Performance of UV/acetylacetone process for saline dye wastewater treatment: Kinetics and mechanism.

Futility of traditional advanced oxidation processes (AOPs) in saline wastewater treatment has stimulated the quest for novel "halotolerant" chemical oxidation technology. Acetylacetone (AA) has proven to be a potent photo-activator in the degradation of dyes, but the applicability of UV/AA for saline wastewater treatment needs to be verified. In this study, degradation of crystal violet (CV) was investigated in the UV/AA system in the presence of various concentrations of exogenic Cl- or Br-. The results reveal that degradation, mineralization and even accumulation of adsorbable organic halides (AOX) were not significantly affected by the addition of Cl- or Br-. Rates of CV degradation were enhanced by elevating either AA dosage or solution acidity. An apparent kinetic rate equation was developed as r = -d[CV]/dt = k[CV]a[AA]b = (7.34 × 10-4 mM1-(a+b) min-1) × [CV]a=0.16 [AA]b=0.97. In terms of results of radical quenching experiments, direct electron/energy transfer is considered as the major reaction mechanism, while either singlet oxygen or triplet state (3(AA)*) might be involved. Based on identification of degradation byproducts, a possible degradation pathway of CV in the UV/AA system is proposed.

Highly efficient and rapid removal of arsenic(iii) from aqueous solutions by nanoscale zero-valent iron supported on a zirconium 1,4-dicarboxybenzene metal-organic framework (UiO-66 MOF).

A zirconium 1,4-dicarboxybenzene metal-organic framework (UiO-66 MOF) was successfully used as a template to enhance the distribution and activity of nanoscale zero-valent iron (NZVI). MOF-NZVI showed good anti-interference ability to co-existing ions (Ca2+, Mn2+, Cu2+, H2PO4 - and SO4 2-) and organic acids (oxalic acid and citric acid). SEM and TEM analyses indicated that the MOF as a support efficiently prevent NZVI from aggregation for quick and effective removal of As(iii). Through the non-linear least-squares (NLLS) adjustment, As(iii) removal by MOF-NZVI could be well fitted by pseudo first and second order reaction kinetics, as well as the Freundlich isotherm. FTIR, XRD and XPS results verified that NZVI and iron oxyhydroxides (Fe3O4, γ-Fe2O3, γ-FeOOH and α-FeOOH) might be responsible for the effective removal of As(iii) and its oxidized product As(v) with an adsorption capacity of 360.6 mg As per g NZVI through chemical oxidation and physical adsorption. This work indicates that MOF-NZVI with good reusability and high efficiency is promising for application in As(iii)-polluted wastewater treatment.

Large greenhouse gases emissions from China's lakes and reservoirs.

Freshwaters are important sources of greenhouse gases (GHGs) to the atmosphere that may partially offset the terrestrial carbon sink. However, current emission estimates from inland waters remain uncertain due to data paucity in key regions with a large freshwater surface area, such as China. Here, we show that the areal fluxes of GHGs (carbon dioxide, methane, and nitrous oxide) from lakes and reservoirs in China are much larger than previous estimates. Our work summarized data from 310 lakes and 153 reservoirs, and revealed diffusive emissions of 1.56 (95% confidence interval: 1.12-2.00) Tg C-CH4/y and 25.2 (20.8-29.5) Tg C-CO2/y from reservoirs and lakes. Chinese lakes and reservoirs emit 175.0 (134.7-215.3) Tg CO2 equivalent, with 73.4% of this forcing contributed by lakes. These aquatic sources are equivalent to 14.1%-22.6% of China's estimated terrestrial carbon sink. Our results suggest a disproportionally high contribution of China's reservoirs and lakes to national and global GHGs emissions, highlighting major data gaps and the need of including more artificial and natural lakes data from developing countries like China in global GHGs budgets.

Extreme drought decouples silicon and carbon geochemical linkages in lakes.

