ABSTRACT
To better understand the impact of long-term irrigation practices on arsenic (As) accumulation in agricultural soils, 100 soil samples from depths of 0-20â¯cm were collected from the Datong basin, where the As-contaminated groundwater has been used for irrigation for several decades. Soil samples were analyzed for major elements, trace elements, and As, Fe speciation. Results reveal As content ranging from 4.00 to 14.5â¯mg/kg, an average of 10.2 ± 2.05â¯mg/kg, consistent with surveys conducted in 1998 and 2007. Arsenic speciation ranked in descending order as follows: As associated with silicate minerals (AsSi, 29.70 ± 7.53â¯%) > amorphous Fe-minerals associated As (AsFeox1, 26.40 ± 3.27â¯%) > crystalline Fe-minerals associated As (AsFeox2, 24.02 ± 4.60â¯%) > strongly adsorbed As (AsSorb, 14.29 ± 2.81â¯%) > As combined with carbonates and Fe-carbonates (AsCar, 2.30 ± 0.44â¯%) > weakly adsorbed As (AsDiss, 2.59 ± 1.00â¯%). The anomalous negative correlation between As and Fe content reflects the primary influence of soil provenance. Evidence from major element compositions and rare earth element patterns indicates that total As and Fe contents in soils are controlled by parent materials, exhibiting distinct north-south differences (As: higher levels in the north, lower levels in the south; Fe: higher levels in the south, lower levels in the north). Evidence from the Chemical Index of Alteration (CIA) and As/Ti ratio suggests that chemical weathering has led to As enrichment in the central basin. Notably, relationships such as AsDiss/Ti, AsSorb/Ti with CIA and total Fe content indicate significant influences of irrigation practices on adsorbed As (both weakly and strongly adsorbed) contents, showing a pattern of higher levels in the central basin and lower levels in the Piedmont. However, total As content remained stable after long-term irrigation, potentially due to the re-release of accumulated As via geochemical pathways during non-irrigated periods. These findings demonstrate that the soil systems can naturally remediate exogenous As contamination induced by irrigation practices. Quantitative assessment of the balance between As enrichment and re-release in soil systems is crucial for preventing soil As contamination, highlighting strategies like water-saving techniques and fallow periods to manage As contamination in agricultural areas using As-contaminated groundwater for irrigation.
ABSTRACT
Arsenic (As) is a groundwater contaminant of global concern. The degradation of dissolved organic matter (DOM) can provide a reducing environment for As release. However, the interaction of DOM with local microbial communities and how different sources and types of DOM influence the biotransformation of As in aquifers is uncertain. This study used optical spectroscopy, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), metagenomics, and structural equation modeling (SEM) to demonstrate the how the biotransformation of As in aquifers is promoted. The results indicated that the DOM in high-As groundwater is dominated by highly unsaturated low-oxygen(O) compounds that are quite humic and stable. Metagenomics analysis indicated Acinetobacter, Pseudoxanthomonas, and Pseudomonas predominate in high-As environments; these genera all contain As detoxification genes and are members of the same phylum (Proteobacteria). SEM analyses indicated the presence of Proteobacteria is positively related to highly unsaturated low-O compounds in the groundwater and conditions that promote arsenite release. The results illustrate how the biogeochemical transformation of As in groundwater systems is affected by DOM from different sources and with different characteristics.
Subject(s)
Arsenic , Groundwater , Metagenomics , Water Pollutants, Chemical , Groundwater/microbiology , Groundwater/chemistry , Arsenic/metabolism , Arsenic/chemistry , Water Pollutants, Chemical/metabolism , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/analysis , Mass Spectrometry , Fourier Analysis , Bacteria/genetics , Bacteria/metabolismABSTRACT
Illite plays an essential role in arsenic (As) transportation in the subsurface. Despite extensive investigations into As adsorption onto illite, debates persist due to the absence of direct evidence revealing the underlying processes. In this research, we conducted batch experiments and employed spherical aberration-corrected scanning transmission electron microscope, X-ray absorption spectroscopy, and density functional theory-based calculations to elucidate the mechanisms for the adsorption of two major inorganic As species (As(III) and As(V)) onto illite. Experimental results indicate adsorption capacities of 0.251 and 0.667 µmol/g for As(III) and As(V) onto illite, respectively. As(III) adsorption occurs within 300 min, whereas As(V) is rapidly adsorbed within 500 min, after which it tends to stabilize. Both As species can adsorbed onto the basal surface via electrostatic forces, where cations act as a bridge, leading to specific-cation effects. Conversely, As adsorption onto the edge surface can be ascribed to inner-sphere complexes via As-O-Al bonds, causing a negatively shifted isoelectric point of illite. These mechanisms collectively account for the partially reversible adsorption and two-stage kinetics pattern. Finally, a process-based surface complexation model was developed to predict As adsorption onto illite, which includes the inner/outer-sphere complexation and monodentate/bidentate complexes.
