H33E-1678
Highly-selective and Regenerable Ion Exchange for Perchlorate Remediation, Recovery, and Environmental Forensics
Perchlorate (ClO4-) has recently emerged as a widespread contaminant found in drinking water and groundwater supplies in the United States and is known to disrupt thyroid function by inhibiting iodide uptake. Among various treatment technologies, the highly-selective and regenerable ion-exchange technology has recently been developed at ORNL for removing ClO4- from contaminated water. The selective ion exchange technology relies on a unique, highly specific resin to trap ClO4- from contaminated water. The treatment system is then regenerated and perchlorate is destroyed. The reaction that destroys ClO4- produces Cl- and Fe(III) that are used to regenerate the resin, resulting in practically zero secondary waste production. In comparison with conventional non-selective ion-exchange technology, this new treatment process is expected to result in not only a reduced O&M cost but also the elimination of the disposal of hazardous wastes containing perchlorate. Additionally, the selective and regenerable ion exchange technology has allowed the quantitative recovery of perchlorate from contaminated water for reuse, or from other environmental matrices such as sediment, groundwater, and salt deposits for perchlorate isotopic and source identification. Naturally-forming perchlorate has been found to contain distinct oxygen and chlorine isotope signatures or anomalies as compared with anthropogenic perchlorate and can thus provide unambiguous identification of the sources of perchlorate contamination as a powerful tool for the forensics of perchlorate in the environment.
H33E-1679
A Colorimetric Bioassay for Perchlorate
Recognition of perchlorate (ClO4-) as a widespread contaminant across the United States and its potential adverse affects towards human health has motivated the EPA to place ClO4- on its contaminant candidate list for drinking water supplies. While a federal MCL has not yet been set, a recommended public health goal of 1 ppb (μg.L-1) was established by the US EPA in 2002. To date, methods of detection require use of sensitive ion chromatographic equipment that are expensive, time consuming, and require highly trained personnel for use. Our studies are focused on the development of a highly sensitive, simple, and robust colorimetric bioassay based on the primary enzyme involved in microbial ClO4- reduction, the perchlorate reductase (Pcr). A previously published assay used reduced methyl viologen (MV, the dye is reduced with sodium hydrosulfite) as an electron donor to demonstrate Pcr activity. The assay directly correlates the amount of MV oxidized with the amount of ClO4- reduced by assuming a transfer of four electrons. To test this assumption, we compared actual concentrations of MV oxidized to ClO4- reduced in this assay. ClO4- concentrations were determined using a Dionex ICS-500 ion chromatography system, while MV concentrations were determined using a standard curve generated at 578 nm. Comparisons between the two revealed that twelve molecules of MV were oxidized for each molecule of ClO4- reduced. The oxidation of these additional eight MV molecules is explained by the interaction of the dye with chlorite (the product of the Pcr reaction) and other contaminants that could be present in the enzyme prep. This unsettling result indicated this assay would be problematic for the detection of ClO4- in soil, which has many chemicals that could react with MV. To improve upon this assay, we have tried to reduce ClO4- using less reactive dyes and reductants. The reductants ascorbic acid, NADH, and dithiothreitol drive Pcr catalyzed ClO4- reduction, however, they are not effective unless an accompanying dye is used as a shuttle. N-methylphenazinium methosulfate (PMS) was selected as the most suitable dye because of its interaction with NADH, an oxygen stable reductant. In addition, the positive redox potential of PMS (Eo' = +80 mV), makes it significantly less reactive than MV (Eo' = -450 mV). A comparison of actual concentrations of ClO4- reduced vs. NADH oxidized show exactly four molecules of NADH oxidized for each molecule of ClO4- that is reduced (8 electrons). These studies have resulted in the successful development of a method that can accurately determine ClO4- concentrations with a small error using the enzyme Pcr and indicate the great potential for the ultimate development of a simple, robust, and highly sensitive colorimetric bioassay for perchlorate that can be widely used to screen laboratory and environmental samples .
