Comparison of Trace Organic Chemical Removal Efficiencies between Aerobic and Anaerobic Membrane Bioreactors Treating Municipal Wastewater.

Evaluating persistent trace organic chemicals (TOrCs) and transformation products (TPs) in membrane bioreactors (MBRs) is essential, given that MBRs are now widely implemented for wastewater treatment and water reuse. This research applied comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOF-MS)-based nontargeted analysis to compare the effectiveness of parallel aerobic and anaerobic MBRs (AeMBRs and AnMBRs, respectively), treating the same municipal wastewater. The average total chromatographic feature peak area abundances were significantly reduced by 84% and 72% from influent to membrane permeate in both the AeMBR and AnMBR (p < 0.05), respectively. However, the reduction of the average number of chromatographic features was significant for only AeMBR treatment (p = 0.006). A similar number of TPs were generated during both AeMBR and AnMBR treatments (165 vs 171 compounds, respectively). The overall results suggest that the AeMBR was more effective for reducing the diversity of TOrCs than the AnMBR, but both aerobic and anaerobic processes had a similar reduction of TOrC abundance. Suspect screening analysis using GC×GC/TOF-MS, which resulted in the tentative identification of 351 TOrCs, proved to be a powerful approach for uncovering compounds previously unreported in wastewater, including many fragrances and personal care products.

Life after a fiery death: Fire and plant biomass loading affect dissolved organic matter in experimental ponds.

Drier and hotter conditions linked with anthropogenic climate change can increase wildfire frequency and severity, influencing terrestrial and aquatic carbon cycles at broad spatial and temporal scales. The impacts of wildfire are complex and dependent on several factors that may increase terrestrial deposition and the influx of dissolved organic matter (DOM) from plants into nearby aquatic systems, resulting in the darkening of water color. We tested the effects of plant biomass quantity and its interaction with fire (burned vs. unburned plant biomass) on dissolved organic carbon (DOC) concentration and degradation (biological vs. photochemical) and DOM composition in 400 L freshwater ponds using a gradient experimental design. DOC concentration increased nonlinearly with plant biomass loading in both treatments, with overall higher concentrations (>56 mg/L) in the unburned treatment shortly after plant addition. We also observed nonlinear trends in fluorescence and UV-visible absorbance spectroscopic indices as a function of fire treatment and plant biomass, such as greater humification and specific UV absorbance at 254 nm (a proxy for aromatic DOM) over time. DOM humification occurred gradually over time with less humification in the burned treatment compared to the unburned treatment. Both burned and unburned biomass released noncolored, low molecular weight carbon compounds that were rapidly consumed by microbes. DOC decomposition exhibited a unimodal relationship with plant biomass, with microbes contributing more to DOC loss than photodegradation at intermediate biomass levels (100-300 g). Our findings demonstrate that the quantity of plant biomass leads to nonlinear responses in the dynamics and composition of DOM in experimental ponds that are altered by fire, indicating how disturbances interactively affect DOM processing and its role in aquatic environments.

Fire transforms effects of terrestrial subsidies on aquatic ecosystem structure and function.