ABSTRACT
Mollisols rich in natural organic matter are a significant sink of carbon (C) and selenium (Se). Climate warming and agricultural expansion to the cold Mollisol regions may enhance soil respiration and biogeochemical cycles, posing a growing risk of soil C and Se loss. Through field-mimicking incubation experiments with uncultivated and cultivated soils from the Mollisol regions of northeastern China, this research shows that soil respiration remained significant even during cold seasons and caused co-emission of greenhouse gases (CO2 and CH4) and methylated Se. Such stimulus effects were generally stronger in the cultivated soils, with maximum emission rates of 7.45 g/m2/d C and 1.42 µg/m2/d Se. For all soil types, the greatest co-emission of CO2 and dimethyl selenide occurred at 25 % soil moisture, whereas measurable CH4 emission was observed at 40 % soil moisture with higher percentages of dimethyl diselenide volatilization. Molecular characterization with three-dimensional fluorescence and ultra-high resolution mass spectrometry suggests that CO2 emission is sensitive to the availability of microbial protein-like substances and free energy from organic carbon biodegradation under variable moisture conditions. Predominant Se binding to biodegradable organic matter resulted in high dependence of Se volatilization on rates of greenhouse gas emissions. These findings together highlight the importance of dynamic organic carbon quality for soil respiration and consequent Mollisol Se loss risk, with implications for science-based management of C and Se resources in agricultural lands to combat with Se deficiency.
Subject(s)
Carbon Dioxide , Greenhouse Gases , Methane , Selenium , Soil , Soil/chemistry , Selenium/analysis , Selenium/metabolism , Greenhouse Gases/analysis , Methane/metabolism , China , Carbon Dioxide/analysis , Soil Microbiology , MethylationABSTRACT
Massive soil erosion occurs in the world's Mollisol regions due to land use change and climate warming. The migration of Mollisol organic matter to river systems and subsequent changes in carbon biogeochemical flow and greenhouse gas fluxes are of global importance but little understood. By employing comparative mesocosm experiments simulating varying erosion intensity in Mollisol regions of northeastern China, this research highlights that erosion-driven export and biomineralization of terrestrial organic matter facilitates CO2 and CH4 emission from receiving rivers. Stronger Mollisol erosion, as represented by a higher soil-to-water ratio in suspensions, increased CO2 efflux, particularly for the paddy Mollisols. This is mechanistically attributable to increased bioavailability of soluble organic carbon in river water that is sourced back to destabilized organic matter, especially from the cultivated Mollisols. Concurrent changes in microbial community structure have enhanced both aerobic and anaerobic processes as reflected by the coemission of CO2 and CH4. Higher greenhouse gas effluxes from paddy Mollisol suspensions suggest that agricultural land use by supplying more nitrogen-containing, higher-free-energy organic components may have enhanced microbial respiration. These new findings highlight that Mollisol erosion is a hidden significant contributor to greenhouse gas emissions from river water, given that the world's four major Mollisol belts are all experiencing intensive cultivation.
