here, we demonstrate a technique for quantifying ionic trapping of injected CO2 as HCO3- using geochemical data collected prior to and during 40 months of CO2 injection into a hydrocarbon reservoir at the International Energy Agency (IEA) Weyburn CO2 Monitoring and Storage Project, Saskatchewan, Canada. As a result of injection of CO2 with a low carbon isotope ratio (delta13C value), fluid and gas samples from four selected production wells showed an increase in HCO3- concentration and a decrease in delta13C values of HCO3- and CO2 over the observation period. Isotope and mass balance calculations indicate that, after 40 months of injection, approximately 80% of the HCO3- in the reservoir brines sampled from the four wells formed via dissolution and dissociation of injected CO2. This chemical and isotopic technique should be applicable to CO2 injection and storage in oil fields and in deep saline aquifers, provided there is sufficient carbon isotopic distinction between injected CO2 and baseline aquifer HCO3- and CO2.     

Environmental controls of cadmium desorption during CO₂ leakage

Geologic carbon sequestration represents a promising option for carbon mitigation. Injected CO(2), however, can potentially leak into water systems, increase water acidity, and mobilize metals. This study used column experiments to quantify the effects of environmental controls on cadmium desorption during CO(2) leakage in subsurface systems without ambient flow. Results show that fast leakage rates are responsible for earlier and larger amounts of Cd desorption. Long weathering time of Cd laden clay leads to low Cd desorption. Calcite content as low as 10% can mitigate the effect of pH reduction and result in zero Cd desorption. Increasing the salinity of the leaking fluid has a relatively minor effect, primarily due to the offsetting impacts of an increased extent of ion exchange and the decrease in CO(2) solubility (and therefore acidity). This work systematically quantifies, for the first time, the effects of environmental controls on Cd desorption and points to key parameters for risk assessment associated with metal mobilization during CO(2) leakage.     

Biofilm hydrous manganese oxyhydroxides and metal dynamics in acid rock drainage

Biofilms in shallow, tailings-associated acid rock drainage (ARD) accumulated metals from May to September, indicating scavenging is stable within these biological solids over seasonal time frames. Results indicate a doubling (Mn, Cr) to over a 6-fold increase (Ni, Co) in biofilm metal concentrations. Biofilm oxygen and pH gradients measured over diel time scales with microelectrodes were observed to be both spatially and temporally variable, indicating that biofilms are highly dynamic geochemical environments. Biofilm metal retention and affinities were element specific indicating different processes control their sequestration. Metals were specifically scavenged by the organic constituents of the biofilm itself (Ni, Co) and associated biominerals of amorphous Mn oxyhydroxides (HMO; Ni, Co, and Cr). Results are consistent with sorption and coprecipitation processes controlling Ni and Co biofilm association, while Cr dynamics appear linked to those of Mn through redox processes. Biofilm HMO concentrations increased seasonally but showed significant diel fluctuations, indicating that both formation and dissolution processes occurred over rapid time scales in these biofilms. Biofilm HMO concentrations increased nocturnally but decreased during daylight hours to late afternoon minima. Under the geochemical conditions of the streams, observed HMO formation rates can only be explained by microbial catalysis. These results are the first to quantitatively examine microbial biofilm metal dynamics using microscale, geochemical techniques at both diel and seasonal time scales. They provide strong evidence for the significant role that microbial activity can play in metal geochemistry in natural environments.     

Characterizing dissolved Cu and Cd uptake in terms of the biotic ligand and biodynamics using enriched stable isotopes

The biotic ligand model considers the biological and geochemical complexities that affect metal exposure. It relates toxicity to the fraction of physiological active sites impacted by reactive metal species. The biodynamic model is a complementary construct that predicts bioaccumulation and assumes that toxicity occurs when influx rates exceed rates of loss and detoxification. In this paper we presume that metal influx rates are mechanistically the resulting processes that characterize transmembrane transport. We use enriched stable isotopes to characterize, both in terms of the biotic ligand and biodynamics, dissolved metal uptake by a freshwater snail at water hardness varying up to 180-fold. Upon 24 h exposure, metal uptake was linear over a range encompassing most environmental concentrations; although saturation kinetics were observed at higher concentrations. Cadmium influx rates correlate with changes in the affinity of the biotic ligand, whereas those of Cu correlate with changes in both site affinity and capacity. A relationship between metal influx rate and ligand character asks whether toxicity is the result of accumulation at the biotic ligand or the rate at which metal is transported by that ligand.     

