Selenite Stable Isotope Fractionation during Abiotic Reduction by Sodium Sulfide.

Reduction of Se(IV) by sulfur reducing bacteria (SRB) can remove Se from groundwater either by direct respiration or the production of H2S(g) and subsequent abiotic reduction. This study examined abiotic Se(IV) reduction by H2S(g) to determine the associated Se isotope fractionation. The extent of fractionation was compared to the results with studies of Se(IV) reduction in systems containing microorganisms to assess whether these processes could be distinguished. A solution containing Na2S was added in increasing concentrations to solutions containing Se(IV) as SeO32- to reduce and precipitate Se. Precipitates with three distinct colors were observed. Powder X-ray diffraction (PXRD) results yielded three distinct spectra for each of the three colors of precipitate, which corresponded to SenS8-n (orange) or Se(0) (red) and S(0) (yellow). The δ82Se values of the residual dissolved Se increased as the aqueous Se concentration decreased. The S/Se in solution affected the isotopic fractionation, with an 82ε of 10.1 ± 0.6‰ observed for solutions with S/Se < 1.7, and of 7.9 ± 0.3‰ for solutions with S/Se > 1.7.

Natural Attenuation of Groundwater Uranium in Post-Neutral-Mining Sites Evidenced from Multiple Isotopes and Dissolved Organic Matter.

Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ34SSO4 and δ18OSO4 values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.

Pollutant Photodegradation Affected by Evaporative Water Concentration in a Climate Change Scenario.

Evaporative water concentration takes place in arid or semi-arid environments when stationary water bodies, such as lakes or ponds, prevalently lose water by evaporation, which prevails over outflow or seepage into aquifers. Absence or near-absence of precipitation and elevated temperatures are important prerequisites for the process, which has the potential to deeply affect the photochemical attenuation of pollutants, including contaminants of emerging concern (CECs). Here we show that water evaporation would enhance the phototransformation of many CECs, especially those undergoing degradation mainly through direct photolysis and triplet-sensitized reactions. In contrast, processes induced by hydroxyl and carbonate radicals would be inhibited. Our model results suggest that the photochemical impact of water evaporation might increase in the future in several regions of the world, with no continent likely being unaffected, due to the effects of local precipitation decrease combined with an increase in temperature that facilitates evaporation.

Elevated Radium Activity in a Hydrocarbon-Contaminated Aquifer.

Hydrocarbon spills that reach the subsurface can modify aquifer geochemical conditions. Biogeochemical zones typically form proximal to the source zone that include iron (Fe(III)) and manganese (Mn(III/IV)) (hydr)oxide reduction, with potential to release associated geogenic contaminants to groundwater. Here, multi-level monitoring systems are used to investigate radium (226Ra, 228Ra) activities in an aquifer contaminated with a mixture of chlorinated solvents, ketones, and aromatics occurring as a dense non-aqueous phase liquid in the source zone. 226Ra activities are up to 10 times higher than background 60 m downgradient from the source zone, where pH is lower, total dissolved solid concentrations are higher, and conditions are methanogenic. Correlations indicate that Fe and Mn (hydr)oxide reduction and sorption site competition are likely responsible for elevated Ra activities within the dissolved phase plume. 226Ra activities return to background within the Fe(III)/SO42--reducing zone 600 m downgradient from the source, near the middle of the dissolved phase plume. Geochemical models indicate that sorption to secondary phases (e.g., clays) is important in sequestering Ra within the plume. Although maximum Ra activities within the plume are well below the U.S. drinking water standard, elevated activities compared to background emphasize the importance of investigating Ra and other trace elements at hydrocarbon-impacted sites.

Kinetics of Hydroxyl Radical Production from Oxygenation of Reduced Iron Minerals and Their Reactivity with Trichloroethene: Effects of Iron Amounts, Iron Species, and Sulfate Reducing Bacteria.