Subject(s)
Carbon , Greenhouse Gases , Rivers , Rivers/chemistry , Soil/chemistry , China , Carbon Dioxide , Methane/metabolismABSTRACT
Organoiodine compounds (OICs) are the dominant iodine species in groundwater systems. However, molecular mechanisms underlying the geochemical formation of geogenic OICs-contaminated groundwater remain unclear. Based upon multitarget field monitoring in combination with ultrahigh-resolution molecular characterization of organic components for alluvial-lacustrine aquifers, we identified a total of 939 OICs in groundwater under reducing and circumneutral pH conditions. In comparison to those in water-soluble organic matter (WSOM) in sediments, the OICs in dissolved organic matter (DOM) in groundwater typically contain fewer polycyclic aromatics and polyphenol compounds but more highly unsaturated compounds. Consequently, there were two major sources of geogenic OICs in groundwater: the migration of the OICs from aquifer sediments and abiotic reduction of iodate coupled with DOM iodination under reducing conditions. DOM iodination occurs primarily through the incorporation of reactive iodine that is generated by iodate reduction into highly unsaturated compounds, preferably containing hydrophilic functional groups as binding sites. It leads to elevation of the concentration of the OICs up to 183 µg/L in groundwater. This research provides new insights into the constraints of DOM molecular composition on the mobilization and enrichment of OICs in alluvial-lacustrine aquifers and thus improves our understanding of the genesis of geogenic iodine-contaminated groundwater systems.
Subject(s)
Groundwater , Iodine , Water Pollutants, Chemical , Iodates , Water Pollutants, Chemical/analysis , Groundwater/chemistry , Water , Environmental MonitoringABSTRACT
The environmental fate of arsenic (As) relies substantially on its speciation, which occurs frequently coupled to the redox transformation of manganese. While trivalent manganese (Mn(III)), which is known for its high reactivity, is believed to play a role in As mobilization by iron (oxyhydr)oxides in dynamic aquifers, the exact roles and underlying mechanisms are still poorly understood. Using increasingly complex batch experiments that mimick As-affected aquifer conditions in combination with time-resolved characterization, we demonstrate that Mn(III)-NOM complexes play a crucial role in the manganese-mediated immobilization of As(III) by ferrihydrite and goethite. Under anaerobic condition, Mn(III)-fulvic acid (FA) rapidly oxidized 31.8% of aqueous As(III) and bound both As(III) and As(V). Furthermore, Mn(III)-FA exerted significantly different effects on the adsorption of As by ferrihydrite and goethite. Mn(III)-FA increased the adsorption of As by 6-16% due to the higher affinity of oxidation-produced As(V) for ferrihydrite under circumneutral conditions. In contrast, As adsorption by crystalline goethite was eventually inhibited due to the competitive effect of Mn(III)-FA. To summarize, our results reveal that Mn(III)-NOM complexes play dual roles in As retention by iron oxides, depending on the their crystallization. This highlights the importance of Mn(III) for the fate of As particularly in redox fluctuating groundwater environments.
ABSTRACT
Geogenic arsenic (As)-contaminated groundwater is a sustaining global health concern that is tightly constrained by multiple interrelated biogeochemical processes. However, a complete spectrum of the biogeochemical network of high-As groundwater remains to be established, concurrently neglecting systematic zonation of groundwater biogeochemistry on the regional scale. We uncovered the geomicrobial interaction network governing As biogeochemical pathways by merging in-field hydrogeochemical monitoring, metagenomic analyses, and ultrahigh resolution mass spectrometry (FT-ICR MS) characterization of dissolved organic matter. In oxidizing to weakly reducing environments, the nitrate-reduction and sulfate-reduction encoding genes (narGHI, sat) inhibited the dissolution of As-bearing iron minerals, leading to lower As levels in groundwater. In settings from weakly to moderately reducing, high abundances of sulfate-reduction and iron-transport encoding genes boosted iron mineral dissolution and consequent As release. As it evolved to strongly reducing stage, elevated abundance of methane cycle-related genes (fae, fwd, fmd) further enhanced As mobilization in part by triggering the formation of gaseous methylarsenic. During redox cycling of N, S, Fe, C and As in groundwater, As migration to groundwater and immobilization in mineral particles are geochemically constrained by basin-scale dynamics of microbial functionality and DOM molecular composition. The study constructs a theoretical model to summarize new perspectives on the biogeochemical network of As cycling.
