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At least 19 records

Targeted detection of Dehalococcoides mccartyi microbial protein biomarkers as indicators of reductive dechlorination activity in contaminated groundwater

Dehalococcoides mccartyi ( Dhc ) bacterial strains expressing active reductive dehalogenase (RDase) enzymes play key roles in the transformation and detoxification of chlorinated pollutants, including chlorinated ethenes. Site monitoring regimes traditionally rely on qPCR to assess the presence of Dhc biomarker genes; however, this technique alone cannot directly inform about dechlorination activity. To supplement gene-centric approaches and provide a more reliable proxy for dechlorination activity, we sought to demonstrate a targeted proteomics approach that can characterize Dhc mediated dechlorination in groundwater contaminated with chlorinated ethenes. Targeted peptide selection was conducted in axenic cultures of Dhc strains 195, FL2, and BAV1. These experiments yielded 37 peptides from housekeeping and structural proteins (i.e., GroEL, EF-TU, rpL7/L2 and the S-layer), as well as proteins involved in the reductive dechlorination activity (i.e., FdhA, TceA, and BvcA). The application of targeted proteomics to a defined bacterial consortium and contaminated groundwater samples resulted in the detection of FdhA peptides, which revealed active dechlorination with Dhc strain-level resolution, and the detection of RDases peptides indicating specific reductive dechlorination steps. The results presented here show that targeted proteomics can be applied to groundwater samples and provide protein level information about Dhc dechlorination activity.

59 BASIC BIOLOGICAL SCIENCES↗

Bacterial Community Dynamics in Dichloromethane-Contaminated Groundwater Undergoing Natural Attenuation

The uncontrolled release of the industrial solvent methylene chloride, also known as dichloromethane (DCM), has resulted in widespread groundwater contamination in the United States. Here we investigate the role of groundwater bacterial communities in the natural attenuation of DCM at an undisclosed manufacturing site in New Jersey. Here, we investigate the bacterial community structure of groundwater samples differentially contaminated with DCM to better understand the biodegradation potential of these autochthonous bacterial communities. Bacterial community analysis was completed using high-throughput sequencing of the 16S rRNA gene of groundwater samples (n = 26) with DCM contamination ranging from 0.89 to 9,800,000 μg/L. Significant DCM concentration-driven shifts in overall bacterial community structure were identified between samples, including an increase in the abundance of Firmicutes within the most contaminated samples. And across all samples, a total of 6,134 unique operational taxonomic units (OTUs) were identified, with 16 taxa having strong correlations with increased DCM concentration. Putative DCM degraders such as Pseudomonas, Dehalobacterium and Desulfovibrio were present within groundwater across all levels of DCM contamination. Interestingly, each of these taxa dominated specific DCM contamination ranges respectively. Potential DCM degrading lineages yet to be cited specifically as a DCM degrading organisms, such as the Desulfosporosinus, thrived within the most heavily contaminated groundwater samples. Co-occurrence network analysis revealed aerobic and anaerobic bacterial taxa with DCM-degrading potential were present at the study site. Our 16S rRNA gene survey serves as the first in situ bacterial community assessment of contaminated groundwater harboring DCM concentrations ranging over seven orders of magnitude. Diversity analyses revealed known as well as potentially novel DCM degrading taxa within defined DCM concentration ranges, indicating niche-specific responses of these autochthonous populations. Altogether, our findings suggest that monitored natural attenuation is an appropriate remediation strategy for DCM contamination, and that high-throughput sequencing technologies are a robust method for assessing the potential role of biodegrading bacterial assemblages in the apparent reduction of DCM concentrations in environmental scenarios.