H33E-1680
Effect of nitrate on microbial perchlorate reduction
Over the last decade perchlorate has been recognized as an important emerging water contaminant that poses a significant public health threat. Because of its chemical stability, low ionic charge density, and significant water solubility microbial remediation has been identified as the most feasible method for its in situ attenuation. Our previous studies have demonstrated that dissimilatory perchlorate reducing bacteria (DPRB) capable of the respiratory reduction of perchlorate into innocuous chloride are ubiquitous in soil and sedimentary environments. As part of their metabolism these organisms reduce perchlorate to chlorite which is subsequently dismutated into chloride and molecular oxygen. These initial steps are mediated by the perchlorate reductase and chlorite dismutase enzymes respectively. Previously we found that the activity of these organisms is dependent on the presence of molybdenum and is inhibited by the presence of oxygen and to different extents nitrate. However, to date, there is little understanding of the mechanisms involved in the regulation of perchlorate reduction by oxygen and nitrate. As a continuation of our studies into the factors that control DPRB activity we investigated these regulatory mechanisms in more detail as a model organism, Dechloromonas aromatica strain RCB, transitions from aerobic metabolism through nitrate reduction to perchlorate reduction. In series of growth transition studies where both nitrate and perchlorate were present, preference for nitrate to perchlorate was observed regardless of the nitrate to perchlorate ratio. Even when the organism was pre-grown anaerobically in perchlorate, nitrate was reduced prior to perchlorate. Using non-growth washed cell suspension, perchlorate- grown D. aromatica was capable of reducing both perchlorate and nitrate concomitantly suggesting the preferentially utilization of nitrate was not a result of enzyme functionality. To elucidate the mechanism for preferential utilization of nitrate, transcripts of perchlorate reductase and chlorite dismutase were analyzed to determine possible transcriptional regulation from nitrate. During growth transition studies, increase in the level of transcripts necessary for nitrate reduction and perchlorate reduction was observed concomitantly with decrease in the concentration of nitrate and perchlorate respectively suggesting transcriptional regulation was involved in the preferential utilization of nitrate and that nitrate might be a transcriptional inhibitor of perchlorate reduction. Again, using non-growth washed cell suspensions of perchlorate grown D. aromatica, a decrease of transcript level of the perchlorate reductase but not the chlorite dismutase was observed after incubation with nitrate. In conclusion, from physiological and molecular evidence, nitrate negatively regulates transcription of perchlorate reductase thus inhibiting perchlorate reduction. This result is unexpected as it is in contrast to the accepted dogma that microorganisms regulate their metabolisms to utilize electron acceptors in a sequential manner based on thermodynamic optimization which would imply that perchlorate should be used preferentially to nitrate.
H33E-1681
Bioelectrical Perchlorate Remediation
Several bioreactor designs are currently available for the ex-situ biological attenuation of perchlorate- contaminated waters and recently, some of these reactor designs were conditionally approved by the California Department of Health Services for application in the treatment of perchlorate contaminated drinking water. However, all of these systems are dependent on the continual addition of a chemical electron donor to sustain microbial activity and are always subject to biofouling and downstream water quality issues. In addition, residual labile electron donor in the reactor effluent can stimulate microbial growth in water distribution systems and contribute to the formation of potentially toxic trihalomethanes during disinfection by chlorination. As part of our ongoing studies into microbial perchlorate reduction we investigated the ability of dissimilatory perchlorate reducing bacteria (DPRB) to metabolize perchlorate using a negatively charged electrode (cathode) in the working chamber of a bioelectrical reactor (BER) as the primary electron donor. In this instance the DPRB use the electrons on the electrode surface either directly or indirectly in the form of electrolytically produced H2 as a source of reducing equivalents for nitrate and perchlorate reduction. As part of this investigation our fed-batch studies showed that DPRB could use electrons from a graphite cathode poised at -500mV (vs. Ag/AgCl) for the reduction of perchlorate and nitrate. We isolated a novel organism, Dechlorospirillum strain VDY, from the cathode surface after 70 days operation which readily reduced 100 mg.L-1 perchlorate in a mediatorless batch bioelectrical reactor (BER) in 6 days. Continuous up-flow BERs (UFBERs) seeded with active cultures of strain VDY continuously treated waters containing 100 mg.L-1 perchlorate with almost 100% efficiency throughout their operation achieving a non-optimized volumetric loading of 60 mg.L-1 reactor volume.day-1. The same UFBERs also treated low-level perchlorate (100 μg.L-1) influent as well as mixed-waste influents more typically found in the environment containing both nitrate and perchlorate. Through extended periods of operation (>70 days), no loss in treatment efficiency was noted and no measurable growth in biomass was observed. Gas phase analysis indicated that low levels of H2 produced at the cathode surface through electrolysis can provide enough reducing equivalents to mediate this metabolism. The results of these studies demonstrate that perchlorate remediation can be facilitated through the use of a cathode as the primary electron donor, and that continuous treatment in such a system approaches current industry standards. This has important implications for the continuous treatment of this critical contaminant in industrial waste streams and drinking water. Such a process has the advantage of long-term, low-maintenance operation with ease of online monitoring and control while limiting the injection of additional chemicals into the water treatment process and outgrowth of the microbial populations. This would negate the need for the continual removal and disposal of biomass produced during treatment and also the downstream issues associated with corrosion and biofouling of distribution systems and the production of toxic disinfection byproducts.
