Arsenic-dissolved organic matter complexation in water soluble extracts from lignite.

Arsenic in groundwater is a global threat to public health. Recently, As mobility has been tied to the concentration and chemical characteristics of dissolved organic matter (DOM) through formation of As-DOM complexes. To date, there has been a wide range of DOM types studied to understand As-DOM interactions, but most of these have focused on surface water derived materials and not groundwater DOM. We address this gap in knowledge by simulating groundwater DOM using water extractable organic matter (WEOM) from two lignite deposits and treating the extracts with increasing concentrations of As. As-DOM complexes were measured using size-exclusion chromatography coupled to multiple detectors including an inductively coupled plasma mass spectrometer (ICPMS) for As detection as well as fluorescence and variable wave detectors for organic matter detection. First, we found two different size fractions of As-DOM, one of ∼1 kDa and another of ∼15 kDa, depending on the DOM types. The smaller As-DOM complex (∼1 kDa) was approximately 10 times more abundant than the larger complex (∼15 kDa). Second, we found that the lignite derived DOMs showed higher conditional distribution coefficients than did the surface water reference material (Suwanee River Natural Organic Matter, SRNOM). Finally, the data showed good fit (R2 > 0.92) to one-site ligand binding models, and the lignite derived DOMs showed higher maximum sorbate concentrations (Bmax) compared to SRNOM. Together, this study shows that As-DOM complexation is an important control on As speciation, even in groundwater systems.

Lipid biomarkers recording marine microbial community structure changes through the Frasnian-Famennian mass extinction event.

Studying the response and recovery of marine microbial communities during mass extinction events provides an evolutionary window through which to understand the adaptation and resilience of the marine ecosystem in the face of significant environmental disturbances. The goal of this study is to reconstruct changes in the marine microbial community structure through the Late Devonian Frasnian-Famennian (F-F) transition. We performed a multiproxy investigation on a drill core of the Upper Devonian New Albany Shale from the Illinois Basin (western Kentucky, USA). Aryl isoprenoids show green sulfur bacteria expansion and associated photic zone euxinia (PZE) enhancement during the F-F interval. These changes can be attributed to augmented terrigenous influxes, as recorded collectively by the long-chain/short-chain normal alkane ratio, carbon preference index, C30 moretane/C30 hopane, and diahopane index. Hopane/sterane ratios reveal a more pronounced dominance of eukaryotic over prokaryotic production during the mass extinction interval. Sterane distributions indicate that the microalgal community was primarily composed of green algae clades, and their dominance became more pronounced during the F-F interval and continued to rise in the subsequent periods. The 2α-methylhopane index values do not show an evident shift during the mass extinction interval, whereas the 3ß-methylhopane index values record a greater abundance of methanotrophic bacteria during the extinction interval, suggesting enhanced methane cycling due to intensified oxygen depletion. Overall, the Illinois Basin during the F-F extinction experienced heightened algal productivity due to intensified terrigenous influxes, exhibiting similarities to contemporary coastal oceans that are currently undergoing globalized cultural eutrophication. The observed microbial community shifts associated with the F-F environmental disturbances were largely restricted to the extinction interval, which suggests a relatively stable, resilient marine microbial ecosystem during the Late Devonian.

Contribution of sedimentary organic matter to arsenic mobilization along a potential natural reactive barrier (NRB) near a river: The Meghna river, Bangladesh.