16S rRNA↗

Hybrid Sorbents for 129 I Capture from Contaminated Groundwater

Radioiodine ( 129 I) poses a risk to the environment due to its long half-life, toxicity, and mobility. It is found at the U.S. Department of Energy Hanford Site due to legacy releases of nuclear wastes to the subsurface where 129 I is predominantly present as iodate (IO 3 – ). To date, a cost-effective and scalable cleanup technology for 129 I has not been identified, with hydraulic containment implemented as the remedial approach. Here, novel high-performing sorbents for 129 I remediation with the capacity to reduce 129 I concentrations to or below the US Environmental Protection Agency (EPA) drinking water standard and procedures to deploy them in an ex-situ pump and treat (P&T) system are introduced. Furthermore, this includes implementation of hybridized polyacrylonitrile (PAN) beads for ex-situ remediation of IO 3 – -contaminated groundwater for the first time. Iron (Fe) oxyhydroxide and bismuth (Bi) oxyhydroxide sorbents were deployed on silica substrates or encapsulated in porous PAN beads. In addition, Fe–, cerium (Ce)–, and Bi–oxyhydroxides were encapsulated with anion-exchange resins. The PAN–bismuth oxyhydroxide and PAN–ferrihydrite composites along with Fe- and Ce-based hybrid anion-exchange resins performed well in batch sorption experiments with distribution coefficients for IO 3 – of >1000 mL/g and rapid removal kinetics. Of the tested materials, the Ce-based hybrid anion-exchange resin was the most efficient for removal of IO 3 – from Hanford groundwater in a column system, with 50% breakthrough occurring at 324 pore volumes. The functional amine groups on the parent resin and amount of active sorbent in the resin can be customized to improve the iodine loading capacity. These results highlight the potential for IO 3 – remediation by hybrid sorbents and represent a benchmark for the implementation of commercially available materials to meet EPA standards for cleanup of 129 I in a large-scale P&T system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Groundwater Contamination, Subsurface Processes, and Remediation Methods: Overview of the Special Issue of Water on Groundwater Contamination and Remediation

This special issue of Water brings together ten studies on groundwater contamination and remediation. Common themes include practical techniques for plume identification and delineation, the central role of subsurface processes, the pervasiveness of non-Fickian transport, and the importance of bacterial communities in the broader context of biogeochemistry.

Mays, David↗

Molybdenum Availability Is Key to Nitrate Removal in Contaminated Groundwater Environments

ABSTRACT The concentrations of molybdenum (Mo) and 25 other metals were measured in groundwater samples from 80 wells on the Oak Ridge Reservation (ORR) (Oak Ridge, TN), many of which are contaminated with nitrate, as well as uranium and various other metals. The concentrations of nitrate and uranium were in the ranges of 0.1 μM to 230 mM and <0.2 nM to 580 μM, respectively. Almost all metals examined had significantly greater median concentrations in a subset of wells that were highly contaminated with uranium (≥126 nM). They included cadmium, manganese, and cobalt, which were 1,300- to 2,700-fold higher. A notable exception, however, was Mo, which had a lower median concentration in the uranium-contaminated wells. This is significant, because Mo is essential in the dissimilatory nitrate reduction branch of the global nitrogen cycle. It is required at the catalytic site of nitrate reductase, the enzyme that reduces nitrate to nitrite. Moreover, more than 85% of the groundwater samples contained less than 10 nM Mo, whereas concentrations of 10 to 100 nM Mo were required for efficient growth by nitrate reduction for two Pseudomonas strains isolated from ORR wells and by a model denitrifier, Pseudomonas stutzeri RCH2. Higher concentrations of Mo tended to inhibit the growth of these strains due to the accumulation of toxic concentrations of nitrite, and this effect was exacerbated at high nitrate concentrations. The relevance of these results to a Mo-based nitrate removal strategy and the potential community-driving role that Mo plays in contaminated environments are discussed.

Thorgersen, Michael P.↗

In situ treatment of arsenic contaminated groundwater by aquifer iron coating: Experimental Study