Silicon and carbon geochemical linkages were usually regulated by chemical weathering and organism activity, but had not been investigated under the drought condition, and the magnitude and extent of drought effects remain poorly understood. We collected a comprehensive data set from a total of 13 sampling sites covering the main water body of the largest freshwater lake system in Australia, the Lower Lakes. Changes to water quality during drought (April 2008-September 2010) and post-drought (October 2010-October 2013) were compared to reveal the effects of drought on dissolved silica (DSi) and bicarbonate (HCO3-) and other environmental factors, including sodium (Na+), pH, electrical conductivity (EC), chlorophyll a (Chl-a), total dissolved solids (TDS), dissolved inorganic nitrogen (DIN), total nitrogen (TN), total phosphorus (TP) and water levels. Among the key observations, concentrations of DSi and DIN were markedly lower in drought than in post-drought period while pH, EC and concentrations of HCO3-, Na+, Chl-a, TDS, TN, TP and the ratio TN:TP had inverse trends. Stoichiometric ratios of DSi:HCO3-, DSi:Na+ and HCO3-:Na+ were significantly lower in the drought period. DSi exhibited significantly negative relationships with HCO3-, and DSi:Na+ was strongly correlated with HCO3-:Na+ in both drought and post-drought periods. The backward stepwise regression analysis that could avoid multicollinearity suggested that DSi:HCO3- ratio in drought period had significant relationships with fewer variables when compared to the post-drought, and was better predictable using nutrient variables during post-drought. Our results highlight the drought effects on variations of water constituents and point to the decoupling of silicon and carbon geochemical linkages in the Lower Lakes under drought conditions.

Dissolution and redistribution of trace elements and nutrients during dredging of iron monosulfide enriched sediments.

The increased use of estuarine waters for commercial and recreational activities is one consequence of urbanisation. Western Australia's Peel-Harvey Estuary highlights the impacts of urbanisation, with a rapidly developing boating industry and periodic dredging activity. The aim of this research is to evaluate the potential mobility of nutrients and trace elements during dredging, and the influence of flocculation on iron and sulfur partitioning in iron monosulfide enriched sediments. Our findings indicate a short-term increase in nitrate, phosphate and ammonium, during dredging through the resuspension of sediments. However, no increase in metal mobilisation during dredging was observed except copper (Cu) and zinc (Zn). Flocculant addition increased the release of nutrients, zinc (Zn) and arsenic (As) from sediments, had no effect on acid volatile sulfides and pyritic sulfur, but corresponded with an initial sharp rise in elemental sulfur concentrations. The run-off water from geofabric bags should be treated to decrease the concentrations of Zn and As to their background levels before releases into the estuary. Long-term impact of dredging on organic matter mineralisation and its subsequent effect on nutrients and trace elements dynamics needs further investigation.

Oxidative transformation of iron monosulfides and pyrite in estuarine sediments: Implications for trace metals mobilisation.

Iron monosulfides are the initial iron sulfide minerals that form under reducing conditions in organic-rich sediments. Frequently referred as monosulfidic black ooze (MBO), these sediments exists in a range of anoxic systems including estuaries, coastal wetlands and permeable reactive barriers. The objective of this study was to investigate the transformation of solid phase sulfur, iron fractions and trace metals mobilisation in organic-rich hypersulfidic sediments during dredging. Two sediments from geographically contrasting sites in the Peel-Harvey Estuary were collected and subjected to oxidation through resuspension over 14 days. During oxidation, redox potential rapidly and continuously increased, although minimal change in pH was observed in both sediments. The majority of FeS was oxidised within 48 h. Although not as dynamic as FeS, unusually high rates of FeS2 oxidation were measured in both sediments at circumneutral pH, with between 39 and 58% of FeS2 oxidised over 14 days. The rapid oxidation of FeS2 may be attributed to the presence of nano-size FeS2 crystals (≈550-860 nm) with a high surface area. Before resuspension, solid bound Fe(total) was most abundant as measured by HCl-extractable Fe(II), followed by organic bound Fe(total) and oxide bound Fe(total). There was a marked decrease in these three fractions in both sediments during resuspension, with an increase in Fe(III) fraction. No significant release of trace metals was observed during resuspension of sulfidic sediments. However, disturbance to these estuarine sediments increases Fe(III) formation and further deteriorates the environment through smothering biological surfaces, deteriorating food sources and the quality of benthic habitats.

Differential effect of biochar upon reduction-induced mobility and bioavailability of arsenate and chromate.