Fire can lead to transitions between forest and grassland ecosystems and trigger positive feedbacks to climate warming by releasing CO2 into the atmosphere. Climate change is projected to increase the prevalence and severity of wildfires. However, fire effects on the fate and impact of terrestrial organic matter (i.e., terrestrial subsidies) in aquatic ecosystems are unclear. Here, we performed a gradient design experiment in freshwater pond mesocosms adding 15 different amounts of burned or unburned plant detritus and tracking the chronology of detritus effects at 10, 31, 59, and 89 days. We show terrestrial subsidies had time- and mass-dependent, non-linear impacts on ecosystem function that influenced dissolved organic carbon (DOC), ecosystem metabolism (net primary production and respiration), greenhouse gas concentrations (carbon dioxide [CO2 ], methane [CH4 ]), and trophic transfer. These impacts were shifted by fire treatment. Burning increased the elemental concentration of detritus (increasing %N, %P, %K), with cascading effects on ecosystem function. Mesocosms receiving burned detritus had lower [DOC] and [CO2 ] and higher dissolved oxygen (DO) through Day 59. Fire magnified the effects of plant detritus on aquatic ecosystem metabolism by stimulating photosynthesis and respiration at intermediate detritus-loading through Day 89. The effect of loading on DO was similar for burned and unburned treatments (Day 10); however, burned-detritus in the highest loading treatments led to sustained hypoxia (through Day 31), and long-term destabilization of ecosystem metabolism through Day 89. In addition, fire affected trophic transfer by increasing autochthonous nitrogen source utilization and reducing the incorporation of 15 N-labeled detritus into plankton biomass, thereby reducing the flux of terrestrial subsidies to higher trophic levels. Our results indicate fire chemically transforms plant detritus and alters the role of aquatic ecosystems in processing and storing carbon. Wildfire may therefore induce shifts in ecosystem functions that cross the boundary between aquatic and terrestrial habitats.

Detection, Quantification, and Simplified Wastewater Surveillance Model of SARS-CoV-2 RNA in the Tijuana River.

The COVID-19 pandemic and the detection of SARS-CoV-2 RNA in sewage has expanded global interest in wastewater surveillance. However, many underserved communities throughout the world lack improved sanitation and use informal combined sanitary and storm sewer systems. Sewage is transported via open channels, ditches, and rivers, where it mixes with surface water and/or stormwater. There is a need to develop better methods for the surveillance of pathogens such as SARS-CoV-2 RNA in this context. We developed a simplified surveillance system and monitored flow rates and concentrations of SARS-CoV-2 RNA in the Tijuana River at two locations downstream of the United States-Mexico border in California, United States. SARS-CoV-2 RNA was detected in the upstream location on six out of eight occasions, two of which were at concentrations as high as those reported in untreated wastewater from California sanitary sewer systems. The virus was not detected in any of the eight samples collected at the downstream (estuarine) sampling location, despite the consistent detection of PMMoV RNA. Synchrony was observed between the number of cases reported in Tijuana and the SARS-CoV-2 RNA concentrations measured with the CDC N1 assay when the latter were normalized by the reported flow rates in the river.

Low maintenance anammox enrichment and nitrogen removal with an anaerobic baffled reactor.

The stringent growth requirements of anammox bacteria may be a challenge for employing the anammox process for nutrient removal at household or decentralized scales, where low maintenance systems are more successful. Enrichment of anammox bacteria was achieved by 100 d using a lab-scale (32 L) anaerobic baffled reactor (ABR). Even though strict anaerobic conditions were not imposed, NH4-N and NO2-N removals of >90% were maintained after ∼100 d, with greatest removals observed in the first two chambers of the four-chamber ABR. Batch anammox activity tests and results of qPCR analyses confirmed the presence of anammox bacteria in all four ABR chambers. Changes in fluorescent peaks and indices supported that intracellular compounds from reactor biomass evolved along the ABR. The presence of denitrifiers, confirmed by qPCR, and lower NO2/NH4 ratios than predicted by stoichiometry indicated that nitrification-denitrification processes also may have contributed to the high N removal in the anammox ABR.

Persistence and removal of trace organic compounds in centralized and decentralized wastewater treatment systems.

The persistence of trace organic chemicals in treated effluent derived from both centralized wastewater treatment plants (WWTPs) and decentralized wastewater treatment systems (DEWATS) is of concern due to their potential impacts on human and ecosystem health. Here, we utilize non-targeted analysis (NTA) with comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC × GC/TOF-MS) to conduct an evaluation of the common persistent and removed compounds found in two centralized WWTPs in the USA and South Africa and one DEWATS in South Africa. Overall, removal efficiencies of chemicals were similar between the treatment plants when they were compared according to the number of chemical features detected in the influents and effluents of each treatment plant. However, the DEWATS treatment train, which has longer solids retention and hydraulic residence times than both of the centralized WWTPs and utilizes primarily anaerobic treatment processes, was able to remove 13 additional compounds and showed a greater decrease in normalized peak areas compared to the centralized WWTPs. Of the 111 common compounds tentatively identified in all three influents, 11 compounds were persistent in all replicates, including 5 compounds not previously reported in effluents of WWTPs or water reuse systems. There were no significant differences among the physico-chemical properties of persistent and removed compounds, but significant differences were observed among some of the molecular descriptors. These results have important implications for the treatment of trace organic chemicals in centralized and decentralized WWTPs and the monitoring of new compounds in WWTP effluent.