Subject(s)
Arsenic , Groundwater , Water Pollutants, Chemical , Arsenic/analysis , Water Pollutants, Chemical/analysis , Groundwater/chemistry , Iron/analysis , Minerals , SulfatesABSTRACT
Mollisols are critical agricultural resources for securing global food supply. Due to its health importance, selenium (Se) fate in the Mollisols attracts growing concerns. Land use change from conventional drylands to paddy wetlands impacts Se bioavailability in the vulnerable Mollisol agroecosystems. The underlying processes and mechanisms however remain elusive. Here, results of flow-through reactor experiments with paddy Mollisols from northern cold-region sites indicate that continuous flooding with surface water for 48 d induced redox zonation that facilitated the loss of Mollisol Se by up to 51%. Further process-based biogeochemical modeling suggests largest degradation rates of dissolved organic matter (DOM) in 30 cm deep Mollisols that contained the highest-level labile DOM and organic-bound Se. Electron shunting from degradation of Se-bearing DOM coupled to reductive dissolution of Se-adsorbed Fe oxides accounts mainly for Se(IV) release into the pore water. Consequent changes in DOM molecular composition make the reservoir of organic-bound Se vulnerable to flooding-induced redox zonation and likely enhance Se loss through destruction of thiolated Se and emission of gaseous Se from the Mollisol layer. This study highlights a neglected scenario where the speciation-driven loss of bioavailable Se from the paddy wetlands can be a significant consequence in the cold-region Mollisol agroecosystems.
Subject(s)
Selenium , Selenium/chemistry , Soil/chemistry , Wetlands , Agriculture , WaterABSTRACT
The genesis of geogenic iodine (I)-contaminated groundwater poses a significant threat to long-term water exploitation. Safe and sustainable water supply, particularly in the northern arid basins, demands a quantitative prediction of the high variability of I distribution over hydrogeological timescales. Here, bioenergetics-informed reactive transport modeling was combined with high-resolution molecular characterization of fueling organic matter to decipher the time-controlled interactions between vertical flow and (bio)geochemical processes in I transport within the Datong aquifers. The declining reactivities of I-bearing organic matter and Fe oxides in the 15-40 m depth decreased the rate of I release, while a growing number of pore volumes flushed through the aquifers to leach out I- and organic I. This removal effect is compensated by the desorption of I- from Fe oxides and secondary FeS generated from the concurrent reduction of Fe oxides and SO42-. Consequently, peak concentrations of groundwater I- may have appeared, depending upon the vertical recharge rate, at the first several pore volumes flushed through the aquifers. The current vertical distributions of the various I species likely represent a quasi-steady state between I mobilization and leaching. These new mechanistic insights into the dynamic hydrogeological-(bio)geochemical processes support secure groundwater use in the I-affected northern arid basins.
Subject(s)
Arsenic , Groundwater , Iodine , Water Pollutants, Chemical , Water Pollutants, Chemical/analysis , Environmental Monitoring , Groundwater/chemistry , Water Supply , OxidesABSTRACT
Mollisols support the most productive agroecosystems in the world. Despite their critical links to food quality and human health, the varying distributions of selenium (Se) species and factors governing Se mobility in the mollisol vadose zone remain elusive. This research reveals that, in northern mollisol agroecosystems, Se hotspots (≥0.32 mg/kg) prevail along the regional river systems draining the Lesser Khingan Mountains, where piedmont Se-rich oil shales are the most probable source of regional Se. While selenate and selenite dominate Se species in the water-soluble and absorbed pools, mollisol organic matter is the major host for Se. Poorly crystalline and crystalline Fe oxides are subordinate in Se retention, hosting inorganic and organic Se at levels comparable to those in the adsorbed pool. The depth-dependent distributions of mollisol Se species for the non-cropland and cropland sites imply a predominance of reduced forms of Se under the mildly acidic and reducing conditions that, in turn, are variably impacted by agricultural land use. These findings therefore highlight that fluvial deposition and land use change together are the main drivers of the spatial variability and speciation of mollisol Se.