In situ arsenic removal from groundwater by an iron coating method has great potential to be a cost effective and simple groundwater remediation technique, especially in rural and remote areas where groundwater is used as the main source of drinking water. The in situ arsenic removal technique was first optimized by simulating arsenic removal in various quartz sand columns under anoxic conditions., Its effectiveness was then evaluated in an actual high-arsenic groundwater environment. The mechanism of arsenic removal by the iron coating was investigated under different conditions using scanning electron microscopy (SEM)/X-ray absorption spectroscopy, an electron microprobe, and Fourier transformation infrared spectroscopy. A 4-step alternative cycle aquifer iron coating method was developed. A continuous injection of 5 mmol/L FeSO4 and 2.5 mmol/L NaClO for 96 hours can create a uniform coating of crystalline goethite on the surface of quartz sand in the columns without causing clogging. At a flow rate of 0.45 cm/min of the injection reagents (vi), the time for arsenic (as Na2HAsO4) to pass through the iron-coated quartz sand column was approximately 35 hours, which was much longer than that for tracer fluorescein sodium (approximately 2 hours). The retardation factor of arsenic was 23, and its adsorption capacity was 0.11 mol As per mol Fe, leading to an excellent arsenic removal. In situ arsenic removal from groundwater in an aquifer was achieved by simultaneous injections of As (V) and Fe (II) reagents. When the arsenic content in the groundwater was 233 μg/L, the aqueous phase arsenic was completely removed with an arsenic adsorption of 0.05 mol As per mol Fe. Arsenic fixation resulted from a process of adsorption/co-precipitation, in which arsenic and iron likely formed the arsenic-bearing iron mineral phases with poor crystallinity by way of bidentate binuclear complexes. Thus, the high arsenic removal efficiency of the technique likely resulted from the expanded specific iron oxide/hydroxide surface area with poor crystallinity and from coprecipitation.

arsenic, remediation, iron, coating↗

Management of multiple groundwater contaminant plumes extending beyond property boundaries at the young - Rainey STAR Center (Science, Technology, and Research Center) - 15623

The US DOE Pinellas Plant-now known as the Young - Rainey STAR Center, located in Largo, Florida-manufactured components for nuclear weapons from 1956 to 1995. During decades of operations, chlorinated solvents were released from a drum storage area and from underground piping at multiple points adjacent to and beneath a 4.5-hectare (11-acre) building. Two groundwater contaminant plumes associated with contaminant sources beneath the building have been identified, delineated, and are being monitored. During a focused delineation campaign in 2008 to better define the plume boundaries prior to municipal construction projects in the area, the plumes were determined to extend beyond the site boundaries, beneath the adjacent roadway easements, and beneath four adjacent privately owned properties. US DOE has performed a number of activities in response to the discovery of the offsite contaminant plumes, including performing a high-resolution delineation of contaminant plumes; coordinating with local municipalities to complete two linear construction projects requiring dewatering in the vicinity of the plumes; performing risk assessment, risk management, risk communication, and community relations tasks associated with the project; coordinating with state regulators to identify a risk-based corrective action regulatory approach; and coordinating with impacted property owners to develop and implement institutional controls. During the replacement of a 1.2-meter (48-inch) municipal potable water line directly over the contaminant plume area, US DOE (1) constructed infrastructure to receive and treat dewatering effluent at a rate of 20 gallons per minute around the clock for 6 weeks, and (2) conducted breathing-zone air monitoring during excavation of a 3.0-meter (10-foot) deep trench. This degree of diligence was necessary to ensure and document that no site workers were exposed to chlorinated solvent vapors during the construction process, and that a large volume of potentially contaminated groundwater was properly treated and dispositioned. US DOE also took aggressive actions to pro-actively address claims regarding loss of property value on two properties associated with the groundwater contamination, which resulted in a teaming arrangement with each party for future management of the ongoing corrective actions. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Florida International University Research on Soil and Groundwater Contamination at DOE's Hanford and Savannah River Sites - 18547