Groundwater-surface water interactions and flux of organic matter and nutrients in an urban, Mediterranean stream.

The chemical quality of dissolved organic matter (DOM) and the speciation of nitrogen exported from urban catchments is of great importance to biogeochemical cycling in riverine and coastal receiving waters. Many urban streams in Mediterranean climates have a flashy hydrologic regime, which would suggest a rapid pulsing and shunting of solutes downstream. However, the role of these systems both as passive pipes for solute transport or as reactors for DOM and nutrient transformation is still an open question for urban, Mediterranean streams. To address this question, we evaluated changes in concentrations of inorganic and organic solutes and DOM optical properties in Alvarado Creek, a perennially-flowing, urban, first-order tributary of the San Diego River in San Diego, CA, USA, during dry weather (baseflow) conditions and during four storm events in 2016-2018. Chloride and sulfate concentrations corroborate the supposed saline groundwater supply that maintains perennial flow and brackish nature in this urban stream. During dry weather, high proportions of protein-like fluorescent component (AC4) and downstream decreases in total dissolved nitrogen (TDN) and nitrate imply in-stream processing (nitrification and denitrification). By contrast, storm hysteresis curves indicate that the supply of DOM and TDN was not exhausted over the duration of a storm event, whereas nitrate was eventually depleted, presumably because nitrification could not keep up with the export of nitrate from source areas. Rapid decreases in chloride during the storm hydrograph coincided with a shift in specific ultraviolet absorbance (SUVA) and fluorescence index (FI) to more terrestrially-derived and aromatic carbon sources, most likely from interflow of stormwater through vadose zone soils. On an annual basis, the export of microbially-derived DOM during dry weather was higher than the export of terrestrially-derived DOM during storm events; both represent important carbon inputs to coastal waters.

An Assessment of Ambient Water Quality and Challenges with Access to Water and Sanitation Services for Individuals Experiencing Homelessness in Riverine Encampments.

Individuals experiencing unsheltered homelessness face significant barriers to accessing water, sanitation, and hygiene services, but the risks associated with this lack of access and barriers to service provision have been largely understudied. We analyzed water samples upstream and downstream of three homeless encampments in the San Diego River watershed and interviewed service providers from public and nonprofit sectors to assess local perceptions about challenges and potential solutions for water and sanitation service provision in this context. Water upstream from encampments contained detectable levels of caffeine and sucralose. Escherichia coli concentrations downstream of the encampments were significantly greater than concentrations upstream, but there was no significant change in the concentrations of other pollutants, including caffeine and sucralose. The HF183 marker of Bacteroides was only detected in one sample upstream of an encampment and was not detected downstream. Overall, there was insufficient evidence to suggest that the encampments studied here were responsible for contributing pollution to the river. Nevertheless, the presence of caffeine, sucralose, and HF183 indicated that there are anthropogenic sources of contamination in the river during dry weather and potential risks associated with the use of this water by encampment residents. Interviews with service providers revealed perceptions that the provision of water and sanitation services for this population would be prohibitively expensive. Interviewees also reported perceptions that most riverbank residents avoided contact with service providers, which may present challenges for the provision of water and sanitation service unless trust is first built between service providers and residents of riverine encampments.

Conceptualizing an Interdisciplinary Collective Impact Approach to Examine and Intervene in the Chronic Cycle of Homelessness.