Heavy metals such as chromium (Cr) and arsenic (As) occur in ionic form in soil, with chromate [Cr(VI)] and arsenate As(V) being the most pre-dominant forms. The application of biochar to Cr(VI) and As(V) spiked and field contaminated soils was evaluated on the reduction processes [(Cr(VI) to Cr(III)] and [As(V) to As(III))], and subsequent mobility and bioavailability of both As(V) and Cr(VI). The assays used in this study included leaching, soil microbial activity and XPS techniques. The reduction rate of As(V) was lower than that of Cr(VI) with and without biochar addition, however, supplementation with biochar enhanced the reduction process of As(V). Leaching experiments indicated Cr(VI) was more mobile than As(V). Addition of biochar reversed the effect by reducing the mobility of Cr and increasing that of As. The presence of Cr and As in both spiked and contaminated soils reduced microbial activity, but with the addition of biochar to these soils, the microbial activity increased in the Cr(VI) contaminated soils, while it was further decreased with As(V) contaminated soils. The addition of biochar was effective in mitigating Cr toxicity by reducing Cr(VI) to Cr(III). In contrast, the conversion process of As(V) to As(III) hastened by biochar was not favourable, as As(III) is more toxic in soils. Overall, the presence of functional groups on biochar promotes reduction by providing the electrons required for reduction processes to occur as determined by XPS data.

Air-water CO2 outgassing in the Lower Lakes (Alexandrina and Albert, Australia) following a millennium drought.

Lakes are an important source and sink of atmospheric CO2, and thus are a vital component of the global carbon cycle. However, with scarce data on potentially important subtropical and tropical areas for whole continents such as Australia, the magnitude of large-scale lake CO2 emissions is unclear. This study presents spatiotemporal changes of dissolved inorganic carbon and water - to - air interface CO2 flux in the two of Australia's largest connected, yet geomorphically different freshwater lakes (Lake Alexandrina and Lake Albert, South Australia), during drought (2007 to September-2010) and post-drought (October 2010 to 2013). Lake levels in the extreme drought were on average approximately 1m lower than long-term average (0.71 m AHD). Drought was associated with an increase in the concentrations of dissolved inorganic species, organic carbon, nitrogen, Chl-a and major ions, as well as water acidification as a consequence of acid sulfate soil (ASS) exposure, and hence, had profound effects on lake pCO2 concentrations. Lakes Alexandrina and Albert were a source of CO2 to the atmosphere during the drought period, with efflux ranging from 0.3 to 7.0 mmol/m(2)/d. The lake air-water CO2 flux was negative in the post-drought, ranging between -16.4 and 0.9 mmol/m(2)/d. The average annual CO2 emission was estimated at 615.5×10(6) mol CO2/y during the drought period. These calculated emission rates are in the lower range for lakes, despite the potential for drought conditions that shift the lakes from sink to net source for atmospheric CO2. These observations have significant implications in the context of predicted increasing frequency and intensity of drought as a result of climate change. Further information on the spatial and temporal variability in CO2 flux from Australian lakes is urgently warranted to revise the global carbon budget for lakes.

Evaluation of Soil Manipulation to Prepare Engineered Earthen Waste Covers for Revegetation.

Seven ripping treatments designed to improve soil physical conditions for revegetation were compared on a test pad simulating an earthen cover for a waste disposal cell. The field test was part of study of methods to convert compacted-soil waste covers into evapotranspiration covers. The test pad consisted of a compacted layer of fine-textured soil simulating a barrier protection layer overlain by a gravelly sand bedding layer and a cobble armor layer. Treatments included combinations of soil-ripping implements (conventional shank [CS], wing-tipped shank [WTS], and parabolic oscillating shank with wings [POS]), ripping depths, and number of passes. Dimensions, dry density, moisture content, and particle size distribution of disturbance zones were determined in two trenches excavated across rip rows. The goal was to create a root-zone dry density between 1.2 and 1.6 Mg m and a seedbed soil texture ranging from clay loam to sandy loam with low rock content. All treatments created V-shaped disturbance zones as measured on trench faces. Disturbance zone size was most influenced by ripping depth. Winged implements created larger disturbance zones. All treatments lifted fines into the bedding layer, moved gravel and cobble down into the fine-textured protection layer, and thereby disrupted the capillary barrier at the interface. Changes in dry density within disturbance zones were comparable for the CS and WTS treatments but were highly variable among POS treatments. Water content increased in the bedding layer and decreased in the protection layer after ripping. The POS at 1.2-m depth and two passes created the largest zone with a low dry density (1.24 Mg m) and the most favorable seedbed soil texture (gravely silt loam). However, ripping also created large soil aggregates and voids in the protection layer that may produce preferential flow paths and reduce water storage capacity.

Changing fluxes of carbon and other solutes from the Mekong River.