Nuclear weapons production and other defense-related activities at U.S. Department of Energy (DOE) sites have resulted in radionuclide and heavy metal contamination in surface and subsurface environments nationwide. The DOE Office of Environmental Management (DOE EM) faces a number of environmental challenges that are technically complex and unique to EM with tremendous associated cleanup costs. The success of the DOE EM mission will require development and insertion of innovative approaches and novel technologies to address the significant challenges associated with the remaining cleanup of contaminated sites. A key focus of the applied research portfolio addresses data gaps related to the behavior and chemistry of radionuclides of concern as well as the co-mingling of these contaminants in groundwater at EM sites such as Hanford, Savannah River, Oak Ridge and others. Florida International University (FIU) is conducting research in conjunction with Pacific Northwest National Laboratory (PNNL) and savannah River National Laboratory (SRNL) scientists to support environmental remediation efforts at Hanford and SRS. This research is focused on remediation technologies for contaminated soil and groundwater as well as the assessment of the fate and transport of contaminants in the environment. The overall objective is to reduce contaminant mobility through the development and application of state-of-the-art scientific and environmental remediation technologies. The FIU strategy is to conduct basic science research that fills knowledge gaps and complements work conducted at DOE sites. Support to Hanford includes contributing to the understanding of {sup 99}Tc chemistry and the fate and transport mechanisms of co-mingled contaminants including {sup 99}Tc, U(VI), Cr, and iodine (I). FIU has also provided basic science research that supports a treatability study currently underway at Hanford, which uses ammonia gas injection to manipulate pH and immobilize U(VI) in the subsurface. In addition, support for long-term monitored natural attenuation is provided through geophysical research that monitors subsurface contaminant and microbial responses. Research to evaluate the environmental factors that control the fate and transport of contaminants and co-contaminants in soil and groundwater is being performed for SRS. This research has contributed to the development, design, and deployment of innovative strategies to enhance the natural attenuation processes and to validate novel in situ remediation technologies. The SRS EM test bed demonstrations directly benefit SRS cleanup initiatives. Current investigations focus on natural organic compounds, such as humate, as a potential amendment for the treatment of uranium in groundwater associated with the SRS F-Area Seepage Basins plume, investigates the synergy between humate and silica to optimize the pH adjustment strategy for uranium remediation and investigates the interaction of Tc and I with soil from the Four Mile Branch wetland. Collaborative relationships between FIU and the national laboratories have provided synergy and benefits over the years to FIU, the national laboratories, the DOE complex, and the DOE EM mission. By working closely with the national laboratories, FIU research is not only closely aligned with the cleanup mission priorities at the DOE sites, but complements and supports the work at national laboratories. This coordination and leveraging of research efforts results in time- and cost-savings, and accelerates progress in the DOE EM environmental restoration mission. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Regulatory and Technical Issues Concerning the Detection and Treatment of NDMA-Contaminated Groundwater at NASA WSTF

The National Aeronautics and Space Administration (NASA) White Sands Test Facility (WSTF) was established in 1963 primarily to provide rocket engine testing services for several NASA programs. The groundwater underlying the site has been contaminated as a result of historical operations. Groundwater contaminants include several volatile organic compounds (VOCs) and two semi-volatile compounds: N-nitrosodimethylamine (NDMA) and N-nitrodimethylamine (DMN). This paper discusses some of the technical, analytical, regulatory, and health risk issues associated with the contaminant plume. The plume has moved approximately 2.5 miles downgradient of the facility industrial boundary, with evidence of continued migration. As a result, NASA has proposed a pump and treat system using air strippers and ultraviolet (UV) oxidation to stabilize future movement of the contaminant plume. The system has been designed to treat 1,076 gallons (4,073 liters) per minute, with provisions for future expansion. The UV oxidation process was selected to treat NDMA-contaminated groundwater based on successes at other NDMA-contaminated sites. Bench- and pilot-scale testing of WSTF groundwater confirmed the ability of UV oxidation to destroy NDMA and generated sufficient data to design the proposed full-scale treatment system. NDMA is acutely toxic and is a probable human carcinogen. EPA-recommended health risk criteria for the residential consumption of NDMA/DMN-contaminated groundwater was used to determine that a 1.0 x 10(exp -6) excess cancer risk corresponds to 1.7 parts per trillion (ppt). EPA analytical methods are unable to detect NDMA and DMN in the low ppt range. EPA's current Appendix IX analytical method used to screen for NDMA, Method 8270, can detect NDMA only at levels that are orders of magnitude greater than the recommended health risk level. Additionally, EPA Method 607, the most sensitive EPA approved method, has a detection limit of 150 ppt. This corresponds to an excess cancer risk of 9.0 x 10(exp -5), which exceeds the State of New Mexico's water quality standard of a cancer risk less than 1 x 10(exp -5). The treatment system has been engineered to treat contaminated groundwater to levels significantly below the New Mexico standard. However, the inability of EPA-approved analytical methods to detect NDMA and DMN at low ppt levels, and to provide verification of compliance with the 1 x 10(exp -5) cancer risk, introduces a notable risk to the long-term operation of the system. WSTF has been working with Southwest Research Institute to develop a non-EPA analytical method that can achieve a reporting limit of 1 ppt, which corresponds to an excess cancer risk of 7.6 x 10(exp -7). WSTF is currently developing a proposal to obtain approval from the New Mexico Environment Department (NMED) of this non-EPA method.

