GIS interpolation is key in assessing spatial and temporal bioremediation of groundwater arsenic contamination.

Arsenic (As) contamination in groundwater is a global crisis that is known to cause cancers of the skin, bladder, and lungs, among other health issues, and affects millions of people around the world. Due to the time and financial constraints associated with establishing in-depth monitoring programs, it is difficult to monitor and map arsenic concentrations over time and across large areas. The goal of this study was to determine the most accurate Geographic Information Systems (GIS) interpolation method for mapping the effects of bioremediation on groundwater arsenic sequestration across a local-scale study area in northwest Florida (~900 m2) over the duration of a nine-month period (pre-injection, one-month post-injection, and nine-months post-injection). We used groundwater data collected from 2018 to 2019 to visualize arsenic contamination over time. Measured arsenic concentrations from 23 wells were grouped into three categories: (1) decreasing, (2) fluctuating, or (3) largely unaffected by the bioremediation procedure. The accuracy of three interpolation methods was also investigated: Inverse Distance Weighted (IDW), Ordinary Kriging (OK), and Empirical Bayesian Kriging (EBK). Statistical results using the leave-one-out cross validation (LOOCV) process showed that OK consistently provided the most accurate predictions of arsenic concentrations across space and time ([Root Mean Square Error (RMSE) = 0.265] and accurately predicted regulatory arsenic concentrations below 0.05 mg/L in nine of 11 wells, while IDW and EBK only accurately predicted four and five wells, respectively. While it was shown that OK tends to underpredict arsenic maxima, this did not affect the overall accuracy of the interpolation compared to results from EBK (RMSE = 0.297) and IDW (RMSE = 0.272). Overall, these interpolations aided in the interpretation of the extent of bioremediation, revealing the need for repeated injections to continuously remove arsenic from the groundwater. The study will provide guidance and evaluation methods for international and governmental organizations, industrial companies, and local communities on how to understand spatial and temporal distributions of arsenic contamination and inform bioremediation efforts at various scales in the future.

Sediment Core Sectioning and Extraction of Pore Waters under Anoxic Conditions.

We demonstrate a method for sectioning sediment cores and extracting pore waters while maintaining oxygen-free conditions. A simple, inexpensive system is built and can be transported to a temporary work space close to field sampling site(s) to facilitate rapid analysis. Cores are extruded into a portable glove bag, where they are sectioned and each 1-3 cm thick section (depending on core diameter) is sealed into 50 ml centrifuge tubes. Pore waters are separated with centrifugation outside of the glove bag and then returned to the glove bag for separation from the sediment. These extracted pore water samples can be analyzed immediately. Immediate analyses of redox sensitive species, such as sulfide, iron speciation, and arsenic speciation indicate that oxidation of pore waters is minimal; some samples show approximately 100% of the reduced species, e.g. 100% Fe(II) with no detectable Fe(III). Both sediment and pore water samples can be preserved to maintain chemical species for further analysis upon return to the laboratory.

Isotopic evidence for anthropogenic impacts on aquatic food web dynamics and mercury cycling in a subtropical wetland ecosystem in the US.

Quantifying and predicting the food web consequences of anthropogenic changes is difficult using traditional methods (based on gut content analysis) because natural food webs are variable and complex. Here, stable and radioactive carbon isotopes are used, in conjunction with nitrogen isotopes and mercury (Hg) concentration data, to document the effects of land-use change on food webs and Hg bioaccumulation in the Everglades - a subtropical wetland ecosystem in the US. Isotopic signatures of largemouth bass and sunfish in reference (relatively pristine) wetlands indicate reliance on the food supply of modern primary production within the wetland. In contrast, both fish in areas impacted by agricultural runoff had radiocarbon ages as old as 540 years B.P., and larger isotopic variability than counterparts in reference wetlands, reflecting differences in the food web between impacted and reference wetlands. Consistent with this difference, particulate and dissolved organic matter in impacted areas had old radiocarbon ages (>600 years B.P.), indicating that old carbon derived from historic peat deposits in the Everglades Agricultural Area was passed along the food chain to consumers. Significant radiocarbon deficiencies in largemouth bass and sunfish, relative to mosquitofish, in impacted areas most likely indicate a reduced dependence on small fish. Furthermore, largemouth bass and sunfish from impacted areas had much lower Hg contents than those from reference wetlands. Taken together, these data suggest a shift toward lower trophic levels and a possible reduction in mercury methylation in impacted wetlands. Our study provides clear evidence that hydrological modification and land-use change in the Everglades have changed the system from one driven primarily by in-situ productivity to one that is partially dependent on allochthonous carbon input from peat soils in the agricultural area and altered the Hg biogeochemical cycle in the wetlands. The results have implications for the restoration and management of wetland ecosystems.