Reactive oxygen species generated during the oxygenation of different ferrous species have been documented at groundwater field sites, but their effect on pollutant destruction remains an open question. To address this knowledge gap, a kinetic model was developed to probe mechanisms of •OH production and reactivity with trichloroethene (TCE) and competing species in the presence of reduced iron minerals (RIM) and oxygen in batch experiments. RIM slurries were formed by combining different amounts of Fe(II) and sulfide (with Fe(II):S ratios from 1:1 to 50:1) or Fe(II) and sulfate with sulfate reducing bacteria (SRB) added. Extents of TCE oxidation and •OH production were both greater with RIM prepared under more reducing conditions (more added Fe(II)) and then amended with O2. Kinetic rate constants from modeling indicate that •OH production from free Fe(II) dominates •OH production from solid Fe(II) and that TCE competes for •OH with Fe(II) and organic matter (OM). Competition with OM only occurs in experiments with SRB, which include cells and their exudates. Experimental results indicate that cells and/or exudates also provide electron equivalents to reform Fe(II) from oxidized RIM. Our work provides new insights into mechanisms and environmental significance of TCE oxidation by •OH produced from oxygenation of RIM. However, further work is necessary to confirm the relative importance of reaction pathways identified here and to probe potentially unaccounted for mechanisms that affect abiotic TCE oxidation in natural systems.

Machine Learning Modeling Based on Microbial Community for Prediction of Natural Attenuation in Groundwater.

Natural attenuation is widely adopted as a remediation strategy, and the attenuation potential is crucial to evaluate whether remediation goals can be achieved within the specified time. In this work, long-term monitoring of indigenous microbial communities as well as benzene, toluene, ethylbenzene, and xylene (BTEX) and chlorinated aliphatic hydrocarbons (CAHs) in groundwater was conducted at a historic pesticide manufacturing site. A machine learning approach for natural attenuation prediction was developed with random forest classification (RFC) followed by either random forest regression (RFR) or artificial neural networks (ANNs), utilizing microbiological information and contaminant attenuation rates for model training and cross-validation. Results showed that the RFC could accurately predict the feasibility of natural attenuation for both BTEX and CAHs, and it could successfully identify the key genera. The RFR model was sufficient for the BTEX natural attenuation rate prediction but unreliable for CAHs. The ANN model showed better performance in the prediction of the attenuation rates for both BTEX and CAHs. Based on the assessments, a composite modeling method of RFC and ANN was proposed, which could reduce the mean absolute percentage errors. This study reveals that the combined machine learning approach under the synergistic use of field microbial data has promising potential for predicting natural attenuation.

The collaborative monitored natural attenuation (CMNA) of soil and groundwater pollution in large petrochemical enterprises: A case study.

A large in-service petrochemical enterprises in Northeast China was taken as the research object, and the Collaborative Monitored Natural Attenuation (CMNA) for soil and groundwater pollution was carried out to remedy combined pollution and reduce environmental risks. The pollutants distributions were obtained based on detailed regional investigation (Mar. 2019), and feature pollutants in soil and groundwater were then screened. The spatiotemporal variations of feature pollutants and relative microbial responses were explored during the CMNA process. Furthermore, the CMNA efficiency of the contaminated site at initial stage was evaluated by calculation of natural attenuation rate constant. The results showed that the feature pollutants in soil were 2,2',5,5'-tetrachlorobiphenyl (2,2',5,5'-TCB) and petroleum hydrocarbons (C10∼C40), and the feature pollutant in groundwater was 1,2-dichloroethane (1,2-DCA). The concentrations of all feature pollutants decreased continuously during four years of monitoring. Feature pollutants played a dominant role in the variability of microbial species both in soil and groundwater, increasing the relative abundance of petroleum tolerant/biodegradation bacteria, such as Actinobacteria, Proteobacteria and Acidobacteriota. The average natural attenuation rate constant of 2,2',5,5'-TCB and C10∼C40 in soil was 0.0012 d-1 and 0.0010 d-1, respectively, meeting the screening value after four years' attenuation. The average natural attenuation rate constant of 1,2-DCA was 0.0004 d-1, which need strengthening measures to improve the attenuation efficiency.

An experimental oil spill at a tidal freshwater wetland along the St. Lawrence River re-visited after 21 years.