H33E-1682
Bioremediation Potential of Perchlorate Contaminated Deep Vadose Zone
Widespread perchlorate contamination was found in the vadose zone near a plant that manufactures ammonium perchlorate above the coastal aquifer of Israel in Ramat Hasharon. As part of the plant's operations, untreated industrial wastewater was disposed of for over 30 years in unlined wastewater ponds and nearby washes, causing contamination of the unsaturated zone (up to 2200 mg kg-1 sediment at a depth of 20 m) and the groundwater below it (up to 300 mg L-1). In this study, we examined the potential for microbial metabolism of perchlorate reduction in the contaminated deep vadose zone profile by native microbial communities. Microbial reduction of perchlorate was found in three of the four sediment samples taken from different depths. The sediments taken from 1 m (shallowest) and 35 m (deepest- close to the water table) showed the fastest degradation rates, while the sediment taken from 15 m showed the slowest rate. No perchlorate reduction was observed in the sediment taken from 20 m, where perchlorate concentrations were highest. These results were correlated to the viable microorganism counts in the profile. In experiments in which the effect of nitrate was examined, the lag time for perchlorate degradation was found to be inversely correlated to the initial nitrate concentration, while the perchlorate-reduction rates were faster in treatments with higher initial nitrate concentrations. We found no perchlorate degradation as long as nitrate was present in the system: perchlorate reduction was initiated only after all of the nitrate had been reduced. Nitrate-reduction rates were correlated to the initial nitrate concentrations and no lag period was observed. Nitrite was temporarily accumulated during nitrate reduction and was totally reduced, like nitrate, after 4 days. Count of viable microbial communities as well as PCR analysis of the chlorite dismutase gene in the native microbial population exposed to high concentrations of perchlorate (10,000-20,000 mg L-1) showed no toxicity effect on the microorganisms, and even promotion of the perchlorate-reducing bacteria. Natural organic matter (NOM) in sediments taken from ground surface could be used as carbon and energy sources for perchlorate-reducing bacteria. The average perchlorate-reduction rate using NOM as the carbon source was 0.45 mg day-1, whereas when acetate was used as the carbon source, it was 7.2 mg day-1.
H33E-1683
Modeling In Situ Bioremediation of Perchlorate-Contaminated Groundwater
Perchlorate-contaminated groundwater is a significant national problem. An innovative technology was recently developed which uses a pair of dual-screened treatment wells to mix an electron donor into perchlorate- contaminated groundwater in order to effect in situ bioremediation of the perchlorate by indigenous perchlorate reducing bacteria (PRB) without the need to extract the contaminated water from the subsurface. The two treatment wells work in tandem to establish a groundwater recirculation zone in the subsurface. Electron donor is added and mixed into perchlorate-contaminated groundwater flowing through each well. The donor serves to stimulate biodegradation of the perchlorate by PRB in bioactive zones that form adjacent to the injection screens of the treatment wells. In this study, a model that simulates operation of the technology was calibrated using concentration data obtained from a field-scale technology evaluation project at a perchlorate-contaminated site. The model simulates transport of perchlorate, the electron donor (citrate, for this study), and competing electron acceptors (oxygen and nitrate) in the groundwater flow field induced by operation of the treatment well pair. A genetic algorithm was used to derive a set of best-fit model parameters to describe the perchlorate reduction kinetics in this field-scale evaluation project. The calibrated parameter values were then used to predict technology performance. The model qualitatively predicted the salient characteristics of the observed data. It appears the model may be a useful tool for designing and operating this technology at other perchlorate-contaminated sites.
H33E-1684
A Novel System for the Separation and Destruction of Perchlorate from Contaminated Waters
The remediation of perchlorate contaminated ground water through conventional ion-exchange technology requires frequent regeneration of the ion exchange resins and subsequent disposal of the regenerate solutions. The disposal of these wastes poses environmental challenges, and it is not an economically favorable option. This research focuses on the development of a two stage process for the separation and destruction of perchlorate from contaminated waters. The separation stage employs a transition metal-functionalized DOW3N- based ion exchangers which has shown promise as a remediation strategy for trace anionic contaminates such as perchlorate and can be successfully regenerated using mild solution conditions. Three transition metals (Fe(III), Ni(II), and Cu(II)) have been used to functionalize Dowex M4195 polymeric ligand exchangers. The resulting materials were compared with respect to their perchlorate selectivity, capacity, kinetics and regeneration efficiency through a series of batch and column experiments. In parallel studies, perchlorate reduction in batch laboratory cultures could indicate the potential to couple these two processes through the biological destruction of perchlorate in regenerant solutions. The destruction of perchlorate through functionalized zero-valent-iron (ZVI) nanoparticles may be an alternative or complimentary second stage to this process. Kinetic data from batch perchlorate reduction experiments in the presence of functionalized ZVI nanoparticles will be included.