Microbial community analysis of Deepwater Horizon oil-spill impacted sites along the Gulf coast using functional and phylogenetic markers.

We investigated the impact of the Deepwater Horizon oil spill on microbial communities in wetland sediment and seawater samples collected from sites along the Gulf shore. Based on GC/MS analysis, the sediment from Bay Jimmy, LA had detectable signs of hydrocarbon contamination, identified as n-alkanes in the GC/MS spectrum similar to that of the Deepwater Horizon source oil (MC-252). To identify changes in microbial assemblage structure and functional diversity in response to hydrocarbon contamination, five genes (bacterial 16S rRNA, Pseudomonas-specific 16S rRNA, alkB, P450, and PAH-RHDα) were selected based on the specific enzymes encoded by bacteria to degrade alkanes or polycyclic aromatic hydrocarbons. A quantitative PCR analysis revealed the presence of alkane and PAH-degrading genes in both contaminated and non-contaminated samples with no significant difference in gene content between contaminated and non-contaminated samples. However, the ribotype analysis based on pyrosequencing identified 17 bacteria genera known for their capacity to degrade hydrocarbons, including Mycobacterium, Novosphingobium, Parvibaculum, Pseudomonas, and Sphingomonas, in the contaminated sediment sample. Furthermore, the contaminated sample had a very high relative abundance of 16S rRNA gene sequences affiliated with the genus Parvibaculum, members of which have been characterized for their degradative abilities. These data suggest that specific bacterial taxa within the genus Parvibaculum have the capacity for hydrocarbon degradation and could use the hydrocarbons as a carbon and energy source, resulting in a dominant population in a hydrocarbon-contaminated soil. In summary, when exposed to the spilled oil, the distinct wetland microbial communities responded with decreased diversity and increased abundance of selective degradative species.

Characterisation of organic matter associated with groundwater arsenic in reducing aquifers of southwestern Taiwan.

Arsenic (As) in groundwaters extensively used by people across the world constitutes a serious public health threat. The importance of organic matter (OM) as an electron donor in microbially-mediated reduction of As(V) or Fe(III)-bearing As-host minerals leading to mobilisation of solid-phase arsenic is widely recognised. Notwithstanding this, there are few studies characterising OM in such aquifers and, in particular, there is a dearth of data from the classic arsenic bearing aquifers in southwestern Taiwan. Organic geochemical analyses of sediments from a known groundwater arsenic hot-spot in southwestern Taiwan revealed contributions of thermally mature and plant derived origin, consistent with OM sources in all other Asian groundwater aquifer sediments analysed to date, indicating comparable sources and routes of OM transfer. The combined results of amended As(V) reduction assays with the organic geochemical analysis revealed that the microbiological process of dissimilatory As(V) reduction is active in this aquifer, but it is not controlled by a specific source of analysed OM. These indicate that (i) part of the OM that was considered to be less bio-available could still be used as an electron donor or (ii) other electron donors, not analysed in present study, could be controlling the rate of As release.

Level and degradation of Deepwater Horizon spilled oil in coastal marsh sediments and pore-water.

This research investigates the level and degradation of oil at ten selected Gulf saltmarsh sites months after the 2010 BP Macondo-1 well oil spill. Very high levels (10-28%) of organic carbon within the heavily oiled sediments are clearly distinguished from those in pristine sediments (<3%). Dissolved organic carbon in contaminated pore-waters, ranging up to hundreds of mg/kg, are 1 to 2 orders of magnitude higher than those at pristine sites. Heavily oiled sediments are characterized by very high sulfide concentrations (up to 80 mg/kg) and abundance of sulfate reducing bacteria. Geochemical biomarkers and stable carbon isotope analyses fingerprint the presence of oils in sediments. Ratios of selected parameters calculated from the gas chromatograph spectra are in a remarkable narrow range among spilled oils and initial BP crude. At oiled sites dominated by C(4) plants, δ(13)C values of sediments (-20.8 ± 2.0‰) have been shifted significantly lower compared to marsh plants (-14.8 ± 0.6‰) due to the inflow of isotopically lighter oil (-27 ± 0.2‰). Our results show that (1) lighter compounds of oil are quickly degraded by microbes while the heavier fractions of oil still remain and (2) higher inputs of organic matter from the oil spill enhance the key microbial processes associated with sulfate reducing bacteria.