In 1999, a tidal wetland located along the St. Lawrence River close to Ste. Croix de Lotbinière (Quebec, Eastern Canada) was the site of an experimental oil spill. Test plots were established and subjected to an experimental crude oil spill to evaluate natural attenuation, nutrient amendment and vegetation cropping as countermeasures. In 2020, this study re-visited the test plots to investigate residual oil and habitat recovery. Only concentrations of mid-chain length n-alkanes (C10-C36), but not of polycyclic aromatic hydrocarbons (PAHs), were significantly above detection limit, and were detected in both test plot and control sediments. Hydrocarbon, total organic carbon, nitrogen and phosphate contents did not differ significantly between test plot and control sediments. Microbial analyses did not detect significant differences in microbial load, microbial diversity or microbial community composition between test plot and control sediments. Key genes for the aerobic and anaerobic degradation of n-alkanes as well as for the aerobic degradation of PAHs were detected in all sediment samples. Associated gene abundances did not differ significantly between test plot and control sediments. This study shows that oil-exposed test plot sediments of the Ste. Croix wetland can be considered completely recovered after 21 years irrespective of the performed countermeasure.

Impact evaluation of typhoons and remediation works on spatiotemporal evolution of air dose rate in two riverside parks in Fukushima, Japan after the Dai-ichi nuclear power plant accident.

This study elucidated the impacts of typhoon events and remediation works on the spatiotemporal evolution of the air dose rate in riverside areas frequented by residents. Spatial distribution of the air dose rate and radiocesium concentration in the sediments were measured in two riverside parks located near each other in Fukushima Prefecture, Japan, for 2015-2020. The air dose rates measured by walk surveys were interpolated using ordinary kriging to generate air dose rate maps, to facilitate a comparison between the results at different points in time during the measurement campaigns. After the typhoons that occurred during 2015-2018, the air dose rate near the riverside in one park decreased, but not in the other, because the erosion and sediment deposition patterns differed between them. This could be due to the presence of a dam upstream, which serves a flood mitigation function. However, the extreme event of typhoon Hagibis in 2019 dropped the air dose rates near the riversides in both parks. In contrast to the typhoon events which affected the riverside areas, remediation works such as decontamination undertaken during 2015-2019 reduced the air dose rates around the garden and lawn areas which are frequently used as recreational sites. Modeling the temporal evolutions in the air dose rates for the entire area of the riverside parks revealed that 35% of the reduction was caused by physical decay of radiocesium on average, 14% by vertical migration of radiocesium in the soil through precipitation, and 51% by the three typhoons and remediation works during 2015-2019. The contribution of 20% from the strongest typhoon Hagibis highlights the fact that floods resulting from large typhoons are effective in causing natural attenuation of air dose rates in riverside parks.

Improving assessment quality of soil natural attenuation capacity at the point and regional scales.

Soil natural attenuation capacity (NAC) is an important ecosystem service that maintains a clean environment for organisms in the soil, which in turn supports other services. However, spatially varying indicator weights were rarely considered in the traditionally-used soil NAC assessment model (e.g., ecosystem-service performance model) at the point scale. Moreover, in the spatial simulation of soil NAC, the traditionally-used geostatistical models were usually susceptible to spatial outliers and ignored valuable auxiliary information (e.g., land-use types). This study first proposed a novel soil NAC assessment method based on the ecosystem-service performance model and moving window-entropy weight method (MW-EW) (NACMW-EW). Next, NACMW-EW was used to assess soil NAC in a typical area in Guixi City, China, and further compared with the traditionally-used NACtra and NACEW. Then, robust sequential Gaussian simulation with land-use types (RSGS-LU) was established for the spatial simulation of NACMW-EW and compared with the traditionally-used SGS, SGS-LU, and RSGS. Last, soil NAC's spatial uncertainty was evaluated based on the 1000 realizations generated by RSGS-LU. The results showed that: (i) MW-EW effectively revealed the spatially varying indicator weights but EW couldn't; (ii) NACMW-EW obtained more reasonable results than NACtra and NACEW; (iii) RSGS-LU (RMSE = 0.118) generated higher spatial simulation accuracy than SGS-LU (RMSE = 0.123), RSGS (RMSE = 0.132), and SGS (RMSE = 0.135); and (iv) the relatively high (P[NACMW-EW(u) > 0.57] ≥ 0.95) and low (P[NACMW-EW(u) > 0.57] ≤ 0.05) threshold-exceeding probability areas were mainly located in the south and east of the study area, respectively. It is concluded that the proposed methods were effective tools for soil NAC assessment at the point and regional scales, and the results provided accurate spatial decision support for soil ecosystem service management.