Homelessness is a persistent problem in the United States in general and in Southern California especially. While progress has been made in reducing the number of people experiencing homelessness in the United States from 2007 (647,000) to 2019 (567,000), it remains an entrenched problem. The purpose of this paper is to outline a novel, interdisciplinary academic-practice partnership model to address homelessness. Where singular disciplinary approaches may fall short in substantially reducing homelessness at the community and population level, our model draws from a collective impact model which coordinates discipline-specific approaches through mutually reinforcing activities and shared metrics of progress and impact to foster synergy and sustainability of efforts. This paper describes the necessary capacity-building at the institution and community level for the model, the complementary strengths and contributions of each stakeholder discipline in the proposed model, and future goals for implementation to address homelessness in the Southern California region.

Persistence and photochemical transformation of water soluble constituents from industrial crude oil and natural seep oil in seawater.

The persistence and transformation of water soluble chemical constituents derived from surface oil from the 2015 Refugio Oil Spill and from a nearby natural seep were evaluated under simulated sunlight conditions. Photoirradiation resulted in enhanced oil slick dissolution, which was more pronounced in spill oil compared to seep oil. Nontargeted analysis based on GC × GC/TOF-MS revealed that photoirradiation promoted oil slick dissolution, and more water soluble compounds were released from spill oil (500 compounds) than from seep oil (180 compounds), most of them (488 in spill oil and 150 in seep oil) still persisting in solution after 67 days of photoirradiation. First-order degradation rate coefficients of humic-like water soluble constituents were found to be 0.26 day-1 and 0.29 day-1 for irradiated spill and seep samples, respectively. The decreases in humic-like fluorescence, specific UV absorbance, and aromatic compounds without corresponding decreases in DOC concentration support indirect photochemical transformation in addition to complete photomineralization.

Sierra Nevada mountain lake microbial communities are structured by temperature, resources and geographic location.

Warming, eutrophication (nutrient fertilization) and brownification (increased loading of allochthonous organic matter) are three global trends impacting lake ecosystems. However, the independent and synergistic effects of resource addition and warming on autotrophic and heterotrophic microorganisms are largely unknown. In this study, we investigate the independent and interactive effects of temperature, dissolved organic carbon (DOC, both allochthonous and autochthonous) and nitrogen (N) supply, in addition to the effect of spatial variables, on the composition, richness, and evenness of prokaryotic and eukaryotic microbial communities in lakes across elevation and N deposition gradients in the Sierra Nevada mountains of California, USA. We found that both prokaryotic and eukaryotic communities are structured by temperature, terrestrial (allochthonous) DOC and latitude. Prokaryotic communities are also influenced by total and aquatic (autochthonous) DOC, while eukaryotic communities are also structured by nitrate. Additionally, increasing N availability was associated with reduced richness of prokaryotic communities, and both lower richness and evenness of eukaryotes. We did not detect any synergistic or antagonistic effects as there were no interactions among temperature and resource variables. Together, our results suggest that (a) organic and inorganic resources, temperature, and geographic location (based on latitude and longitude) independently influence lake microbial communities; and (b) increasing N supply due to atmospheric N deposition may reduce richness of both prokaryotic and eukaryotic microbes, probably by reducing niche dimensionality. Our study provides insight into abiotic processes structuring microbial communities across environmental gradients and their potential roles in material and energy fluxes within and between ecosystems.

Fluorescence-based monitoring of anthropogenic pollutant inputs to an urban stream in Southern California, USA.

Fluorescence spectroscopy has been increasingly used to detect sewage and other anthropogenic contaminants in surface waters. Despite progress in successfully detecting bacterial and sewage inputs to rivers over diverse spatial scales, the use of fluorescence-based in-situ sensors to track contaminant inputs during storm events and to discern bacterial contamination from background natural organic matter (NOM) fluorescence have received less attention. A portable, submersible fluorometer equipped with tryptophan (TRP)-like and humic-like fluorescence sensors was used to track inputs of untreated wastewater added to natural creek water in a laboratory sewage spill simulation. Significant, positive correlations were observed between TRP fluorescence, the TRP:humic ratio, percent wastewater, and Escherichia coli concentrations, indicating that both the TRP sensor and the TRP:humic ratio tracked wastewater inputs against the background creek water DOM fluorescence. The portable fluorometer was subsequently deployed in an urban creek during a storm in 2018. The peak in TRP fluorescence was found to increase with the rising limb of the hydrograph and followed similar temporal dynamics to that of caffeine and fecal indicator bacteria, which are chemical and biological markers of potential fecal pollution. Results from this study demonstrate that tracking of TRP fluorescence intensity and TRP:humic ratios, with turbidity correction of sensor outputs, may be an appropriate warning tool for rapid monitoring of sewage or other bacterial inputs to aquatic environments.