Development of a hybrid process and system model for the assessment of wellbore leakage at a geologic CO2 sequestration site

Sequestration of CO2 in geologic reservoirs is one of the promising technologies currently being explored to mitigate anthropogenic CO2 emissions. Large-scale deployment of geologic sequestration will require seals with a cumulative area amounting to hundreds of square kilometers per year and will require a large number of sequestration sites. We are developing a system-level model, CO2-PENS, that will predict the overall performance of sequestration systems while taking into account various processes associated with different parts of a sequestration operation, from the power plant to sequestration reservoirs to the accessible environment. The adaptability of CO2-PENS promotes application to a wide variety of sites, and its level of complexity can be increased as detailed site information becomes available. The model CO2-PENS utilizes a science-based-prediction approach by integrating information from process-level laboratory experiments, field experiments/observations, and process-level numerical modeling. The use of coupled process models in the system model of CO2-PENS provides insights into the emergent behavior of aggregate processes that could not be obtained by using individual process models. We illustrate the utility of the concept by incorporating geologic and wellbore data into a synthetic, depleted oil reservoir. In this sequestration scenario, we assess the fate of CO2 via wellbore release and resulting impacts of CO2 to a shallow aquifer and release to the atmosphere.     

Probabilistic design of a near-surface CO2 leak detection system

A methodology is developed for predicting the performance of near-surface CO(2) leak detection systems at geologic sequestration sites. The methodology integrates site characterization and modeling to predict the statistical properties of natural CO(2) fluxes, the transport of CO(2) from potential subsurface leakage points, and the detection of CO(2) surface fluxes by the monitoring network. The probability of leak detection is computed as the probability that the leakage signal is sufficient to increase the total flux beyond a statistically determined threshold. The methodology is illustrated for a highly idealized site monitored with CO(2) accumulation chamber measurements taken on a uniform grid. The TOUGH2 code is used to predict the spatial profile of surface CO(2) fluxes resulting from different leakage rates and different soil permeabilities. A response surface is fit to the TOUGH2 results to allow interpolation across a continuous range of values of permeability and leakage rate. The spatial distribution of leakage probability is assumed uniform in this application. Nonlinear, nonmonotonic relationships of network performance to soil permeability and network density are evident. In general, dense networks (with ～10-20 m between monitors) are required to ensure a moderate to high probability of leak detection.     

Research for deployment: incorporating risk, regulation, and liability for carbon capture and sequestration

Carbon capture and sequestration (CCS) has the potential to enable deep reductions in global carbon dioxide (CO2) emissions, however this promise can only be fulfilled with large-scale deployment. For this to happen, CCS must be successfully embedded into a larger legal and regulatory context, and any potential risks must be effectively managed. We developed a list of outstanding research and technical questions driven by the demands of the regulatory and legal systems for the geologic sequestration (GS) component of CCS. We then looked at case studies that bound uncertainty within two of the research themes that emerge. These case studies, on surface leakage from abandoned wells and groundwater quality impacts from metals mobilization, illustrate how research can inform decision makers on issues of policy, regulatory need, and legal considerations. A central challenge is to ensure that the research program supports development of general regulatory and legal frameworks, and also the development of geological, geophysical, geochemical, and modeling methods necessary for effective GS site monitoring and verification (M&V) protocols, as well as mitigation and remediation plans. If large-scale deployment of GS is to occur in a manner that adequately protects human and ecological health and does not discourage private investment, strengthening the scientific underpinnings of regulatory and legal decision-making is crucial.     