Wiebe, D. T.↗

Improving Long-term Monitoring of Contaminated Groundwater at Sites where Attenuation-based Remedies are Deployed

This study presents an effective approach to tackle the challenge of long-term monitoring of contaminated groundwater sites where remediation leaves residual contamination in the subsurface. Traditional long-term monitoring of contaminated groundwater sites focuses on measuring contaminant concentrations and is applicable to sites where contaminant mass is removed or degraded to a level below the regulatory standard. The traditional approach is less effective at sites where risk from metals or radionuclides continues to exist in the subsurface after remedial goals are achieved. We propose a long-term monitoring strategy for this type of waste site that focuses on measuring the hydrological and geochemical parameters that control attenuation or remobilization of contaminants while de-emphasizing contaminant-concentration measurements. Furthermore, we demonstrate how this approach would be more effective than traditional long-term monitoring, using a site in South Carolina, USA, where groundwater is contaminated by several radionuclides. A comprehensive enhanced attenuation remedy has been implemented at the site to minimize discharge of contamination to surface water. The immobilization of contaminants occurs in three locations by manipulation of hydrological and geochemical parameters, as well as by natural attenuation processes. Deployment of our proposed long-term monitoring strategy will combine subsurface and surface measurements using spectroscopic tools, geophysical tools, and sensors to monitor the parameters controlling contaminant attenuation. The advantage of this approach is that it will detect the potential for contaminant remobilization from engineered and natural attenuation zones, allowing potential adverse changes to be mitigated before contaminant attenuation is reversed.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Optimized Machine Learning Model for Predicting Groundwater Contamination

The use of physical models to predict groundwater contaminant movement remains technically challenging due to the complexity of the phenomena, the heterogeneity of key parameters in nature, and the presence of poorly defined interactive and feedback processes. New approaches to address these challenges are needed. In this study, we evaluate various Artificial Intelligence (AI)-based approaches to understand a hexavalent chromium (Cr(VI)) plumes located on the U.S. Department of Energy’s (DOE) Hanford Site in Richland, WA. The groundwater monitoring dataset used in this study included data from the 100 Area along the Columbia River and included data collected between 2010 to 2019. This study investigates the most prominent contaminant, Cr(VI), with the Extreme Gradient Boosting (XGBoost) machine learning model. The XGBoost models were compared with optimized versions using an Empirical Bayes Search Cross-Validation technique for better prediction. The optimized XGBoost model yielded an R^2 value of 0.99 on the training set and 0.85 on the testing set, whereas XGBoost without optimization yielded a value of 0.83 on the training set and 0.85 on the testing set. This paper provides an overview of a computational method for groundwater contamination modeling that shows promise for improving current remediation efforts.

Mazumdar, Hirak↗

Parameter estimation and prediction for groundwater contamination based on measure theory

The problem of groundwater contamination in an aquifer is one with many uncertainties. Properly quantifying these uncertainties is es- sential in order to make reliable probabilistic based predictions and decisions regarding remediation strategies. In this work, a measure-theoretic frame- work is employed to quantify uncertainties in a simpli ed groundwater con- tamination transport model. Given uncertain data from observation wells, the stochastic inverse problem is solved numerically to obtain a probability measure on the space of unknown model parameters characterizing ground- water ow and contaminant transport in an aquifer, as well as unknown model boundary or source terms such as the contaminant source release into the environment. This probability measure is used to make predictions of future contaminant concentrations and to analyze possible remediation techniques. The ability to identify regions of small but nonzero probability using this method is illustrated.

54 ENVIRONMENTAL SCIENCES↗

Fitness factors impacting survival of a subsurface bacterium in contaminated groundwater