Effects of acidification on the optical properties of dissolved organic matter from high and low arsenic groundwater and surface water.

The optical properties of bulk dissolved organic matter (DOM) at ambient pH and upon acidification (pH ~2) by hydrochloric acid (HCl) or nitric acid (HNO3) were examined in groundwater and surface water samples from the Bengal Basin. Samples of shallow high arsenic (As) and deep low As groundwaters and surface waters from the same geographic area were collected and preserved with HCl and HNO3. The optical properties of groundwater samples responded to acidification differently than those of the surface water samples. The intensity of humic-like and protein-like fluorescence decreased by 47% and 80%, respectively, upon acidification with HCl in groundwater but remained unchanged in surface water samples. Similarly, the humification index (HIX) decreased only in surface waters (from 6.6 to 3.7) and remain unchanged in groundwaters upon HCl acidification. The absorbance at 254 nm (Abs254) was not affected by HCl acidification; however, HNO3 acidification increased Abs254 in groundwater (by 9-fold) as well as in surface water samples (by 3-fold), possibly due to inherent absorbance of HNO3 at 254 nm. Humic- and protein-like fluorescence intensities decreased by HNO3 acidification by 49% and 78% respectively, which may be attributed to aggregation losses and changes in the protonation states of amines, hydroxyls and carboxylic functional groups. Parallel factor (PARAFAC) analysis revealed a unique component that resulted from the acidification of samples with HNO3. The other fluorescence indices such as fluorescence index (FI) and freshness index (ß:α) remained unchanged upon either type of acidification of surface water as well as groundwater samples. These results reflect the effects of pH perturbation in groundwater environments where DOC concentrations may be lower as compared to surface water environments and provide insights into the structural, molecular and reactive properties of DOM in these environments.

Influence of monsoonal recharge on arsenic and dissolved organic matter in the Holocene and Pleistocene aquifers of the Bengal Basin.

Arsenic (As) mobilization in the Bengal Basin aquifers has been studied for several decades due to the complex redox bio-geochemistry, dynamic hydrogeology and complex nature of dissolved organic matter (DOM). Earlier studies have examined the changes in groundwater As in the dry season before monsoon and during the wet season after monsoonal recharge. To investigate the more immediate influence of recharge during the active monsoon period on As mobilization and DOM character, groundwater samples were analyzed in the pre-monsoon and during the active monsoon period. Groundwater samples were collected from shallow (<40 m) and deep (>40 m) tube-wells in West Bengal, India. Dissolved AsT in shallow groundwater ranged from 50 to 315 µg/L exceeding the WHO guideline of 10 µg/L. Shallow groundwater also showed high total dissolved nitrogen, carbon to nitrogen (C:N) <1, and humic-like DOM with a humic:protein ratio >1. By contrast, deep groundwaters contained AsT between 0.5 and 11 µg/L with carbonaceous and protein-like DOM, C:N >1, and humic:protein <1. Stable isotopes of δ18O and δ2H and Cl/Br results indicated three recharge scenarios in the shallow aquifer including direct recharge of dilute rainwater, evaporated surface water, and anthropogenically impacted surface water. Monsoonal recharge did not cause notable changes in AsT in deep or shallow groundwater, including two As hotspots in the Pleistocene aquifer. However, the monsoon did result in a two-fold decrease in SUVA254, increase in nitrite and nitrate in the shallow groundwater. The DOM in the deep groundwater at the two As hotspots (with AsT 132 and 715 µg/L) had optical properties with much greater humic-like DOM than the surrounding groundwater, which had low AsT and highly protein-like DOM. Overall, these results support that protein-like DOM associated with low groundwater As concentrations and suggest that the monsoonal influence on nitrate and nitrite is limited to shallow aquifers.