Semianalytical solution for CO2 leakage through an abandoned well

Capture and subsequent injection of carbon dioxide into deep geological formations is being considered as a means to reduce anthropogenic emissions of CO2 to the atmosphere. If such a strategy is to be successful, the injected CO2 must remain within the injection formation for long periods of time, at least several hundred years. Because mature continental sedimentary basins have a century-long history of oil and gas exploration and production, they are characterized by large numbers of existing oil and gas wells. For example, more than 1 million such wells have been drilled in the state of Texas in the United States. These existing wells represent potential leakage pathways for injected CO2. To analyze leakage potential, modeling tools are needed that predict leakage rates and patterns in systems with injection and potentially leaky wells. A new semianalytical solution framework allows simple and efficient prediction of leakage rates for the case of injection of supercritical CO2 into a brine-saturated deep aquifer. The solution predicts the extent of the injected CO2 plume, provides leakage rates through an abandoned well located at an arbitrary distance from the injection well, and estimates the CO2 plume extent in the overlying aquifer into which the fluid leaks. Comparison to results from a numerical multiphase flow simulator show excellent agreement. Example calculations show the importance of outer boundary conditions, the influence of both density and viscosity contrasts in the resulting solutions, and the potential importance of local upconing around the leaky well. While several important limiting assumptions are required, the new semianalytical solution provides a simple and efficient procedure for estimation of CO2 leakage for problems involving one injection well, one leaky well, and multiple aquifers separated by impermeable aquitards.     

Assessing the impact of animal waste lagoon seepage on the geochemistry of an underlying shallow aquifer

Evidence of seepage from animal waste holding lagoons at a dairy facility in the San Joaquin Valley of California is assessed in the context of a process geochemical model that addresses reactions associated with the formation of the lagoon water as well as reactions occurring upon the mixture of lagoon water with underlying aquifer material. Comparison of model results with observed concentrations of NH4+, K+, PO4(3-), dissolved inorganic carbon, pH, Ca2+, Mg2+, SO4(2-), Cl-, and dissolved Ar in lagoon water samples and groundwater samples suggests three key geochemical processes: (i) off-gassing of significant quantities of CO2 and CH4 during mineralization of manure in the lagoon water, (ii) ion exchange reactions that remove K+ and NH4+ from seepage water as it migrates into the underlying anaerobic aquifer material, and (iii) mineral precipitation reactions involving phosphate and carbonate minerals in the lagoon water in response to an increase in pH as well as in the underlying aquifer from elevated Ca2+ and Mg2+ levels generated by ion exchange. Substantial off-gassing from the lagoons is further indicated by dissolved argon concentrations in lagoon water samples that are below atmospheric equilibrium. As such, Ar may serve as a unique tracer for lagoon water seepage since under-saturated Ar concentrations in groundwater are unlikely to be influenced by any processes other than mechanical mixing.     

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite--water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [P(CO2) = 10(-3.5) atm and approximately 0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L(-1), [As(V)]0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L(-1), [As(V)]0 = 0.5 mM and I = 0.01 M NaCI], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (P(CO2) = 10(-3.5) atm) than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear ( 2.8 A) and bidentate binuclear (approximately equal to 3.3 A) bonding at pH 4.5-8 and loading levels of 0.46-3.10 microM m(-2). Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P(CO2) = 10(-3.5) atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO2(g).     

CO₂ sequestration through mineral carbonation of iron oxyhydroxides

Carbon dioxide sequestration via the use of sulfide reductants and mineral carbonation of the iron oxyhydroxide polymorphs lepidocrocite, goethite, and akaganeite with supercritical CO(2) (scCO(2)) was investigated using in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The exposure of the different iron oxyhydroxides to aqueous sulfide in contact with scCO(2) at ～70-100 °C resulted in the partial transformation of the minerals to siderite (FeCO(3)) and sulfide phases such as pyrite (FeS(2)). The relative yield of siderite to iron sulfide bearing mineral product was a strong function of the initial sulfide concentration. The order of mineral reactivity with regard to the amount of siderite formation in the scCO(2)/sulfide environment for a specific reaction time was goethite < lepidocrocite ≤ akaganeite. Given the presence of goethite in sedimentary formations, this conversion reaction may have relevance to the subsurface sequestration and geologic storage of carbon dioxide.     