Many factors contribute to the ability of a microbial species to persist when encountering complexly contaminated environments, including time of exposure, the nature and concentration of contaminants, availability of nutritional resources, and possession of a combination of appropriate molecular mechanisms needed for survival. Herein we sought to identify genes that are most important for survival of Gram-negative Enterobacteriaceae in contaminated groundwater environments containing high concentrations of nitrate and metals using the metal-tolerant Oak Ridge Reservation isolate, Pantoea sp. MT58 (MT58). Survival fitness experiments in which a randomly barcoded transposon insertion (RB-TnSeq) library of MT58 was exposed directly to contaminated Oak Ridge Reservation groundwater samples from across a nitrate and mixed metal contamination plume were used to identify genes important for survival with increasing exposure times and concentrations of contaminants, and availability of a carbon source. Genes involved in controlling and using carbon, encoding transcriptional regulators, and related to Gram-negative outer membrane processes were among those found to be important for survival in contaminated Oak Ridge Reservation groundwater. A comparative genomics analysis of 75 Pantoea genus strains allowed us to further separate the survival determinants into core and non-core genes in the Pantoea pangenome, revealing insights into the survival of subsurface microorganisms during contaminant plume intrusion.

59 BASIC BIOLOGICAL SCIENCES↗

Fe doped TiO{sub 2} photocatalyst for the removal of As(III) under visible radiation and its potential application on the treatment of As-contaminated groundwater

Highlights: • Incorporation of Fe in TiO{sub 2} lattice extended absorption to visible light region. • TiO{sub 2}–Fe 1.0 in anatase crystalline form was synthesized by sol–gel method. • TiO{sub 2}–Fe 1.0 showed the highest photocatalytic activity for As(III) oxidation. • TiO{sub 2}–Fe 1.0 had the highest adsorption capacity for the removal of generated As(V). • TiO{sub 2}–Fe is a promising material on the treatment of As contaminated groundwater. - Abstract: The Fe doped TiO{sub 2} catalyst was evaluated under visible radiation for As(III) removal. The TiO{sub 2}–Fe was synthesized by sol–gel technique at 0.0, 1.0, 2.5, 5.0 and 10.0 wt% iron doping concentrations. The semiconductors were characterized by X-ray diffraction, diffuse reflectance UV–vis, Raman spectroscopy, nitrogen physisorption, SEM–EDS and potentiometric titration for point of zero charge determination. The photocatalytic oxidation of As(III) was assessed in aqueous suspension contained 5 mg L{sup −1} As(III) at pH 7 with 0.25 g L{sup −1} catalyst loading. The incorporation of iron ions in TiO{sub 2} lattice extended the absorption to visible light region and create surface oxygen vacancies which favor photocatalytic oxidation reaction of As(III) using a small doping amount of Fe (1.0 wt%) in TiO{sub 2} powder. Additionally, TiO{sub 2}–Fe 1.0 showed the highest adsorption capacity for As(V) removal compared to sol–gel TiO{sub 2} and P25 indicating that this catalyst is a promising material for As contaminated groundwater treatment.

36 MATERIALS SCIENCE↗

Characterization of the extremely arsenic-resistant Brevibacterium linens strain AE038-8 isolated from contaminated groundwater in Tucuman, Argentina

Brevibacterium linens AE038-8, isolated from As-contaminated groundwater in Tucumán (Argentina), is highly resistant to arsenic oxyanions, being able to tolerate up to 1 M As(V) and 75 mM As(III) in a complex medium. Strain AE038-8 was also able to reduce As(V) to As(III) when grown in complex medium but paradoxically it could not do this in a defined minimal medium with sodium acetate and ammonium sulfate as carbon and nitrogen sources, respectively. No oxidation of As(III) to As(V) was observed under any conditions. Here, three copies of the ars operon comprising arsenic resistance genes were found on B. linens AE038-8 genome. In addition to the well known arsC , ACR3 and arsR , two copies of the arsO gene of unknown function were detected.

54 ENVIRONMENTAL SCIENCES↗

Microbial Functional Gene Diversity Predicts Groundwater Contamination and Ecosystem Functioning

Contamination from anthropogenic activities has significantly impacted Earth’s biosphere. However, knowledge about how environmental contamination affects the biodiversity of groundwater microbiomes and ecosystem functioning remains very limited. Here, we used a comprehensive functional gene array to analyze groundwater microbiomes from 69 wells at the Oak Ridge Field Research Center (Oak Ridge, TN), representing a wide pH range and uranium, nitrate, and other contaminants. We hypothesized that the functional diversity of groundwater microbiomes would decrease as environmental contamination (e.g., uranium or nitrate) increased or at low or high pH, while some specific populations capable of utilizing or resistant to those contaminants would increase, and thus, such key microbial functional genes and/or populations could be used to predict groundwater contamination and ecosystem functioning. Our results indicated that functional richness/diversity decreased as uranium (but not nitrate) increased in groundwater. In addition, about 5.9% of specific key functional populations targeted by a comprehensive functional gene array (GeoChip 5) increased significantly (P < 0.05) as uranium or nitrate increased, and their changes could be used to successfully predict uranium and nitrate contamination and ecosystem functioning. Here, this study indicates great potential for using microbial functional genes to predict environmental contamination and ecosystem functioning.