A comparative study on arsenic and humic substances in alluvial aquifers of Bengal delta plain (NW Bangladesh), Chianan plain (SW Taiwan) and Lanyang plain (NE Taiwan): implication of arsenic mobilization mechanisms.

Humic substances in groundwater and aquifer sediments from the arsenicosis and Blackfoot disease (BFD) affected areas in Bangladesh (Bengal delta plain) and Taiwan (Lanyang plain and Chianan plain) were characterized using fluorescence spectrophotometry and Fourier transform infrared (FT-IR) spectroscopy. The results demonstrate that the mean concentration of As and relative intensity of fluorescent humic substances are higher in the Chianan plain groundwater than those in the Lanyang plain and Bengal delta plain groundwater. The mean As concentrations in Bengal delta plain, Chianan plain, and Lanyang plain are 50.65 µg/l (2.8-170.8 µg/l, n=20), 393 µg/l (9-704 µg/l, n=5), and 104.5 µg/l (2.51-543 µg/l, n = 6), respectively. Average concentrations and relative fluorescent intensity of humic substances in groundwater are 25.381 QSU (quinine standard unit) and 17.78 in the Bengal delta plain, 184.032 QSU and 128.41 in the Chianan plain, and 77.56 QSU and 53.43 in the Lanyang plain. Moreover, FT-IR analysis shows that the humic substances extracted from the Chianan plain groundwater contain phenolic, alkanes, aromatic ring and amine groups, which tend to form metal carbon bonds with As and other trace elements. By contrast, the spectra show that humic substances are largely absent from sediments and groundwater in the Bengal delta plain and Lanyang plain. The data suggest that the reductive dissolution of As-adsorbed Mn oxyhydroxides is the most probable mechanism for mobilization of As in the Bengal delta plain. However, in the Chianan plain and Lanyang plain, microbially mediated reductive dissolution of As-adsorbed amorphous/crystalline Fe oxyhydroxides in organic-rich sediments is the primary mechanism for releasing As to groundwater. High levels of As and humic substances possibly play a critical role in causing the unique BFD in the Chianan plain of SW Taiwan.

Implications of organic matter on arsenic mobilization into groundwater: evidence from northwestern (Chapai-Nawabganj), central (Manikganj) and southeastern (Chandpur) Bangladesh.