Organohalide Respiration with Diclofenac by Dehalogenimonas.

Diclofenac (DCF) is a pharmaceutically active contaminant frequently found in aquatic ecosystems. The transformation pathways and microbiology involved in the biodegradation of DCF, particularly under anoxic conditions, remain poorly understood. Here, we demonstrated microbially mediated reductive dechlorination of DCF in anaerobic enrichment culture derived from contaminated river sediment. Over 90% of the initial 76.7 ± 3.6 µM DCF was dechlorinated at a maximum rate of 1.8 ± 0.3 µM day-1 during a 160 days' incubation. Mass spectrometric analysis confirmed that 2-(2-((2-chlorophenyl)amino)phenyl)acetic acid (2-CPA) and 2-anilinophenylacetic acid (2-APA) were formed as the monochlorinated and nonchlorinated DCF transformation products, respectively. A survey of microbial composition and Sanger sequencing revealed the enrichment and dominance of a new Dehalogenimonas population, designated as Dehalogenimonas sp. strain DCF, in the DCF-dechlorinating community. Following the stoichiometric conversion of DCF to 2-CPA (76.0 ± 2.1 µM) and 2-APA (3.7 ± 0.8 µM), strain DCF cell densities increased by 24.4 ± 4.4-fold with a growth yield of 9.0 ± 0.1 × 108 cells per µmol chloride released. Our findings expand the metabolic capability in the genus Dehalogenimonas and highlight the relevant roles of organohalide-respiring bacteria for the natural attenuation of halogenated contaminants of emerging concerns (e.g., DCF).

Occurrence of polycyclic aromatic compounds and potentially toxic elements contamination and corresponding interdomain microbial community assembly in soil of an abandoned gas station.

Bacteria, archaea and fungi usually coexist in various soil habitats and play important roles in biogeochemical cycle and remediation of contamination. Despite their significance, their combined bioassembly pattern, ecological interactions and driving factors in contaminated soils still remain obscure. To fill the gap, a systemic investigation on the characteristics of microbial community including bacteria, archaea and fungi, assembly patterns and environmental driving factors was conducted in an abandoned gas station soils which were contaminated by polycyclic aromatic compounds and potentially toxic elements for decades. The results showed that the soils were contaminated excessively by benzo[a]pyrene (0.46-2.00 mg/kg) and Dibenz[a,h]anthracene (0.37-1.30 mg/kg). Multitudinous contaminant-degrading/resistant microorganisms and unigenes were detected, indicating potential of the soils to mitigate the pollution. Compared with fungi and archaea, the bacteria had higher community diversity and were more responsive to seasonal shifts. Functional genes (nidB, nahAb, nahAa, adhP, adh, adhC, etc.) involved in biodegradation were highly enriched in summer (1.96% vs 1.80%). The co-occurrence network analysis showed summer communities exhibit a more robust network structure and positive interactions than winter communities. The fungi Neocucurbitaria, Penicillium, Fusarium, Chrysosporium, Knufia, Filobasidium, Wallemia and Rhodotorula were identified as the keystone taxa, indicating that fungi also had important positions in the interdomain molecular ecological networks of both seasons. The network topological properties and |ßNTI| (66.7%-93.3% greater than 2) results indicated the deterministic assembly processes of the microbial communities in the contaminated soil. Acenaphthylene, benzo[b]fluoranthene, indeno[1,2,3-cd]perylene, benzo[g,h,i]pyrene and 9-fluorenone were the key environmental factors driving the deterministic assembly processes of the interdomain microbial community in the contaminated soil. These findings extended our knowledge of interdomain microbial community assembly mechanisms and ecological patterns in natural attenuation and provide valuable guidance in associated bioremediation strategies.

Natural attenuation of sulfometuron-methyl in seawater: Kinetics, intermediates, toxicity change and ecological risk assessment.