Removal of heavy metals from mine waters by natural zeolites

In this study, we investigated the removal of Fe, Pb, Cd, and Zn from synthetic mine waters by a natural zeolite. The emphasis was given to the zeolite's behavior toward a few cations in competition with each other. Pb was removed efficiently from neutral as well as from acidic solutions, whereas the uptake of Zn and Cd decreased with low pH and high iron concentrations. With increasing Ca concentrations in solution, elimination of Zn and Cd became poorer while removal of Pb remained virtually unchanged. The zeolite was stable in acidic solutions. Disintegration was only observed below pH 2.0. Forward- and back-titration of synthetic acidic mine water were carried out in the presence and absence of zeolite to simulate the effects of a pH increase by addition of neutralizing agents and a re-acidification which can be caused by subsequent mixing with acidic water. The pH increase during neutralization causes precipitation of hydrous ferric oxides and decreased dissolved metal concentrations. Zeolite addition further diminished Pb concentrations but did not have an effect on Zn and Cd concentrations in solution. During re-acidification of the solution, remobilization of Pb was weaker in the presence than in the absence of zeolite. No substantial differences were observed for Fe, Cd, and Zn immobilization. The immobilization of the metals during pH increase and the subsequent remobilization caused by re-acidification can be well described by a geochemical equilibrium speciation model that accounts for metal complexation at hydrous ferric oxides, for ion exchange on the zeolite surfaces, as well as for dissolution and precipitation processes.     

Cadmium exposure and phosphorus limitation increases metal content in the freshwater alga Chlamydomonas reinhardtii

The characteristics of metal accumulation in freshwater microalgae are important to elucidate for a full understanding of metal cycling and toxicity in a freshwater system. This study has utilized an elemental profiling approach to investigate the impacts of Cd exposure and phosphorus (P) availability on metal accumulation after 7 days in batch culture-grown Chlamydomonas reinhardtii. Multivariate statistical analysis of the elemental data demonstrated distinct responses between both stresses. Sublethal concentrations of Cd (up to 15 μM) caused increased accumulation of Co. Cu, Fe, and Zn content also increased in response to enhanced Cd concentrations but only when P availability was low. While Cd exposure effected the accumulation of a few specific metals, P limitation increased the accumulation of all essential trace metals and macronutrients analyzed including Co, Fe, K, Na, and Zn but not Mn. The accumulation of Cd also markedly increased in response to P limitation. The impact of P availability on essential metal accumulation was the same when either inorganic P or an organic P source (glycerophosphate) was used. These results highlight the potential risks of metal toxicity for freshwater microalgae and aquatic food chains when P availability is limiting and which can be exacerbated by Cd pollution.     

Kinetics of microbial and chemical reduction of humic substances: implications for electron shuttling

Humic substances (HS) are redox-active natural organic compounds and serve as electron shuttles between microorganisms and iron(III) minerals. Here we demonstrate that electron shuttling is possible only at concentrations of dissolved HS of at least 5-10 mg C/L. Although such concentrations can be found in many rivers, lakes, and even in some aquifers there are also many marine and freshwater systems with DOC < 5 mg C/L where consequently electron shuttling is not expected to happen. We found that in the case of HS concentrations which do not limit electron shuttling, Geobacter sulfurreducens transfers electrons to HS at least 27 times faster than to Fe(III)hydroxide. Microbially reduced HS transfer electrons to ferrihydrite at least 7 times faster than cells thereby first demonstrating that microbial mineral reduction via HS significantly accelerates Fe(III) mineral reduction and second that electron transfer from reduced HS to Fe(III) minerals represents the rate-limiting step in microbial Fe(III) mineral reduction via HS. Microbial reduction of HS transfers as many electrons to HS as chemical reduction with H2 indicating that all redox-active functional groups that can be reduced at a redox potential of -418 mV (Eh(0) of H2/H+ redox couple at pH 7) can also be reduced by microorganisms.     

CO2 modeling in a deep saline aquifer: a predictive uncertainty analysis using design of experiment

When field data are limited, stratigraphic models are used instead of detailed, fully heterogeneous models (FHM) to represent deep saline aquifers in numerical simulations of CO2 storage. This study evaluates parameter sensitivity and prediction uncertainty of three stratigraphic models of decreasing complexity (i.e., facies, layered, formation) against that of a FHM. For select simulation outcomes (i.e., CO2 mass profiles, gas plume shape, brine leakage), parameter sensitivity and associated prediction uncertainty are compared among the models, with the FHM serving as a reference. The analysis is conducted using the computationally efficient design of experiment (DoE) and response surface (RS) methodology. Results suggest that when a competent caprock exists (permeability <1 × 10(-4) mD), the facies and layered models are capable of capturing the most important sensitivity parameters of the FHM, that is, residual gas saturation, heterogeneity variance, and salinity. Using the important parameters identified by DoE, RS modeling then suggests that the same two models also capture the ranges of predictions in mobile gas, trapped gas, and brine leakage. The formation model is less accurate in capturing the sensitivity and prediction ranges of the FHM, although it is accurate in predicting brine leakage into the overlying formation.     