Boreholes (50 m depth) and piezometers (50 m depth) were drilled and installed for collecting As-rich sediments and groundwater in the Ganges, Brahmaputra, and Meghna flood plains for geochemical analyses. Forty-one groundwater samples were collected from the three areas for the analyses of cations (Ca(2+), Mg(2+), K(+), Na(+)), anions (Cl(-), NO(3)(-), SO(4)(2-)), total organic carbon (TOC), and trace elements (As, Mn, Fe, Sr, Se, Ni, Co, Cu, Mo, Sb, Pb). X-ray powder diffraction (XRD) and X-ray fluorescence (XRF) were performed to characterize the major mineral and chemical contents of aquifer sediments. In all three study areas, results of XRF analysis clearly show that fine-grained sediments contain higher amounts of trace element because of their high surface area for adsorption. Relative fluorescent intensity of humic substances in groundwater samples ranges from 30 to 102 (mean 58 ± 20, n = 20), 54-195 (mean 105 ± 48, n = 10), and 27-243 (mean 79 ± 71, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Arsenic concentration in groundwater (20-50 m of depth) ranges from 3 to 315 µg/L (mean 62.4 ± 93.1 µg/L, n = 20), 16.4-73.7 µg/L (mean 28.5 ± 22.4 µg/L, n = 10) and 4.6-215.4 µg/L (mean 30.7 ± 62.1 µg/L, n = 11) in the Ganges, Brahmaputra and Meghna flood plains, respectively. Specific ultra violet adsorption (SUVA) values (less than 3 m(-1) mg(-1) L) indicate that the groundwater in the Ganges flood plain has relatively low percentage of aromatic organic carbon compared to those in the Brahmaputra and Meghna flood plains. Arsenic content in sediments ranges from 1 to 11 mg/kg (mean 3.5 ± 2.7 mg/kg, n = 17) in the three flood plains. Total organic carbon content is 0.5-3.7 g/kg (mean 1.9 ± 1.1 g/kg) in the Ganges flood plain, 0.5-2.1 g/kg (mean: 1.1 ± 0.7 g/kg) in the Brahmaputra flood plain and 0.3-4.4 g/kg (mean 1.9 ± 1.9 g/kg) in the Meghna flood plain. Arsenic is positively correlated with TOC (R(2) = 0.50, 0.87, and 0.85) in sediments from the three areas. Fourier transform infrared (FT-IR) analysis of the sediments revealed that the functional groups of humic substances in three areas include amines, phenol, alkanes, and aromatic carbon. Arsenic and Fe speciation in sediments were determined using XANES and the results imply that As(V) and Fe(III) are the dominant species in most sediments. The results also imply that As (V) and Fe (III) in most of the sediment samples of the three areas are the dominant species. X-ray absorption fine structure (EXAFS) analysis shows that FeOOH is the main carrier of As in the sediments of three areas. In sediments, As is well correlated with Fe and Mn. However, there is no such correlation observed between As and Fe as well as As and Mn in groundwater, implying that mobilizations of Fe, Mn, and As are decoupled or their concentrations in groundwater have been affected by other geochemical processes following reductive dissolution of Fe or Mn-hydroxides. For example, dissolved Fe and Mn levels may be affected by precipitation of Fe- and Mn-carbonate minerals such as siderite, while liberated As remains in groundwater. The groundwaters of the Brahmaputra and Meghna flood plains contain higher humic substances in relative fluorescence intensity (or fluorescence index) and lower redox potential compared to the groundwater of Ganges flood plain. This leads to the release of arsenic and iron to groundwater of these three plains in considerable amounts, but their concentrations are distributed in spatial variations.

Characterization of copper bioreduction and biosorption by a highly copper resistant bacterium isolated from copper-contaminated vineyard soil.

Copper is an essential but toxic heavy metal that negatively impacts living systems at high concentration. This study presents factors affecting copper bioremoval (bioreduction and biosorption) by a highly copper resistant monoculture of Pseudomonas sp. NA and copper bioremoval from soil. Seven bacteria resistant to high concentration of Cu(II) were isolated from enrichment cultures of vineyard soils and mining wastes. Culture parameters influencing copper bioreduction and biosorption by one monoculture isolate were studied. The isolate was identified by 16S rRNA gene sequence analysis as a Pseudomonas sp. NA (98% similarity to Pseudomonas putida, Pseudomonas plecoglossicida and other Pseudomonas sp.). The optimal temperature for growth was 30 degrees C and bioremoval of Cu(II) was maximal at 35 degrees C. Considerable growth of the isolate was observed between pH 5.0 and 8.0 with the highest growth and biosorption recorded at pH 6.0. Maximal bioreduction was observed at pH 5.0. Cu(II) bioremoval was directly proportional to Cu(II) concentration in media. Pseudomonas sp. NA removed more than 110mg L(-1) Cu(II) in water within 24h through bioreduction and biosorption at initial concentration of 300mg L(-1). In cultures amended with 100mg L(-1), 20.7mg L(-1) of Cu(II) was biologically reduced and more than 23mg L(-1) of Cu(II) was biologically removed in 12h. The isolate strongly promoted copper bioleaching in soil. Results indicate that Pseudomonas sp. NA has good potential as an agent for removing copper from water and soil.

Occurrence of arsenic in core sediments and groundwater in the Chapai-Nawabganj District, northwestern Bangladesh.