This research aims to evaluate the environmental feasibility of sulfometuron-methyl (SM) as a growth inhibitor for restricting the growth of Spartina alterniflora. To achieve this purpose, the natural attenuation characteristics, ecological risk, degradation pathway, and comprehensive toxicity changes of SM in seawater were investigated under the simulated marine environmental conditions of Jiaozhou Bay, China. The natural attenuation of SM in seawater followed first-order reaction kinetics with a rate constant (K) of 0.0694 d-1 and a half-life of 9.99 days. When photolysis, hydrolysis, and biodegradation pathways act alone, the rate constants K of SM were 0.0167, 0.0143, and 0.0099 d-1 respectively, indicating that their contributions to the total removal of SM decreased in turn. The calculation results of risk quotient (RQ) showed that the seawater containing 10 mg/L of SM demonstrated a very high risk to marine diatom Skeletonema costatum before and after 21 days of attenuation with RQ values of 24.46 and 6.32, respectively, however, the risk to other marine organisms (fish, crustaceans, and bivalves) decreased from moderate (RQ < 1) to low (RQ < 0.01). Four attenuation products of SM were identified and two degradation pathways of SM in seawater were proposed. Based on the rate of inhibition of bioluminescence, SM in seawater was not harmful to Photobacterium phosphoreum T3, whereas the toxicity of seawater containing SM increased with the extension of attenuation time, suggesting the formation of intermediate products with high aquatic toxicity. According to the toxicity values predicted by ECOSAR, the toxicity of one identified attenuation product was higher than that of SM. To the best of our knowledge, this is the first report on the attenuation characteristics and toxicity changes of SM in seawater. The results indicated that the toxicity of both SM and its degradation products to non-target marine organisms should be considered in evaluating the feasibility of SM in controlling coastal Spartina alterniflora.

Assessment of aerobic biodegradation of lower-chlorinated benzenes in contaminated groundwater using field-derived microcosms and compound-specific carbon isotope fractionation.

Biodegradation of lower chlorinated benzenes (tri-, di- and monochlorobenzene) was assessed at a coastal aquifer contaminated with multiple chlorinated aromatic hydrocarbons. Field-derived microcosms, established with groundwater from the source zone and amended with a mixture of lower chlorinated benzenes, evidenced biodegradation of monochlorobenzene (MCB) and 1,4-dichlorobenzene (1,4-DCB) in aerobic microcosms, whereas the addition of lactate in anaerobic microcosms did not enhance anaerobic reductive dechlorination. Aerobic microcosms established with groundwater from the plume consumed several doses of MCB and concomitantly degraded the three isomers of dichlorobenzene with no observable inhibitory effect. In the light of these results, we assessed the applicability of compound stable isotope analysis to monitor a potential aerobic remediation treatment of MCB and 1,4-DCB in this site. The carbon isotopic fractionation factors (ε) obtained from field-derived microcosms were -0.7‰ ± 0.1 ‰ and -1.0‰ ± 0.2 ‰ for MCB and 1,4-DCB, respectively. For 1,4-DCB, the carbon isotope fractionation during aerobic biodegradation was reported for the first time. The weak carbon isotope fractionation values for the aerobic pathway would only allow tracing of in situ degradation in aquifer parts with high extent of biodegradation. However, based on the carbon isotope effects measured in this and previous studies, relatively high carbon isotope shifts (i.e., ∆δ13C > 4.0 ‰) of MCB or 1,4-DCB in contaminated groundwater would suggest that their biodegradation is controlled by anaerobic reductive dechlorination.

Soil microbial communities-mediated bioattenuation in simulated aquifer storage and recovery (ASR) condition: Long-term study.

This study evaluated the long-term organic removal performance and microbial community shift in simulated aquifer storage and recovery (ASR) conditions. For this purpose, anoxic soil box systems were operated at 15 °C for one year. The results showed that the assimilable organic carbon (AOC) concentration in the anoxic soil box systems was successfully decreased by 79.1%. The dissolved organic carbon (DOC) concentration increased during the initial operational periods; however, it subsequently decreased during long-term operation. Readily biodegradable organic fractions (i.e., low-molecular weight (LMW) neutrals and LMW acids) decreased along with time elapsed, whereas non-biodegradable fraction (i.e., humic substances) increased. Proteobacteria and Acidobacteriota were predominant in the anoxic box systems throughout the operational periods. Firmicutes and Bacteroidota suddenly increased during the initial operational period while Gemmatimonadota slightly increased during prolonged long-term operation. Interestingly, the microbial community structures were significantly shifted with respect to the operational periods while the effects of AOC/NO3- addition were negligible. Various bacterial species preferring low temperature or anoxic conditions were detected as predominant bacteria. Some denitrifying (i.e., Noviherbaspirillum denitrificans) and iron reducing bacteria (i.e., Geobacter spp.) appeared during the long-term operation; these bacterial communities also acted as organic degraders in the simulated ASR systems. The findings of this study suggest that the application of natural bioattenuation using indigenous soil microbial communities can be a promising option as an organic carbon management strategy in ASR systems.