Elevated dissolved arsenic (As) concentrations in the shallow aquifers of Bangladesh are primarily caused by microbially-mediated reduction of As-bearing iron (Fe) (oxy)hydroxides in organic matter (OM) rich, reducing environments. Along the Meghna River in Bangladesh, interactions between the river and groundwater within the hyporheic zone cause fluctuating redox conditions responsible for the formation of a Fe-rich natural reactive barrier (NRB) capable of sequestering As. To understand the NRB's impact on As mobility, the geochemistry of riverbank sediment (<3 m depth) and the underlying aquifer sediment (up to 37 m depth) was analyzed. A 24-hr sediment-water extraction experiment was performed to simulate interactions of these sediments with oxic river water. The sediment and the sediment-water extracts were analyzed for inorganic and organic chemical parameters. Results revealed no differences between the elemental composition of riverbank and aquifer sediments, which contained 40 ± 12 g/kg of Fe and 7 ± 2 mg/kg of As, respectively. Yet the amounts of inorganic and organic constituents extracted were substantially different between riverbank and aquifer sediments. The water extracted 6.4 ± 16.1 mg/kg of Fe and 0.03 ± 0.02 mg/kg of As from riverbank sediments, compared to 154.0 ± 98.1 mg/kg of Fe and 0.55 ± 0.40 mg/kg of As from aquifer sediments. The riverbank and aquifer sands contained similar amounts of sedimentary organic matter (SOM) (17,705.2 ± 5157.6 mg/kg). However, the water-extractable fraction of SOM varied substantially, i.e., 67.4 ± 72.3 mg/kg in riverbank sands, and 1330.3 ± 226.6 mg/kg in aquifer sands. Detailed characterization showed that the riverbank SOM was protein-like, fresh, low molecular weight, and labile, whereas SOM in aquifer sands was humic-like, older, high molecular weight, and recalcitrant. During the dry season, oxic conditions in the riverbank may promote aerobic metabolisms, limiting As mobility within the NRB.

Markers of polychlorinated biphenyl (PCB) degradation in highly contaminated soil of Central Russia.

The highly polychlorinated biphenyl (PCB)-contaminated historical soil is located in the Serpukhov region (Central Russia). This study evaluates the processes of PCB degradation in the soil under natural conditions. Compositions of industrial mixtures (Sovol, Sovtol, and trichlorodiphenyl) were compared with PCB-contaminated soil from different depths. An increased number of dichlorobiphenyls (6 congeners) were determined in the deeper soil horizons (40-60 cm) in comparison with the surface layer (1 congener). Non-associated with industrial mixture congener, PCB 11 was determined in some soil layers with concentrations reaching 3.6 mg/kg. PCB 11 can be considered as a potential marker of activated degradation processes in highly contaminated soils with industrial mixtures. Aegopodium podagraria reduced total PCB concentrations in the contaminated soil to 25% during pot experiments. Prospective precursors of PCB 11 were significantly depleted (62-88%) after phytoremediation, but this did not increase PCB 11 concentration in the soil.

Temporal and spatial variation of polychlorinated biphenyls (PCBs) contamination in environmental compartments of highly polluted area in Central Russia.

This study highlights the fact that serious contamination from polychlorinated biphenyls (PCBs) still exists in Serpukhov City (Russia). The research help to determine the temporal (16- and 24-year periods) and spatial PCBs distribution in the environmental compartments of the studied region. Samples of soil, sediments, water and plants were analysed in order to establish their contamination levels. The most recent data on the Serpukhov City's soil contamination showed that the PCBs concentrations varies from 0.0009 to 1169 mg/kg depending on the sampling point and the distance from the pollution source. The temporal trends of the contamination distribution with the soil depth showed contamination migration in the upper soil layers of the highly polluted site. The high level of water pollution (11.5 µg/L) in the proximity to the contamination source and the sediments contamination (0.098-119 mg/kg) were determined, as well as the water migration pathways of the PCBs that were prevalent in the studied region. The PCB congener group (by the level of chlorination) analysis showed that heptachlorinated biphenyls were only found in the soils in close proximity to the contamination place, while biphenyls with Cl ≤ 6 were found in the soil samples downstream of the condenser plant and with Cl ≤ 5 in the soil samples upstream of the plant. The plant uptake of PCBs, even on the extremely contaminated site, was shown. In turn, this research present new knowledge necessary for the development of a contaminated territory remediation strategy.