Subject(s)
Selenium Compounds , Selenium , Humans , Selenious Acid , Agriculture , Selenic Acid , WaterABSTRACT
The distribution, speciation, and bioavailability of selenium (Se) - an essential micronutrient for human beings - in agricultural soils influence the resource recovery of agricultural benefits and the sustainable use of Se in agroecosystems. Quantitative understanding in this regard however remains limited in the world's mollisol agroecosystems, despite their critical importance in securing global food supply. Herein, a systematic investigation of Se in the river sediment-irrigation water-mollisols-rhizosphere-rice seeds continuum, at the core zone of the northern mollisol regions, was conducted to elucidate the hydrological-hydrogeochemical processes and mechanisms responsible for the distribution and bioavailability of Se. The content of total Se in the mollisols ranged between 0.12 and 0.54 mg/kg with an average of 0.31 mg/kg. At the riverside flood plains, humic-acid bound Se accounted on average for 39 % of total Se. This pool of Se can be transformed to water-soluble and ion-exchangeable Se(VI), supporting a higher potential of Se bioavailability at riparian agricultural mollisols. For mollisol lands far from the river channels, the topography affects the speciation and partitioning of Se presumably through regulating water retention and organic matter transport. Moreover, altering pH and redox conditions in response to irrigation with the river water may boost Se bioavailability in weakly acidic and high Eh mollisols. It can be in part ascribed to the transformation of organic-bound Se along with infiltrated oxygenated water that leads to the increase of water-soluble and ion-exchangeable Se. These findings reinforce that hydrological-hydrogeochemical perturbations due to irrigation with surface water need to be assessed carefully in the management of Se resources in the mollisol agroecosystems.
Subject(s)
Selenium , Humans , Selenium/metabolism , Biological Availability , Agriculture , Soil/chemistry , WaterABSTRACT
The prevalence of arsenic (As)-affected groundwater in the Late Pleistocene and Holocene aquifers leads to serious arsenicosis worldwide. However, the geogenic foundational processes underlying the high As aquifers remain elusive. Here we present joint lines of evidences from chronological, sediment geochemical and geomicrobial analysis that climate change since the Last Glacial Maximum (LGM) initiates the genesis of high As aquifers in the central Yangtze River Basin, which represents Quaternary alluvial-lacustrine floodplains affected by arsenicosis occurrence. Optically stimulated luminescence-based sediments dating and grain size characterization indicate that the LGM depositional boundary also separates the Late-Pleistocene/Holocene high arsenic aquifers from the underlying arsenic-depleted aquifers. Further examination of solid-phase As/Fe/S speciation and associated microbial communities function suggests that the pre-LGM depositional environments characteristic of S metabolism engender the fixation of As in pyrite, whereas during the post-LGM period climate change to warm and humid leads to As repartitioning to Fe/Mn oxides in response to strong chemical weathering. This may have contributed to a dynamic fate of As in the post-LGM depositional environments and thus a highly variable aqueous As concentrations over depth. Our results highlight the important roles of climate change has played in the genesis of high As aquifers, with implications for other LGM-affected regions worldwide as well as for the evolution of high arsenic aquifers under future climate change.
Subject(s)
Arsenic , Groundwater , Water Pollutants, Chemical , Arsenic/metabolism , Climate Change , Groundwater/chemistry , Rivers , Water Pollutants, Chemical/chemistryABSTRACT
Flavins and siderophores secreted by various plants, fungi and bacteria under iron (Fe) deficient conditions play important roles in the biogeochemical cycling of Fe in the environment. Although the mechanisms of flavin and siderophore mediated Fe(III) reduction and dissolution under anoxic conditions have been widely studied, the influence of these compounds on Fe(II) oxidation under oxic conditions is still unclear. In this study, we investigated the kinetics of aqueous Fe(II) (17.8 µM) oxidation by O2 at pH 5â7 in the presence of riboflavin (oxidized (RBF) and reduced (RBFH2)) and desferrioxamine B (DFOB) as representative flavins and siderophores, respectively. Results showed that the addition of RBF/RBFH2 or DFOB markedly accelerates the oxidation of aqueous Fe(II) by O2. For instance, at pH 6, the rate of Fe(II) oxidation was enhanced 20â70 times when 10 µM RBFH2 was added. The mechanisms responsible for the accelerated Fe(II) oxidation are related to the redox reactivity and complexation ability of RBFH2, RBF and DFOB. While RBFH2 does not readily complex Fe(II)/Fe(III), it can activate O2 and generate reactive oxygen species, which then rapidly oxidize Fe(II). In contrast, both RBF and DFOB do not reduce O2 but react with Fe(II) to form RBF/DFOB-complexed Fe(II), which in turn accelerates Fe(II) oxidation. Furthermore, the lower standard reduction potential of the Fe(II)-DFOB complex, compared to the Fe(II)-RBF complex, correlates with a higher oxidation rate constant for the Fe(II)-DFOB complex. Our study reveals an overlooked catalytic role of flavins and siderophores that may contribute to Fe(II)/Fe(III) cycling at oxic-anoxic interfaces.