Rivers are an important aquatic conduit that connects terrestrial sources of dissolved inorganic carbon (DIC) and other elements with oceanic reservoirs. The Mekong River, one of the world's largest rivers, is firstly examined to explore inter-annual fluxes of dissolved and particulate constituents during 1923-2011 and their associated natural or anthropogenic controls. Over this period, inter-annual fluxes of dissolved and particulate constituents decrease, while anthropogenic activities have doubled the relative abundance of SO4(2-), Cl(-) and Na(+). The estimated fluxes of solutes from the Mekong decrease as follows (Mt/y): TDS (40.4) > HCO3(-) (23.4) > Ca(2+) (6.4) > SO4(2-) (3.8) > Cl(-) (1.74)~Na(+) (1.7) ~ Si (1.67) > Mg(2+) (1.2) > K(+ 0.5). The runoff, land cover and lithological composition significantly contribute to dissolved and particulate yields globally. HCO3(-) and TDS yields are readily predicted by runoff and percent of carbonate, while TSS yield by runoff and population density. The Himalayan Rivers, including the Mekong, are a disproportionally high contributor to global riverine carbon and other solute budgets, and are of course underlined. The estimated global riverine HCO3(-) flux (Himalayan Rivers included) is 34,014 × 10(9) mol/y (0.41 Pg C/y), 3915 Mt/y for solute load, including HCO3(-), and 13,553 Mt/y for TSS. Thereby this study illustrates the importance of riverine solute delivery in global carbon cycling.

Distribution of iron- and sulfate-reducing bacteria across a coastal acid sulfate soil (CASS) environment: implications for passive bioremediation by tidal inundation.

Coastal acid sulfate soils (CASS) constitute a serious and global environmental problem. Oxidation of iron sulfide minerals exposed to air generates sulfuric acid with consequently negative impacts on coastal and estuarine ecosystems. Tidal inundation represents one current treatment strategy for CASS, with the aim of neutralizing acidity by triggering microbial iron- and sulfate-reduction and inducing the precipitation of iron-sulfides. Although well-known functional guilds of bacteria drive these processes, their distributions within CASS environments, as well as their relationships to tidal cycling and the availability of nutrients and electron acceptors, are poorly understood. These factors will determine the long-term efficacy of "passive" CASS remediation strategies. Here we studied microbial community structure and functional guild distribution in sediment cores obtained from 10 depths ranging from 0 to 20 cm in three sites located in the supra-, inter- and sub-tidal segments, respectively, of a CASS-affected salt marsh (East Trinity, Cairns, Australia). Whole community 16S rRNA gene diversity within each site was assessed by 454 pyrotag sequencing and bioinformatic analyses in the context of local hydrological, geochemical, and lithological factors. The results illustrate spatial overlap, or close association, of iron-, and sulfate-reducing bacteria (SRB) in an environment rich in organic matter and controlled by parameters such as acidity, redox potential, degree of water saturation, and mineralization. The observed spatial distribution implies the need for empirical understanding of the timing, relative to tidal cycling, of various terminal electron-accepting processes that control acid generation and biogeochemical iron and sulfur cycling.

Methane and CO2 emissions from China's hydroelectric reservoirs: a new quantitative synthesis.

Controversy surrounds the green credentials of hydroelectricity because of the potentially large emission of greenhouse gases (GHG) from associated reservoirs. However, limited and patchy data particularly for China is constraining the current global assessment of GHG releases from hydroelectric reservoirs. This study provides the first evaluation of the CO2 and CH4 emissions from China's hydroelectric reservoirs by considering the reservoir water surface and drawdown areas, and downstream sources (including spillways and turbines, as well as river downstream). The total emission of 29.6 Tg CO2/year and 0.47 Tg CH4/year from hydroelectric reservoirs in China, expressed as CO2 equivalents (eq), corresponds to 45.6 Tg CO2eq/year, which is 2-fold higher than the current GHG emission (ca. 23 Tg CO2eq/year) from global temperate hydropower reservoirs. China's average emission of 70 g CO2eq/kWh from hydropower amounts to 7% of the emissions from coal-fired plant alternatives. China's hydroelectric reservoirs thus currently mitigate GHG emission when compared to the main alternative source of electricity with potentially far great reductions in GHG emissions and benefits possible through relatively minor changes to reservoir management and design. On average, the sum of drawdown and downstream emission including river reaches below dams and turbines, which is overlooked by most studies, represents the equivalent of 42% of the CO2 and 92% of CH4 that emit from hydroelectric reservoirs in China. Main drivers on GHG emission rates are summarized and highlight that water depth and stratification control CH4 flux, and CO2 flux shows significant negative relationships with pH, DO, and Chl-a. Based on our finding, a substantial revision of the global carbon emissions from hydroelectric reservoirs is warranted.