Dissolved fulvic acids from a high arsenic aquifer shuttle electrons to enhance microbial iron reduction.

It was demonstrated more than two decades ago that microorganisms use humic substances, including fulvic acid (FA), as electron shuttles during iron (Fe) reduction in anaerobic soils and sediments. The relevance of this mechanism for the acceleration of Fe(III) reduction in arsenic-laden groundwater environments is gaining wider attention. Here we provide new evidence that dissolved FAs isolated from sediment-influenced surface water and groundwater in the Bengal Basin were capable of electron shuttling between Geobacter metallireducens and Fe(III). Moreover, all four Bangladesh sediment-derived dissolved FAs investigated in this study had higher electron accepting capacity (176 to 245µmol/g) compared to aquatic FAs, such as Suwanee River Fulvic Acid (67µmol/g). Our direct evidence that Bangladesh FAs are capable of intermediate electron transfer to Fe(III) supports other studies that implicate electron shuttling by sediment-derived aqueous humics to enhance Fe reduction and, in turn, As mobility. Overall, the finding of greater electron accepting capacity by dissolved FAs from groundwater and other sediment-influenced environments advances our understanding of mechanisms that control Fe reduction under conditions where electron transfer is the rate limiting step.

Deposition rates of viruses and bacteria above the atmospheric boundary layer.

Aerosolization of soil-dust and organic aggregates in sea spray facilitates the long-range transport of bacteria, and likely viruses across the free atmosphere. Although long-distance transport occurs, there are many uncertainties associated with their deposition rates. Here, we demonstrate that even in pristine environments, above the atmospheric boundary layer, the downward flux of viruses ranged from 0.26 × 109 to >7 × 109 m-2 per day. These deposition rates were 9-461 times greater than the rates for bacteria, which ranged from 0.3 × 107 to >8 × 107 m-2 per day. The highest relative deposition rates for viruses were associated with atmospheric transport from marine rather than terrestrial sources. Deposition rates of bacteria were significantly higher during rain events and Saharan dust intrusions, whereas, rainfall did not significantly influence virus deposition. Virus deposition rates were positively correlated with organic aerosols <0.7 µm, whereas, bacteria were primarily associated with organic aerosols >0.7 µm, implying that viruses could have longer residence times in the atmosphere and, consequently, will be dispersed further. These results provide an explanation for enigmatic observations that viruses with very high genetic identity can be found in very distant and different environments.

A soil column study to evaluate treatment of trace elements from saline industrial wastewater.

Industrial wastewater from the flue gas desulfurization (FGD) process is characterized by the presence of trace elements of concern, such as selenium (Se) and boron (B) and relatively high salinity. To simulate treatment that FGD wastewater undergoes during transport through soils in subsurface treatment systems, a column study (140-d duration) was conducted with native Kansas soil and saline FGD wastewater, containing high Se and B concentrations (170 µg/L Se and 5.3 mg/L B) and negligible arsenic (As) concentration (∼1.2 µg/L As). Se, B, and As, and dissolved organic carbon concentrations and organic matter spectroscopic properties were measured in the influent and outflow. Influent Se concentrations were reduced by only ∼half in all treatments, and results suggest that Se sorption was inhibited by high salinity of the FGD wastewater. By contrast, relative concentrations (C/Co) of B in the outflow were typically <10%, suggesting that B sequestration may have been enhanced by higher salinity. Unexpected elevated As concentrations in the outflow (at >150 µg/L in the treatment with labile organic carbon addition) suggest that soils not previously known to be geogenic arsenic sources have the potential to release As to groundwater in the presence of high salinity wastewater and under reducing conditions.

Water soluble organic aerosols in the Colorado Rocky Mountains, USA: composition, sources and optical properties.