Effects of controlled atmospheres on microbial spoilage, electrolyte leakage and sugar content of fresh 'ready-to-use' grated carrots

The effects of controlled atmospheres (CO2 concentrations ranging from 0.03 to 40% and O2 concentrations ranging from 21 to 1%, measured in pack) were studied on fresh 'ready-to-use' grated carrots, stored at 10°C. High CO2 or low O2 conditions favour the growth of lactic acid bacteria (LAB) on grated carrots, but not in a sterile carrot medium, and induce an increased potassium ion leakage. A 25% CO2 and 2% O2 atmosphere improves retention of sugars.
Grated carrots were inoculated by a strain of Leuconostoc mesenteroides , which caused increased potassium ion leakage and exudation only under an atmosphere containing 40% CO2 and 10% O2.
The origin of the spoilage of 'ready-to-use' grated carrots is discussed.     

Natural occurrence of hexavalent chromium in the Aromas Red Sands Aquifer, California

To address increasing concerns of chromium contamination in the drinking water of Santa Cruz County, we designed a study to investigate the source(s) and spatial gradients of the chromium concentration and speciation in local aquifers. This study was catalyzed by a report (January 2001) bythe Soquel Creek Water District of elevated hexavalent chromium concentrations ranging from 6 to 36 microg L(-1), approaching the state's maximum concentration limit of 50 microg L(-1), in the Aromas Red Sands aquifer. To test the accuracy of those preliminary measurements, we collected groundwater using trace metal clean techniques from 11 sites in Santa Cruz County, including 10 from the aquifer with reportedly elevated chromium concentrations and 1 from an adjacent aquifer, the Purisima, and analyzed them fortotal chromium using inductively couple plasma mass spectrometry. Nine of the reportedly 10 contaminated sites had total chromium concentrations ranging from 5 to 39 microg L(-1), while one from the control site was below the limit of detection (0.01 microg L(-1)). We also measured the speciation of chromium at all sites using a solid supported membrane extraction coupled with graphite furnace atomic absorption spectrometry and determined that on average 84% of total chromium was Cr(VI). In addition to the groundwater analyses, a series of extractions were performed on sediment samples from both the Aromas Red Sands and Purisima aquifers. These tests were used to empirically characterize sediment trace metal (Cr, Fe, Mn) distributions in five phases providing information about the origin, availability, reactivity, and mobilization of these trace metals. Results from groundwater and sediment samples indicate that the chromium is naturally occurring in the Aromas Red Sands aquifer, possibly by Cr(III) mineral deposits being oxidized to Cr(VI) by manganese oxides in the aquifer.     

Rate and extent of aqueous perchlorate removal by iron surfaces

The rate and extent of perchlorate reduction on several types of iron metal was studied in batch and column reactors. Mass balances performed on the batch experiments indicate that perchlorate is initially sorbed to the iron surface, followed by a reduction to chloride. Perchlorate removal was proportional to the iron dosage in the batch reactors, with up to 66% removal in 336 h in the highest dosage system (1.25 g mL(-1)). Surface-normalized reaction rates among three commercial sources of iron filings were similar for acid-washed samples. The most significant perchlorate removal occurred in solutions with slightly acidic or near-neutral initial pH values. Surface mediation of the reaction is supported by the absence of reduction in batch experiments with soluble Fe2+ and also by the similarity in specific reaction rate constants (kSA) determined for three different iron types. Elevated soluble chloride concentrations significantly inhibited perchlorate reduction, and lower removal rates were observed for iron samples with higher amounts of background chloride contamination. Perchlorate reduction was not observed on electrolytic sources of iron or on a mixed-phase oxide (Fe3O4), suggesting that the reactive iron phase is neither pure zerovalent iron nor the mixed oxide alone. A mixed valence iron hydr(oxide) coating or a sorbed Fe2+ surface complex represent the most likely sites for the reaction. The observed reaction rates are too slow for immediate use in remediation system design, but the findings may provide a basis for future development of cost-effective abiotic perchlorate removal techniques.