ABSTRACT
The Fe-modified biochar (FeBC) was used to remove aqueous As(III/V), and the role of oxygen (O2) in As removal was investigated by integrating aqueous and solid analyses. The removal efficiencies for As(III) and As(V) increased from 86.4% and 99.2% under anoxic conditions, respectively, to >99.9% when O2 was available. FeBC removed As(III) from As(III)-spiked systems by surface-oxidation following adsorption, where oxidation of As(III) was promoted by O2. As(V) was first reduced, re-oxidized in solutions, and then adsorbed to FeBC in As(V)-spiked systems, where reduction of As(V) was inhibited at the presence of O2. Both As(III) and As(V) were bidentate corner-sharing complexed to Fe oxides/hydroxides on FeBC, with As coordinated to Fe at ~3.4 Å according to As extended X-ray absorption fine structure (EXAFS) modeling. These findings identified the effect of ambient O2 in As(III/V) redox transformations and removal, guiding the further application of FeBC in environmental treatment.
Subject(s)
Arsenic , Adsorption , Charcoal , Oxidation-Reduction , OxygenABSTRACT
The accumulation of arsenic (As) in agrarian soils poses a potential long-term risk to human health, and this accumulation largely depends on the adsorption behavior of As onto soil minerals. This study considered the adsorption of As(III) onto natural soils from the Datong Basin, focusing on the quantification of the adsorption capacities of soil minerals and further the prediction of As(III) adsorption isotherms of the bulk soils. Linear programming calculations show that Fe-bearing minerals, illite, dolomite, and soil organic matter all contribute to As(III) adsorption, on average accounting for 73.9, 11.4, 8.2, and 6.5% of the overall adsorption capacity of soil to As(III), respectively. However, not all the Fe-bearing minerals in soils can adsorb As(III). Evidence from the sequential chemical extractions shows that 90.1% of the soil Fe is associated with silicates (FeSi), while results of the linear programming calculations suggest that FeSi cannot adsorb As(III). Based on the above results, a surface complexation model well predicts the experimental As(III) adsorption isotherms for aeolian and riverine soils. However, the adsorption of As(III) onto lacustrine soils is underestimated in both linear programming calculations and surface complexation modeling. This study highlights the importance of both Fe-bearing minerals and non-Fe minerals for As(III) adsorption and the difference in the adsorption capacity between various soil minerals. It further suggests that more comprehensive considerations are necessary when building a reactive transport model for As(III) in soil systems.
ABSTRACT
A highly specific DNA-functionalized hydrogel sensing layer was integrated with the diffusive gradients in thin films (DGT) technique for the direct determination of aqueous mercury(II). The DNA-functionalized layer in the DGT unit exhibited both high affinity (complexation constant Kc = 1019.8 at 25 °C) and high binding capacity (9.5 mg Hg disk-1) toward Hg2+. The diffusion coefficient for Hg2+ complexed with common inorganic ligands was an order of magnitude higher than that for Hg2+ complexed with natural dissolved organic matter: 9.0 × 10-6 versus 9.8 × 10-7 cm2 s-1 at 25 °C. The performance of the DNA-DGT sensor was further assessed under variable pH (3-10) and temperature (5-40 °C) conditions, as well as across a range of hydrochemically diverse artificial and natural freshwaters. The observed effects of the environmental and solution compositional variables on Hg2+ binding to the DNA in the sensing layer were successfully accounted for by equilibrium speciation calculations and temperature-corrected, multicomponent diffusion coefficients for aqueous Hg(II). The results therefore support the use of the DNA-DGT sensor as an alternative to traditional sampling and analysis methods for measuring aqueous Hg(II) concentrations down to the nanomolar level in freshwater environments.