H33E-1685
Soil Flushing Through a Thick Vadose Zone: Perchlorate Removal Documented at Edwards AFB, California
There are currently few viable alternatives for perchlorate remediation in the vadose zone, particularly for the relatively thick vadose zones that are typical in the arid southwest where many perchlorate sites occur. Perchlorate in the vadose zone occurs in the form of highly soluble salts that may represent a risk to human or ecological receptors, and may also represent a threat to the underlying groundwater. A soil flushing treatability study was conducted at Edwards Air Force Base in the Mojave Desert of southern California at a site with a 129-foot thick vadose zone consisting primarily of clayey sand. This study utilized an infiltration gallery in conjunction with extraction, treatment, and re-injection of groundwater at the site, which contained perchlorate-contaminated soil and groundwater. The study objective was to evaluate the effectiveness of the infiltration gallery to 1) introduce treated groundwater back into the aquifer and 2) wash the perchlorate from the vadose zone soils to the aquifer. The infiltration gallery consisted of slotted PVC pipes within a highly permeable engineered bed of washed gravel. The initial water introduced into the gallery was amended with potassium bromide tracer. A downhole neutron probe was used to track the movement of the wetting front downward and outward from the gallery. Successive neutron measurements in vertical access tubes revealed that the introduced water reached the 125-foot bottom of the access tubes 14 weeks after the water was introduced into the gallery. The bromide tracer was detected in groundwater immediately below the gallery approximately 1 week later. The infiltration gallery was able to sustain an average flow rate of 2.3 gallons per minute. Prior to infiltration, the perchlorate concentration in groundwater below the gallery was 4,500 µg/L. Approximately 18 weeks after the start of infiltration, a perchlorate spike of 72,400 µg/L was detected below the gallery. The increase in perchlorate groundwater concentrations indicates the transfer of perchlorate from the vadose zone to the saturated zone, where it was readily captured by an adjacent groundwater extraction well. Continued flushing of treated water through the vadose and saturated zones resulted in a rapid decline in perchlorate groundwater concentrations. Confirmation soil boreholes documented the effectiveness of the soil treatment after perchlorate groundwater concentrations returned to their pre-soil flushing levels. This treatability study demonstrates that perchlorate can be removed from a thick sandy vadose zone by controlled infiltration with associated hydraulic control of groundwater to capture the leached perchlorate. The treatability study results also indicates that an infiltration gallery may provide 1) a cost-effective alternative to injection wells for reintroducing treated groundwater to the aquifer and 2) an effective mechanism for the delivery of amendments to the vadose zone and aquifer for promoting enhanced biodegradation of perchlorate in soil and groundwater.
H33E-1686
Formation Of Perchlorate By Ozonation Of Aqueous Oxy-chlorine Anions: An Insight To Natural Perchlorate Formation
Perchlorate (ClO4-) is a natural and anthropogenic contaminant of increasing concern. Natural perchlorate was first identified in Chilean nitrates from the Atacama dessert over 100 years ago. However, only in the last two years has the occurrence of natural perchlorate been seriously considered as a potential exposure source. Although there has been considerable research effort in understanding the occurrence, remediation, and impact of ClO4- in the environment, relatively little information is available regarding the mechanism(s) responsible for ClO4- formation. Perchlorate productions from ozone oxidation of chlorine and oxy- chlorine anions (Cl-, OCl-, ClO2-and ClO3-) were conducted in continuous flow reactors at constant ozone concentrations (approximately 6 mg L-1) and at varying concentrations of chlorine materials (ranging from 10 to 1000 mg L-1). Sub samples from both the main reaction flask and alkaline trapping flasks were taken over varying time intervals and the concentrations of oxy-chlorine anions including ClO4- were measured using various ion chromatographic methods whereas OCl- was determined iodometrically using the spectrophotometer. The experiment time ranged from 6 hrs to 7 days depending on the rate of decomposition of the reactants. Results indicate that ClO4- is readily formed during the ozonation of ClO2- and OCl- solutions (maximum conversion of 2.7 %) whereas the Cl- and ClO3- solutions produced relatively lower quantities of ClO4- ( maximum conversion of 0.02 %) . Further the presence of ClO2- in the initial OCl- solution is suspected to significantly contribute the total ClO4- generated augmenting the role of ClO2- in ClO4- formation as mentioned in recent study on the photochemical reactions of oxy-chlorine anions.
H33E-1687
Multiple Sulfate Isotopic Evidence on the Formation of Oxide Copper Ore at Spence, Atacama Desert, Northern Chile
In the Atacama Desert of northern Chile, one of the world's richest metallogenic provinces, porphyry copper deposits are characterized by the unique occurrence of atacamite in their oxidized zones. The origin and formation of the oxide zone of these copper deposits is, however, controversial. It was proposed that Cl-rich deep formation water pumping-up events along faults by earthquakes, after onset of the hyperaridity, were required (Cameron et al., 2007). Their model would imply that supplies of saline deep formation water from fractures to the surface should have left behind a homogeneous or fracture-controlled salt profile from surface down to the oxide zone. While no excluding the deep formation water model in other deposit, here we propose that, in our sampling region, the alternative saline source, which is critical for atacamite formation, could be locally evaporated groundwater, Cl-rich salts leached from arid surface by meteoric water, or brines from eastern salar basins at a time when the climate in northern Chile was changing from arid to hyperarid. At this climate transition, arid- requiring minerals such as atacamite in the oxide zone were formed and, more importantly, preserved upon evaporation beneath the surface alluvial deposits. Since salt accumulation at the surface remain active during hyperarid condition, our model would predict that water-soluble salt profile from surface to the oxide zone should have a characteristic pattern: salts with an atmospheric component on the surface gradually transitioning to salts of the oxide ore zone on the bottom and a mixing zone in between. To test these two alternative models, we focus on sulfate salts, one of the common water-soluble salts in arid environments. An added advantage is that sulfate accumulated on desert surface has a secondary atmospheric component that bears a unique triple oxygen isotope signature, easily distinguishable from sulfate formed by the oxidation of sulfide minerals at the oxide ore zone. Samples were collected from a drill core that extends from surface soil to an oxide zone where gypsum and jarosite coexist with atacamite at Spence, a supergene enriched copper porphyry deposit located between Calama and Antofagasta. We found that at 15 to ~100 m depths, the Δ17O and δ34S both decrease while the δ18O increases steadily with depths, suggesting a binary mixing of two distinct sulfate sources, with the surface sulfate having Δ17O, δ34S, and δ18O at +0.55‰, +5.80‰, and +10.80‰, while the deep oxide-ore- zone sulfate at -0.23‰, +3.6‰, and+19.8‰, respectively. The surface sulfate has reached a maximum depth of ~ 50 meters, as marked by the disappearance of positive Δ17O signals at that depth. The intact preservation of this transitional sulfate mixing profile supports our model, a model that does not require a deep formation water source for atacamite formation in oxide zone of Spence copper porphyry deposit.