Improving the Bioremediation and in situ Production of Biocompounds of a Biodiesel-Contaminated Soil.

We aimed to produce simultaneously biosurfactants and lipases in solid state fermentation (SSF) using Aspergillus niger, followed by the use of the fermented media on the bioremediation of oily contaminated soil, in order to valuate agro industrial residuals and reduce the contamination. The biocompounds were produced using wheat bran and corncob (80:20), 5% of soybean oil and 0.5% of sugar cane molasses in SSF for 4 d, producing 4.58 ± 0.69 UE of emulsifying activity and 7.77 ± 1.52 U of lipolytic activity. This fermented media was used in the bioremediation of a 20% biodiesel contaminated soil, evaluating for 90 d microbial growth, contaminant degradation, and production of lipases and biosurfactants in soils. Six experimental strategies (natural attenuation; biostimulation + bioaugmentation + biocompounds; biostimulation + biosurfactant; biocompounds extract; biostimulation; adsorption of contaminant) were realized. The highest degradation of contaminant was verified in 90 d, of 74.40 ± 1.76%, and the production of biosurfactants and lipases in situ in the soil was found in 30 d (6.02 ± 0.24% of reduction in surface tension and 6.62 ± 0.17 UL of lipid activity in soil) for the same experiment (biostimulation + bioaugmentation + biocompounds). The addition of biostimulation + biosurfactant promotes higher biodegradation (66.00 ± 0.92%) of the contaminant than the biocompounds extract (59.58 ± 0.34%). The use of a solid fermented culture medium containing both biocompounds was feasible for the treatment of contaminants, demonstrating the potential for environmental application without the need for purification processes.

Phytoremediation of potentially toxic elements using constructed wetlands in coastal areas with a mining influence.

This paper proposes the use of wetlands as a phytoremediation strategy for areas of mining and maritime influence in the southeast of Spain. Potentially toxic elements (PTEs) tolerant and salinity-resistant macrophytes (Phragmites australis, Juncus effusus and Iris pseudacorus) have been used. The experiment is carried out in an aerobic artificial wetland using representative sediments affected by mining activities in the study area. Selected species were placed in pots containing substrates made with different mixtures of topsoil and/or peat, mining residues (black or yellow sand). After six months, rhizosphere, root and aerial parts were collected. A transfer study of As, Pb, Zn and Cu is performed, determining contents in rhizosphere and plant (aerial and underground part). From these data, the TF and BCF were calculated for each plant in 15 different substrates. The work is complemented by an initial study of scanning electron microscopy (SEM-EDX) of plants. The obtained results indicate a tolerance of the metallophytes to these PTEs, which may favour the obtaining of a naturalized habitat that acts as an effective protective barrier to the ecosystem, that is easy to maintain and that avoid the risk of transfer to the trophic chain. The use of these species can be a complement to the chemical stabilization proposed for the whole area and carried out in experimental plots. Because they are perennial plants, it is necessary to continue with the experiments and obtain results in a longer period of time that allows to evaluate yield and stabilization.

Anaerobic 1,4-dioxane biodegradation and microbial community analysis in microcosms inoculated with soils or sediments and different electron acceptors.