Subject(s)
Mercury , Water Pollutants, Chemical , DNA , Diffusion , Environmental Monitoring , Fresh Water , Mercury/analysis , Water Pollutants, Chemical/analysisABSTRACT
Flavin-mediated electron transfer is an important pathway for Fe(III) reduction by dissimilatory iron-reducing bacteria. Although the mechanisms and kinetics of Fe(III) reduction by reduced flavins have been widely studied, the reaction between Fe(II) and oxidized flavins is rarely investigated. Results of this study show that under anoxic conditions, Fe(II) can be oxidized by the oxidized forms of riboflavin (RBF) and flavin mononucleotide (FMN) at pH 7-9. For instance, at pH 9, 73% of 17.8 µM Fe(II) was oxidized by 10 µM RBF within 20 min. Both the rate and extent of oxidation increased with increasing concentrations of oxidized flavins and increasing solution pH. Thermodynamic calculations and kinetic analyses implied that the oxidation of Fe(II) proceeded predominantly via the autodecomposition of Fe2+-RBF- and Fe2+-FMN- complexes, along with minor contributions from direct oxidation of Fe(II) by flavins and flavin radicals. Our findings suggest that the reoxidation of Fe(II) by oxidized flavins may be a rate-controlling factor in microbial Fe(III) reduction via flavin-mediated electron transfer.
Subject(s)
Ferric Compounds , Flavins , Electron Transport , Ferrous Compounds , Flavin Mononucleotide/metabolism , Flavins/metabolism , Oxidation-Reduction , RiboflavinABSTRACT
A long-lasting challenge in eliminating the worldwide impact of geogenic arsenic (As)-contaminated groundwater is the development of efficient, in-situ treatment technologies that are applicable in decentralized and rural areas. Here we present a managed aquifer rehabilitation (MAR) approach based on the in-situ creation of Fe-oxide scavengers for remediating As-contaminated groundwater. The Fe-oxide coatings on sediment surfaces were generated via periodic injection of Fe2+ and ClO- solutions into an As-affected sandy aquifer at the Datong Basin, northern China for 25 days. This treatment prompted the buildup of weakly alkaline/circumneutral and oxidizing conditions to enhance As(III) oxidation in the target aquifer. Dissolved As concentrations decreased from the initial average 78.0 to 9.8 µg/L over the 25-d amendment. Sediment imaging by scanning electron microscope-X-ray energy dispersive spectroscopy confirms the deposition of Fe-rich precipitates on sediment surfaces with the simultaneous retention of As, and high density electrical tomography suggests the occurrence of such a process throughout the target zone. Further X-ray diffraction analysis and sequential chemical extraction reveal that the neo-formed Fe minerals comprised both poorly crystalline (e.g., ferrihydrite) and better crystalline (e.g., goethite) Fe oxides. The process-based reactive-transport modeling for the variations of As species in the treated groundwater supports that the new Fe-oxide minerals, most probably goethite, acted as efficient removers of aqueous As. The low As level of â¼10 µg/L was maintained during the following 215-d monitoring, demonstrating the long effectiveness of the MAR approach. This study highlights the feasibility of As immobilization by manipulating in-situ Fe-oxide coating on sandy sediments at the pilot scale. The MAR technology may be applicable for As-affected aquifers with controlled oxidizing conditions in the Datong Basin and likely other high-As regions with similar hydrogeochemical settings.
Subject(s)
Arsenic , Groundwater , Water Pollutants, Chemical , China , Geologic Sediments , IronABSTRACT
Mercury (Hg) is a toxic metal posing major health risks to human beings and wildlife. The characterization of Hg fate and transport in aquatic environments is hindered by a lack of sensitive, selective and easily field-deployable analytical techniques. Here we assess the reliability and performance of a Hg2+ sensor based on the selective binding of Hg2+ to a thymine-rich DNA under environmentally-relevant conditions. Experimental results indicate that the interactions between the DNA and SYBR Green I, which produce the detection fluorescence signal, are significantly impacted by pH, metal ligands and natural dissolved organic matter (NDOM). These interferences are largely eliminated by immobilizing the DNA in a polyacrylamide hydrogel, although high concentrations of NDOM, such as fulvic acids, still affect the sensor's performance due to competitive binding of Hg2+. The binding of Hg2+ to NDOM, however, can be accounted for via equilibrium speciation calculations, which also yield the complexation constant for Hg2+ binding to the DNA in the hydrogel. The equilibrium calculations reproduce the results for the entire set of experimental conditions, from simple electrolyte solutions to complex aqueous compositions mimicking natural lake waters, and across large ranges of pH (3-10) and temperature (5-50⯰C).