H33E-1688
Distribution of Perchlorate in Aquifers Used for Public Water Supply in California, USA
Perchlorate has been detected in public-supply wells that tap aquifers in many parts of California. Two data sets are available, one collected by the California Department of Public Health (CDPH) for compliance of drinking water with health-based standards, and one by the California State Water Resources Control Board Groundwater Ambient Monitoring and Assessment Program (GAMA) for statewide assessment of the quality of untreated groundwater. The GAMA Priority Basin project is conducted by the USGS. GAMA uses a reporting limit (RL) of 0.5 μg/L, and samples primarily public-supply wells. The wells are selected on a spatially distributed, randomized network designed to permit statistically robust characterization of aquifer water quality in study areas and comparisons on regional and statewide scales. CDPH uses an RL of 4 μg/L and includes all public- supply wells for which data are available. The two datasets yield different distributions of perchlorate detections. GAMA data for 14 study areas (766 wells), representing 60 of the 116 priority groundwater basins in California, have a 22% detection frequency for perchlorate at RL= 0.5 μg/L, 3% at RL= 4 μg/L, and < 2% greater than the California Notification Level (NL) of 6 μg/L. In contrast, CDPH data for the same areas (2930 wells) have a 10% frequency at RL= 4 μg/L and 7% greater than the NL. The higher detection frequency in the CDPH database may be due to the high density of wells in a region with many known industrial, aerospace, and military perchlorate users. Among the 14 GAMA study areas, 2 had no detections of perchlorate. Detection frequency was > 40% in 3 areas with high densities of known perchlorate users. Ten areas had detection frequencies between 6 and 37%. Perchlorate has several sources in California: natural, legacy fertilizers, use of Colorado River water on the landscape, and industrial, aerospace, and military users. The distribution of perchlorate detections, combined with other water-quality and tracer data collected by GAMA are expected to aid in the determination of the relative importance of these various sources of perchlorate to groundwater in different regions of California.
H33E-1689
Fate and Transport of Perchlorate at California's Stringfellow Superfund Site
Geologic conditions exert primary control over the fate and transport of perchlorate at the Stringfellow Superfund site. A buried valley filled with alluvium has been defined that extends from Pyrite Canyon, location of the former Stringfellow acid pits, down to near the Santa Ana River. The buried valley is cut into the underlying granitic bedrock, and appears to be a paleo-channel of the ancestral Pyrite Creek. The groundwater hydraulic gradient aligns closely with the buried valley, as does the perchlorate plume. The buried valley appears to be a preferential pathway for contaminant migration. Perchlorate concentrations in the downgradient portion of the plume have been slowly decreasing over time, suggesting that the groundwater extraction wells are effective at cutting off the source. Perchlorate degradation, however, appears to be minimal over most of the sandy aerobic aquifer, as concentrations of perchlorate persist over a 5-mile long plume. Scattered concentrations of perchlorate in the 1 to 12 ug/L range are widespread over a broad area adjacent to the plume and appear to be unrelated to the plume. Hydrogeologic analysis and perchlorate isotope analysis are being used to investigate whether these outlying concentrations may be related to the historic use of perchlorate- bearing mineral nitrate fertilizer. At the distal end of the plume, a marked change in the fate of perchlorate occurs beneath the Santa Ana River. Sampling of mini-piezometers installed into the river sediments shows that the perchlorate and nitrate concentrations fall to below detection as the aquifer environment changes from oxidizing to reducing conditions. In this local environment, it appears that anaerobic biodegradation reduces the perchlorate and nitrate. As a result of degradation of perchlorate, and possibly mixing of infiltrating river water beneath the losing portions of the river, perchlorate concentrations decrease to below 6 ug/L downgradient of the river. This presentation will show how geologic conditions and the geochemical environment affect the fate and transport of perchlorate at the Stringfellow site.