Coprecipitated arsenate inhibits thermal transformation of 2-line ferrihydrite: implications for long-term stability of ferrihydrite.

2-line ferrihydrite, a ubiquitous iron oxy-hydroxide found in natural and engineered systems, is an efficient sink for the toxic metalloids such as arsenic. While much is known of the excellent capacity of ferrihydrite to coprecipitate arsenate, there is little information concerning the long-term stability of arsenate-accumulated ferrihydrite. By thermal treatment methodology, the expedited transformation of ferrihydrite in the presence of coprecipitated arsenate was studied at varying As/Fe ratios (0-0.5) and different heating temperature (40, 300, 450, 600°C). Pure and transformed minerals were characterized by thermogravimetry (TG), X-ray diffraction (XRD), Electron Spin Resonance (ESR), Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-EDX) and Fourier Transform Infrared Spectroscopy (FTIR). Arsenate was found to retard the thermal transformation of ferrihydrite. The extents of ferrihydrite transformation to hematite decreased with increasing As/Fe ratios, but increased at a higher heating temperature. It is predicted that the coprecipitated arsenate can stabilize the amorphous iron oxides against the transformation to more crystalline solids. Arsenate concentration appears to play an important role in this predicted long-term stability.

Selective oxidation of arsenite by peroxymonosulfate with high utilization efficiency of oxidant.

Oxidation of arsenite (As(III)) is a critical yet often weak link in many current technologies for remediating contaminated groundwater. We report a novel, efficient oxidation reaction for As(III) conversion to As(V) using commercial available peroxymonosulfate (PMS). As(III) is rapidly oxidized by PMS with a utilization efficiency larger than 90%. Increasing PMS concentrations and pH accelerate oxidation of As(III), independent to the availability of dissolved oxygen. The addition of PMS enables As(III) to oxidize completely to As(V) within 24 h, even in the presence of high concentrations of radical scavengers. On the basis of these observations and theoretical calculations, a two-electron transfer (i.e., oxygen atom transfer) reaction pathway is proposed. Direct oxidation of As(III) by PMS avoids the formation of nonselective reactive radicals, thus minimizing the adverse impact of coexisting organic matter and maximizing the utilization efficiency of PMS. Therefore, this simple approach is considered a cost-effective water treatment method for the oxidation of As(III) to As(V).

Chemical weathering and CO2 consumption in the Lower Mekong River.

Data on river water quality from 42 monitoring stations in the Lower Mekong Basin obtained during the period 1972-1996 was used to relate solute fluxes with controlling factors such as chemical weathering processes. The total dissolved solid (TDS) concentration of the Lower Mekong varied from 53 mg/L to 198 mg/L, and the median (114 mg/L) was compared to the world spatial median value (127 mg/L). Total cationic exchange capacity (Tz(+)) ranged from 729 to 2,607 µmolc/L, and the mean (1,572 µmolc/L) was 1.4 times higher than the world discharge-weighted average. Calcium and bicarbonate dominated the annual ionic composition, accounting for ~70% of the solute load that equalled 41.2×10(9)kg/y. TDS and major elements varied seasonally and in a predictable way with river runoff. The chemical weathering rate of 37.7t/(km(2)y), with respective carbonate and silicate weathering rates of 27.5t/(km(2) y) (13.8mm/ky) and 10.2t/(km(2) y) (3.8mm/ky), was 1.5 times higher than the global average. The CO2 consumption rate was estimated at 191×10(3)molCO2/(km(2)y) for silicate weathering, and 286×10(3)molCO2/(km(2)y) by carbonate weathering. In total, the Mekong basin consumed 228×10(9)molCO2/y and 152×10(9)molCO2/y by the combined weathering of carbonate and silicate, constituting 1.85% of the global CO2 consumption by carbonate weathering and 1.75% by silicates. This is marginally higher than its contribution to global water discharge ~1.3% and much higher than (more than three-fold) its contribution to world land surface area. Remarkable CO2 consumed by chemical weathering (380×10(9)mol/y) was similar in magnitude to dissolved inorganic carbon as HCO3(-) (370×10(9)mol/y) exported by the Mekong to the South China Sea. In this landscape, atmospheric CO2 consumption by rock chemical weathering represents an important carbon sink with runoff and physical erosion controlling chemical erosion.