54 ENVIRONMENTAL SCIENCES↗

The Nature and State of Groundwater Contamination at the Nevada National Security Site: What Have We Learned from Decades of Groundwater Analysis? - 20337

The regulatory framework for remediating radionuclide contamination from underground nuclear testing at the Nevada National Security Site (NNSS) is based on a combination of characterization and modeling studies, monitoring, and institutional controls [1]. Currently, tritium is the largest contributor (∼90%) to the estimated 44.6 million-curie radionuclide inventory resulting from underground testing [2]. Because of its short half-life (12.32 years), its relative contribution reduces below 10% of the total radiologic inventory over the next 120 years as a result of radioactive decay. Although tritium levels are observed well above the Safe Drinking Water Act (SDWA) maximum contaminant levels (MCLs) in groundwater, other radionuclides are well below their MCLs except within the nuclear test near-field (nuclear test cavity and chimney) environment. In fact, most device-derived radionuclides are below their MCL in groundwater even in samples collected from this near-field environment. The distribution of radionuclides following the nuclear detonation greatly influences the availability of potential contaminants for groundwater transport. Tritium is initially distributed in the gas phase, later as tritiated water in steam, and finally as liquid water, and is available to groundwater transport away from the near-field environment. Other radionuclides that are mobile in groundwater are {sup 14}C, {sup 36}Cl, {sup 99}Tc, and {sup 129}I though their radiologic inventory is small when compared to tritium. Many radionuclides (e.g. U, Pu, Am) are incorporated to a significant extent into the melt glass at the bottom of the cavity and are accessible to groundwater primarily through the slow process of glass dissolution. These radionuclides are also adsorbed to the surfaces of the crushed rock within the cavity and chimney which limits their migration in groundwater. Although colloid facilitated transport of radionuclides at the NNSS has been observed [3], radionuclide concentrations decrease with time and migration distances due to desorption and colloid filtration processes. Current studies indicate that radionuclides associated with colloids are unlikely to migrate downgradient from NNSS underground nuclear tests at concentrations above the SDWA MCL [4][5]. The results of over 50 years of sampling, along with an understanding of these post detonation processes, indicate that tritium is the only contaminant of concern downgradient of testing and that even tritium will not exceed its MCL in groundwater after ∼120 years. Although other longer-lived radionuclides may continue to be released slowly from the near-field environment they will likely never reach levels exceeding their MCLs in groundwater downgradient of the NNSS. Groundwater monitoring will continue to verify these observations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

In Situ Monitoring of Groundwater Contamination Using the Kalman Filter

This study presents a Kalman filter-based framework to establish a real-time in situ monitoring system for groundwater contamination based on in situ measurable water quality variables, such as specific conductance (SC) and pH. First, this framework uses principal component analysis (PCA) to identify correlations between the contaminant concentrations of interest and in situ measurable variables. It then applies the Kalman filter to estimate contaminant concentrations continuously and in real-time by coupling data-driven concentration-decay models with the previously identified data correlations. We demonstrate our approach with historical groundwater data from the Savannah River Site F-Area: We use SC and pH data to estimate tritium and uranium concentrations over time. Results show that the developed method can estimate these contaminant concentrations based on in situ measurable variables. The estimates remain reliable with less frequent or no direct measurements of the contaminant concentrations, while capturing the dynamics of short- and long-term contaminant concentration changes. In addition, we show that data mining, such as PCA, is useful to understand correlations in groundwater data and to design long-term monitoring systems. As a result, the developed in situ monitoring methodology is expected to improve long-term groundwater monitoring by continuously confirming the contaminant plume's stability and by providing an early warning system for unexpected changes in the plume's migration.

54 ENVIRONMENTAL SCIENCES↗