H33E-1690
Enriched Perchlorate and Relationship with Other Major Anions in Atmospherically Derived Deposits of Nitrate of the Mojave Desert
Perchlorate has been known to be present in salt deposits from the Atacama Desert for over a century. Its presence is typically associated with NO3-, although relatively few samples from the Atacama have been evaluated. Perchlorate in the Atacama nitrate deposits has a substantial Δ17O anomaly strongly suggesting an atmospheric origin, or at least a production mechanism involving O3 (e.g. surface oxidation). Reports of natural ClO4- in North America have been increasing recently. These reports indicate that ClO4- is widely distributed in groundwater and in unsaturated surface soils. However, most reported occurrences have been at low concentrations. Because of the association of ClO4- with NO3- in the Atacama deposits, previously identified NO3- deposits with atmospheric components in North America were investigated for the occurrence of ClO4-. These nitrate deposits are located in the Death Valley region of the Mojave Dessert and have been previously characterized with respect to chemical composition and isotopic ratios of N, O, and S. Perchlorate concentrations varied but, in general, were significantly higher (1 mg/kg) than in most other reported occurrences. Although the Mojave deposits were enriched in ClO4-, the relative molar ratios of NO3- or Cl- to ClO4- were significantly higher (105-106 and 104 for Cl-/ClO4- and NO3-/ClO4- respectively) than those of the Atacama deposits (1-102 and 101-102 for Cl-/ClO4- and NO3-/ClO4-, respectively ) even for samples highly enriched in NO3- (1~5% of soil by weight). NO3-/Cl- molar ratios are roughly similar between the deposits (0.83 and 0.2-0.8 for Atacama and Death Valley, respectively) if similar grades of NO3-ores (1-20%) are compared. Molar ratios of Cl-/ClO4- and NO3-/ClO4- in the Mojave deposits are similar to those reported for both groundwater and unsaturated zone samples in the U.S. attributed to natural sources. Possible reasons for the large discrepancies in molar ratios between the Chilean and North American samples include differences in post depositional segregation or degradation, or differences in production mechanisms and/or extent of ClO4- production relative to other atmospherically deposited species.
H33E-1691
Systematics of Natural Perchlorate in Precipitation, Soils, and Plants at the Amargosa Desert Research Site, Nye County, Nevada
Naturally occurring perchlorate is known to be associated with nitrate deposits of the hyperarid Atacama Desert in Chile, and recent large-scale sampling has identified a substantial reservoir (up to 1 kg/ha) of natural perchlorate in diverse unsaturated zones of the arid and semiarid Southwestern United States (Rao et al., 2007, ES&T, DOI: 10.1021/es062853i). The objective of the Amargosa Desert work is to develop a better understanding of the deposition, accumulation, and biological cycling of perchlorate in arid environments. Occurrence of perchlorate was evaluated by sampling shallow soil profiles up to 3 m in depth at four different locations and at two different time periods, and by sampling dominant plant species growing near the subsurface profiles. Deposition of perchlorate was evaluated by analyzing both bulk deposition (precipitation plus dry fall, collected under oil) collected on site and wet deposition samples collected by the National Atmospheric Deposition program at a nearby site. Soil samples and atmospheric-deposition samples were tested for both perchlorate (ClO4- ) and major anions. Perchlorate concentrations (0.2-20 µg/kg) were variable with depth in soil profiles and generally correlated most highly with chloride (Cl-) and nitrate (NO3-), although the intensity of these relations differed among profiles. Plant concentrations were generally above 1 mg/kg, suggesting ClO4- accumulation. Concentrations of ClO4- were generally much greater in total deposition than wet deposition samples, indicating a substantial dryfall component of meteoric deposition. This presentation will present the mass distribution and variability of perchlorate in bulk deposition, soils, and plants. Reasons for observed relations between subsurface concentrations of perchlorate and other anions will be explored. http://nevada.usgs.gov/adrs/
H33E-1692
Perchlorate Mobilization Related to Land Use Change in the Southern High Plains, USA
Perchlorate, derived from precipitation and dry fallout, has accumulated in the unsaturated zone in semiarid regions, similar to chloride. Potential impacts of these perchlorate reservoirs on groundwater contamination depend on mobilization. The purpose of this study was to evaluate mobilization of perchlorate reservoirs related to land-use change from natural to agricultural ecosystems based on data from the southern High Plains where large perchlorate concentrations (<e; 60 ppb in groundwater) have been found in the Ogallala aquifer. Boreholes were drilled and sampled beneath natural ecosystems and beneath rainfed and irrigated agricultural ecosystems. Large inventories of perchlorate were found beneath natural grassland and shrubland ecosystems, similar to those found in previous studies in this region (234-1050 g perchlorate per ha; 2.5-7.2 ppb perchlorate in soil pore water). Perchlorate concentrations in these natural profiles is highly correlated with chloride concentrations, suggesting a similar source (precipitation and dry fallout) and evapotranspirative enrichment process over up to ~ 30,000 yr in some profiles. Profiles beneath rainfed agriculture show downward displacement of perchlorate bulges to a maximum depth of 8.3 m in the sampled profiles. High correlations between perchlorate and chloride concentrations in profiles beneath rainfed agriculture indicate that chloride profiles can be used to predict perchlorate mobility. Chloride profiles indicate the perchlorate should be completely flushed through the unsaturated zone in the southeastern part of the study area and partially flushed in other regions of the southern High Plains. Profiles beneath irrigated agriculture are variable. Chloride was completely flushed and there was no detectable perchlorate in one of the profiles, indicating that irrigation return flow had mobilized chloride and perchlorate to the aquifer in this setting. The other profiles did not extend deep enough to determine the fate of the natural salt bulges; however, chloride and perchlorate bulges near the root zone are attributed to more recent deficit irrigation within the last couple of decades that is causing soil salinization. Groundwater perchlorate contamination is likely to increase in the future with more widespread flushing of naturally occurring perchlorate beneath cultivated regions.