1,4-Dioxane, a probable human carcinogen, is a co-contaminant at many chlorinated solvent-contaminated sites. Although numerous 1,4-dioxane-degrading aerobic bacteria have been isolated, almost no information exists on the microorganisms able to degrade this chemical under anaerobic conditions. Here, the potential for 1,4-dioxane biodegradation was examined using multiple inocula and electron acceptor amendments. The inocula included uncontaminated agricultural soils and river sediments as well as sediments from two 1,4-dioxane contaminated sites. Five separate experiments involved the examination of triplicate live microcosms and abiotic controls for approximately 1 year. Compound-specific isotope analysis (CSIA) was used to further investigate biodegradation in a subset of the microcosms. Also, DNA was extracted from microcosms exhibiting 1,4-dioxane biodegradation for microbial community analysis using 16S rRNA gene amplicon high-throughput sequencing. Given the long incubation periods, it is likely that electron acceptor depletion occurred and methanogenic conditions eventually dominated. The iron/EDTA/humic acid or sulfate amendments did not result in 1,4-dioxane biodegradation in the majority of cases. 1,4-dioxane biodegradation was most commonly observed in the nitrate amended and no electron acceptor treatments. Notably, both contaminated site sediments illustrated removal in the samples compared to the abiotic controls in the no electron acceptor treatment. However, it is important to note that the degradation was slow (with concentration reductions occurring over approximately 1 year). In two of the three cases examined, CSIA provided additional evidence for 1,4-dioxane biodegradation. In one case, the reduction in 1,4-dioxane in the samples comparing the controls was likely too low for the method to detect a significant 13C/12C enrichment. Further research is required to determine the value of measuring 2H/1H for generating evidence for the biodegradation of this chemical. The microbial community analysis indicated that the phylotypes unclassified Comamonadaceae and 3 genus incertae sedis were more abundant in 1,4-dioxane-degrading microcosms compared to the live controls (no 1,4-dioxane) in microcosms inoculated with contaminated and uncontaminated sediment, respectively. The relative abundance of known 1,4-dioxane degraders was also investigated at the genus level. The soil microcosms were dominated primarily by Rhodanobacter with lower relative abundance values for Pseudomonas, Mycobacterium, and Acinetobacter. The sediment communities were dominated by Pseudomonas and Rhodanobacter. Overall, the current study indicates 1,4-dioxane biodegradation under anaerobic and, likely methanogenic conditions, is feasible. Therefore, natural attenuation may be an appropriate cleanup technology at sites where time is not a limitation.

Enhanced long-term attenuation of 1,4-dioxane in bioaugmented flow-through aquifer columns.

Long term natural attenuation of 1,4-dioxane (dioxane) and its enhanced biodegradation after bioaugmentation with Pseudonocardia dioxanivorans CB1190 were assessed using flow-through aquifer columns. Natural attenuation of dioxane was not observed even after 2 years of acclimation. However, dioxane removal was observed in the bioaugmented columns (34% when the influent was 200 µg/L and 92% for 5 mg/L). The thmA gene that encodes the tetrahydrofuran monooxygenase that initiates dioxane degradation by CB1190 was only detected at the inoculation port and persisted for months after inoculation, implying the resiliency of bioaugmentation and its potential to offer long-term enhanced biodegradation capabilities. However, due to extensive clumping and limited mobility of CB1190, the augmented catabolic potential may be restricted to the immediate vicinity of the inoculation port. Accordingly, bioaugmentation with CB1190 seems more appropriate for the establishment of biobarriers. Bioaugmentation efficiency was associated with the availability of oxygen. Aeration of the column influent to increase dissolved oxygen significantly improved dioxane removal (p < 0.05), suggesting that (for sites with oxygen-limiting conditions) bioaugmentation can benefit from engineered approaches for delivering additional oxygen.

Application of stable isotopes and dissolved ions for monitoring landfill leachate contamination.

We evaluated groundwater contamination by landfill leachate at a municipal landfill and characterized isotopic and hydrogeochemical evidence of the degradation and natural attenuation of buried organic matter at the study site. Dissolved ion content was generally much higher in the leachate than in the surrounding groundwater. The leachate was characterized by highly elevated bicarbonate and ammonium levels and a lack of nitrate and sulfate, indicating generation under anoxic conditions. Leachate δD and δ13CDIC values were much higher than those of the surrounding groundwater; some groundwater samples near the landfill showed a significant contamination by the leachate plume. Hydrochemical characteristics of the groundwater suggest that aquifer geology in the study area plays a key role in controlling the natural attenuation of leachate plumes in this oxygen-limited environment.