Groundwater and core sediments of two boreholes (to a depth of 50m) from the Chapai-Nawabganj area in northwestern Bangladesh were collected for arsenic concentration and geochemical analysis. Groundwater arsenic concentrations in the uppermost aquifer (10-40m of depth) range from 2.8microgL(-1) to 462.3microgL(-1). Groundwater geochemical conditions change from oxidized to successively more reduced, higher As concentration with depth. Higher sediment arsenic levels (55mgkg(-1)) were found within the upper 40m of the drilled core samples. X-ray absorption near-edge structure spectroscopy was employed to elucidate the arsenic speciation of sediments collected from two boreholes. Environmental scanning electron microscopy and transmission X-ray microscopy were used to investigate the characteristics of FeOOH in sediments which adsorb arsenic. In addition, a pH-Eh diagram was drawn using the Geochemist's Workbench (GWB) software to elucidate the arsenic speciation in groundwater. The dominant groundwater type is Ca-HCO(3) with high concentrations of As, Fe and Mn but low levels of NO(3)(-) and SO(4)(2-). Sequential extraction analysis reveals that Mn and Fe hydroxides and organic matter are the major leachable solids carrying As. High levels of arsenic concentration in aquifers are associated with fine-grained sediments. Fluorescent intensities of humic substances indicate that both groundwater and sediments in this arsenic hotspot area contain less organic matter compared to other parts of Bengal basin. Statistical analysis clearly shows that As is closely associated with Fe and Mn in sediments while As is better correlated with Mn in groundwater. These correlations along with results of sequential leaching experiments suggest that reductive dissolution of MnOOH and FeOOH mediated by anaerobic bacteria represents an important mechanism for releasing arsenic into the groundwater.

Geochemistry of high arsenic groundwater in Chia-Nan plain, Southwestern Taiwan: possible sources and reactive transport of arsenic.

Major ion, trace element, and stable isotope analyses were performed on groundwater samples collected during November 2005 and 2006 in Chia-Nan plain of southwestern Taiwan to examine As mobilization in aquifers. The high concentrations of As, Fe and Mn in the groundwater is consistent with low Eh values (under moderately reduced state). Moreover, the observed Na/Cl and SO(4)/Cl molar ratios in groundwater demonstrate the influence of seawater intrusion. Seawater intrusion could provide required electron acceptors (i.e., SO(4)) for bacterial sulfate reduction and promote reducing conditions that are favorable for As mobilization. The concurrent increases in the concentrations of Fe and Mn from 2005 to 2006 may be caused by bacterial Fe(III) and Mn(IV) reduction. Geochemical modeling demonstrate that As(III) is the dominant As species and the presence of Fe-bearing carbonates, sulfides, and oxide phases may locally act as potential sinks for As. Mud volcano fluids were also collected and analyzed to assess the possible source of As in the Chia-Nan plain groundwater. The oxygen and hydrogen isotopic signatures indicate that the As-rich mud volcano fluids may have been modified by chemical exchange with (18)O-rich crustal rocks and possibly originated from mixing of deep brines with circulating meteoric water. Thus As in the Chia-Nan plain groundwater may have been evolved from deep crustal fluids or rock sources. The hydrogeochemistry and widespread As enrichment in groundwater of Chia-Nan plain result from multiple processes, e.g., de-watering of deep crustal fluids, seawater intrusion, and biogeochemical cycling of Fe, As, and S in alluvial sediments.

Effects of inorganic nutrient levels on the biodegradation of benzene, toluene, and xylene (BTX) by Pseudomonas spp. in a laboratory porous media sand aquifer model.

The effect of inorganic nutrients (sulfate, phosphate, and ammonium chloride) on the aerobic biodegradation of benzene, toluene, and xylene (BTX) by Pseudomonas spp. was studied in the laboratory using a glass sand tank. The increase of nutrient levels resulted in enhanced bacterial growth and BTX degradation. Sulfate and phosphate serve as key electron acceptors in the microbiological processes degrading BTX. The observed bacterial morphological changes during BTX degradation reveal that the filamentous bacteria were the dominant species at low temperatures about 20 degrees C. The spherical and rod-shaped cells became dominant at higher temperatures ranging from 25 degrees C to 28 degrees C. When the BTX mixture was allowed to be biodegraded for longer incubation periods of 21-42 h at high phosphate concentrations, large amounts of rod-shaped cells were clustered. The morphological adaptation appears to be controlled by the temperature and nutrient levels in the sandy medium where Pseudomonas spp. thrives.