H33E-1693
Perchlorate in the San Antonio Segment of the Edwards Aquifer, Texas
Perchlorate has been detected in drinking-water supplies and can have adverse health effects on humans by disrupting thyroid function. Perchlorate and other constituents were analyzed from ground-water samples that were collected in 2004-06 from 99 wells completed in the San Antonio segment of the Edwards aquifer as part of the U.S. Geological Survey National Water-Quality Assessment Program. The fractured karstic carbonate Edwards aquifer, declared a sole-source aquifer by the U.S. Environmental Protection Agency, supplies nearly one-half million acre-feet per year for drinking water and other uses. Wells were located in a variety of land-use settings that included rangeland, agriculture, and urban; well types included domestic, public, and observation. Perchlorate was detected in 98 percent of the samples, and concentrations ranged from less than 0.05 to 3 micrograms per liter (μg/L). Five samples contained concentrations greater than 1 μg/L and were from wells in the urban northern San Antonio area. The results from three samples that contained perchlorate at concentrations greater than 2 μg/L are anomalous. Chloride concentration ranged from 5.6 to 69 milligrams per liter, typical for freshwater in the Edwards aquifer. No significant (r2 greater than 0.7) correlations were observed when perchlorate concentrations were correlated with depth to water, total depth of well, or concentrations of bicarbonate, nitrate, phosphate, sulfate, bromide, chloride, fluoride, calcium, magnesium, potassium, sodium, strontium, and dissolved solids. Tritium concentrations ranged from 1.2 to 2.9 tritium units in 31 of the 99 samples and indicate at least some fraction of modern water (post-atmospheric nuclear tests). No correlation between apparent tritium age and perchlorate concentration was observed, a possible indication that anthropogenic influences are not affecting observed perchlorate concentrations. The molar ratio of chloride to perchlorate ranged from 17,000 to 320,000 with a mean of 94,000. Most of the ratios are similar to those computed in a study of naturally occurring perchlorate in the southern High Plains aquifer. Ratios for the three anomalous samples are more similar to those observed in a study of the Rio Grande aquifer system in the Basin and Range physiographic province. Results of this study indicate that perchlorate might be a widespread naturally-occurring constituent in the Edwards aquifer at relatively low concentrations less than 3 μg/L.
H33E-1694
Comparison of Iron Sulfide and Zero-Valent Iron as Reactive Materials for the Removal of Arsenic From Groundwater
Zero-valent iron (ZVI) installed in permeable reactive barriers (PRBs) has been shown to be an effective remediation agent for several contaminants, including arsenic (As), a redox-active oxyanion present in reduced form as arsenite, AsO3(3-), and in oxidized form as arsenate, AsO4(3-). Work performed has shown greater removal of arsenic by iron sulfide (FeS), as mackinawite, than by ZVI under anaerobic conditions, recommending the use of FeS in PRB systems. For both ZVI and FeS PRB systems, the interaction of the reactive porous media with groundwater species, and calcium and carbonate in particular, is key to maintaining the permeability and reactivity of the PRB, both of which are necessary for continued treatment. If geochemical conditions are favorable, CaCO3(s) may precipitate, thus reducing permeability and passivating the reactive surface, preventing further remediation. In a statistical review of field PRB performance (Henderson and Demond, Env. Eng. Sci., 2007), it was found that alkalinity, as an indicator of the potential for precipitation of carbonate solids, was correlated to increased risk of PRB failure. A combination of experimental and geochemical modeling approaches is being used to investigate the quantity of calcium carbonate formation in anaerobic FeS and ZVI systems. Column tests with FeS to date have resulted in behavior unlike that observed with ZVI. In the ZVI columns, a pH increase has allowed the precipitation of CaCO3(s), which led to a reduction in permeability. In the FeS columns, the effluent pH and aqueous calcium concentrations were essentially the same as the influent, suggesting that the buffer capacity of carbonate prevented a pH increase, thus precluding the precipitation of CaCO3(s). Geochemical modeling suggests that the interaction of carbonate and FeS may self-regulate in PRB systems: at high carbonate concentrations, when the precipitation of CaCO3(s) could reduce permeability, the buffer capacity provided by the carbonate precludes the pH rise necessary for precipitation. Based on this work, it appears that FeS has additional attributes that recommend it as a reactive medium for in situ removal of arsenic from groundwater.
H33E-1695
Field Scale Transport of Chromate in Groundwater From Cooling Tower Wastes
Chromate (Cr(VI)) was used extensively in evaporative cooling systems to prevent corrosion and scale formation. Waters from the cooling systems were discharged to ponds that were intended as evaporation ponds, but there were instances where the wastewaters infiltrated into the soil and released chromate to groundwater. Cooling tower discharges containing chromate also have elevated salt concentrations compared to the ambient groundwater because of the intended evaporative cooling process. Density driven flow and emplacement of contaminated brines should thus be expected. This conceptual model is being evaluated by the analysis of field data at two natural gas compressor facilities in the deserts of southeastern California. These facilities continuously released chromate containing water to unlined evaporation ponds for more than a decade, and subsequent investigations have identified groundwater plumes containing chromate. At one site, extensive remediation over a 15 year period has limited the plume migration but has not reduced groundwater concentrations. At the other site, density-stratified flow is observed. While there are uncertainties in the amounts released, the data available at these sites suggest that remedial approaches based on groundwater extraction are not effective in removing the source of chromate contamination from emplaced pockets of highly concentrated cooling tower discharge. Long term data sets collected during site investigations and remediation are valuable sources of data on field scale transport of highly mobile contaminants such as chromate.