Atmospheric aerosols have been shown to be an important input of organic carbon and nutrients to alpine watersheds and influence biogeochemical processes in these remote settings. For many remote, high elevation watersheds, direct evidence of the sources of water soluble organic aerosols and their chemical and optical characteristics is lacking. Here, we show that the concentration of water soluble organic carbon (WSOC) in the total suspended particulate (TSP) load at a high elevation site in the Colorado Rocky Mountains was strongly correlated with UV absorbance at 254 nm (Abs254, r = 0.88 p < 0.01) and organic carbon (OC, r = 0.95 p < 0.01), accounting for >90% of OC on average. According to source apportionment analysis, biomass burning had the highest contribution (50.3%) to average WSOC concentration; SOA formation and motor vehicle emissions dominated the contribution to WSOC in the summer. The source apportionment and backward trajectory analysis results supported the notion that both wildfire and Colorado Front Range pollution sources contribute to the summertime OC peaks observed in wet deposition at high elevation sites in the Colorado Rocky Mountains. These findings have important implications for water quality in remote, high-elevation, mountain catchments considered to be our pristine reference sites.

Dissolved Organic Matter Quality in a Shallow Aquifer of Bangladesh: Implications for Arsenic Mobility.

In some high arsenic (As) groundwater systems, correlations are observed between dissolved organic matter (DOM) and As concentrations, but in other systems, such relationships are absent. The role of labile DOM as the main driver of microbial reductive dissolution is not sufficient to explain the variation in DOM-As relationships. Other processes that may also influence As mobility include complexation of As by dissolved humic substances, and competitive sorption and electron shuttling reactions mediated by humics. To evaluate such humic DOM influences, we characterized the optical properties of filtered surface water (n = 10) and groundwater (n = 24) samples spanning an age gradient in Araihazar, Bangladesh. Further, we analyzed large volume fulvic acid (FA) isolates (n = 6) for optical properties, C and N content, and (13)C NMR spectroscopic distribution. Old groundwater (>30 years old) contained primarily sediment-derived DOM and had significantly higher (p < 0.001) dissolved As concentration than groundwater that was younger than 5 years old. Younger groundwater had DOM spectroscopic signatures similar to surface water DOM and characteristic of a sewage pollution influence. Associations between dissolved As, iron (Fe), and FA concentration and fluorescence properties of isolated FA in this field study suggest that aromatic, terrestrially derived FAs promote As-Fe-FA complexation reactions that may enhance As mobility.

Carbon, metals, and grain size correlate with bacterial community structure in sediments of a high arsenic aquifer.

Bacterial communities can exert significant influence on the biogeochemical cycling of arsenic (As). This has globally important implications since As in drinking water affects the health of over 100 million people worldwide, including in the Ganges-Brahmaputra Delta region of Bangladesh where geogenic arsenic in groundwater can reach concentrations of more than 10 times the World Health Organization's limit. Thus, the goal of this research was to investigate patterns in bacterial community composition across gradients in sediment texture and chemistry in an aquifer with elevated groundwater As concentrations in Araihazar, Bangladesh. We characterized the bacterial community by pyrosequencing 16S rRNA genes from aquifer sediment samples collected at three locations along a groundwater flow path at a range of depths between 1.5 and 15 m. We identified significant differences in bacterial community composition between locations in the aquifer. In addition, we found that bacterial community structure was significantly related to sediment grain size, and sediment carbon (C), manganese (Mn), and iron (Fe) concentrations. Deltaproteobacteria and Chloroflexi were found in higher proportions in silty sediments with higher concentrations of C, Fe, and Mn. By contrast, Alphaproteobacteria and Betaproteobacteria were in higher proportions in sandy sediments with lower concentrations of C and metals. Based on the phylogenetic affiliations of these taxa, these results may indicate a shift to more Fe-, Mn-, and humic substance-reducers in the high C and metal sediments. It is well-documented that C, Mn, and Fe may influence the mobility of groundwater arsenic, and it is intriguing that these constituents may also structure the bacterial community.