H33E-1696
Characterizing Field Biodegradation of N-nitrosodimethylamine (NDMA) in Groundwater with Active Reclaimed Water Recharge
N-Nitrosodimethylamine (NDMA) is an emerging contaminant in groundwater, because of its aqueous miscibility, exceptional animal toxicity, and human carcinogenicity. NDMA detections in groundwater have been tracked to either decomposition of unsymmetrical dimethylhydrazine (UDMH) used in rocket fuel facilities or chlorine disinfection in wastewater reclamation plants. Laboratory experiments on both unsaturated and saturated soil samples have demonstrated that NDMA can be biodegraded by microbial activity, under both aerobic and anaerobic conditions. However, very limited direct evidence for its biodegradation has been found from the field in saturated groundwater. Our research aimed to evaluate photolysis and biodegradation of NDMA occurring along the full travel path - from wastewater reclamation plant effluent, through rivers and spreading grounds, to groundwater. For this evaluation, we established an extensive monitoring network to characterize NDMA concentrations at effluent discharge points, surface water stations, and groundwater monitoring and production wells, during the operation of the Montebello Forebay Groundwater Recharge facilities in Los Angeles County, California. Field monitoring for NDMA has been conducted for more than six years, including 32 months of relatively lower NDMA concentrations in effluent, 43 months of elevated NDMA effluent concentrations, and 7 months with significantly reduced NDMA effluent concentrations. The NDMA effluent concentration increase and significant concentration decrease were caused by changes in treatment processes. The NDMA sampling data imply that significant biodegradation occurred in groundwater, accounting for a 90% mass reduction of NDMA over the six-year monitoring period. In addition, the occurrence of a discrete well monitored effluent release during the study period allowed critical analysis of the fate of NDMA in a well- characterized, localized groundwater flow subsystem. The data indicate that 80% of the recharged NDMA mass was biodegraded in groundwater with the remaining mass pumped out by extraction wells. To reproduce the observation data, a groundwater flow and transport model was developed and calibrated against groundwater elevation and NDMA concentration data. The calibrated half-life of NDMA in groundwater is 69 days, which is consistent with the values obtained through laboratory incubation using soil samples from the Montebello Forebay Spreading Grounds. Given the photolysis of NDMA in surface water and biodegradation in groundwater observed during this study, reclaimed wastewater with limited NDMA concentrations can be safely used for groundwater recharge under the study area conditions.
H33E-1697
Perchlorate in the Hydrologic Cycle - An Overview of Sources and Occurrence
Perchlorate (ClO4-) in water and food is of concern due to deleterious health affects associated with hypothyroidism. The presence of widespread perchlorate in 0-to-28 ka-old pristine ground water of the Middle Rio Grande Basin (Plummer et al., 2006, ES&T, DOI:10.1021/es051739h), in ground water >1 mile from agricultural activities in the Southern High Plains (Rajagapolan et al., 2006, ES&T, DOI:10.1021/es052155i), and in unsaturated zones throughout the arid and semiarid southwestern United States (Rao et al., 2007, ES&T, DOI:10.1021/es062853i) clearly indicates that perchlorate is a non-exotic component of the hydrologic cycle, at least in dry environments. The natural system has been greatly perturbed in places by human activities. Most anthropogenic inputs are associated with the manufacture and use of explosives and rocket fuel, providing concentrated sources of excess perchlorate to the hydrologic cycle. Perchlorate-containing fertilizers and irrigation provide dispersed sources within and down-gradient from agricultural areas. Natural sources include photochemically mediated reactions involving ozone at the land surface and in the lower atmosphere. A growing body of work indicates that a small, but persistent, meteoric source acting over thousands of years can explain observed accumulations of unsaturated-zone perchlorate in arid regions. In addition to meteoric sources, oxyanions produced during volcanogenic processes can include appreciable amounts of natural perchlorate. Terrestrial plants take up perchlorate in soil water, with some species of xerophytic succulents concentrating the anion to high levels. Similarly, perchlorate in marine plants indicates that perchlorate is part of marine biochemical cycles. Perchlorate-bearing marine sediments of late Tertiary age suggest that perchlorate has been part of global geochemical cycles for millions of years and, furthermore, can be preserved in the subsurface despite the nearly ubiquitous presence of perchlorate-reducing bacteria in natural environments. New methods involving various combinations of ion chromatography, mass spectroscopy, and molecular biology are providing improved tools for understanding perchlorate in natural and perturbed systems. With large-scale sampling underway, a better understanding of the sources, sinks, and transformations of perchlorate in the hydrologic cycle is starting to emerge.