Arsenic(III) and iron(II) co-oxidation by oxygen and hydrogen peroxide: divergent reactions in the presence of organic ligands.

Iron-catalyzed oxidation of As(III) to As(V) can be highly effective for toxic arsenic removal via Fenton reaction and Fe(II) oxygenation. However, the contribution of ubiquitous organic ligands is poorly understood, despite its significant role in redox chemistry of arsenic in natural and engineered systems. In this work, selected naturally occurring organic ligands and synthetic ligands in co-oxidation of Fe(II) and As(III) were examined as a function of pH, Fe(II), H2O2, and radical scavengers (methanol and 2-propanol) concentration. As(III) was not measurably oxidised in the presence of excess ethylenediaminetetraacetic acid (EDTA) (i.e. Fe(II):EDTA<1:1), contrasting with the rapid oxidation of Fe(II) by O2 and H2O2 at neutral pH under the same conditions. However, partial oxidation of As(III) was observed at a 2:1 ratio of Fe(II):EDTA. Rapid Fe(II) oxidation in the presence of organic ligands did not necessarily result in the coupled As(III) oxidation. Organic ligands act as both iron speciation regulators and radicals scavengers. Further quenching experiments suggested both hydroxyl radicals and high-valent Fe species contributed to As(III) oxidation. The present findings are significant for the better understanding of aquatic redox chemistry of iron and arsenic in the environment and for optimization of iron-catalyzed arsenic remediation technology.

Simultaneous redox conversion of chromium(VI) and arsenic(III) under acidic conditions.

Arsenic and chromium are often abundant constituents of acid mine drainage (AMD) and are most harmful as arsenite (As(III)) and hexavalent (Cr(VI)). To simultaneously change their oxidation state from As(III) to As(V), and Cr(VI) to Cr(III), is a potentially effective and attractive strategy for environmental remediation. The coabundance of As(III) and Cr(VI) in natural environments indicates their negligible direct interaction. The addition of H2O2 enables and greatly accelerates the simultaneous oxidation of As(III) and reduction of Cr(VI). These reactions are further enhanced at acidic pH and higher concentrations of Cr(VI). However, the presence of ligands (i.e., oxalate, citrate, pyrophosphate) greatly retards the oxidation of As(III), even though it enhances the reduction of Cr(VI). To explain these results we propose a reaction mechanism where Cr(VI) is primarily reduced to Cr(III) by H2O2, via the intermediate tetraperoxochromate Cr(V). Cr(V) is then involved in the formation of (•)OH radicals. In the presence of ligands, the capacity of Cr(V) to form (•)OH radicals, which are primarily responsible for As(III) oxidation, is practically inhibited. Our findings demonstrate the feasibility for the coconversion of As(III) and Cr(VI) in AMD and real-world constraints to this strategy for environmental remediation.

Decoupling between water column oxygenation and benthic phosphate dynamics in a shallow eutrophic estuary.

Estuaries are crucial biogeochemical filters at the land-ocean interface that are strongly impacted by anthropogenic nutrient inputs. Here, we investigate benthic nitrogen (N) and phosphorus (P) dynamics in relation to physicochemical surface sediment properties and bottom water mixing in the shallow, eutrophic Peel-Harvey Estuary. Our results show the strong dependence of sedimentary P release on Fe and S redox cycling. The estuary contains surface sediments that are strongly reducing and act as net P source, despite physical sediment mixing under an oxygenated water column. This decoupling between water column oxygenation and benthic P dynamics is of great importance to understand the evolution of nutrient dynamics in marine systems in response to increasing nutrient loadings. In addition, the findings show that the relationship between P burial efficiency and bottom water oxygenation depends on local conditions; sediment properties rather than oxygen availability may control benthic P recycling. Overall, our results illustrate the complex response of an estuary to environmental change because of interacting physical and biogeochemical processes.

Sulfate availability drives divergent evolution of arsenic speciation during microbially mediated reductive transformation of schwertmannite.

The effect of SO4(2-) availability on the microbially mediated reductive transformation of As(V)-coprecipitated schwertmannite (Fe8O8(OH)3.2(SO4)2.4(AsO4)0.004) was examined in long-term (up to 400 days) incubation experiments. Iron EXAFS spectroscopy showed siderite (FeCO3) and mackinawite (FeS) were the dominant secondary Fe(II) minerals produced via reductive schwertmannite transformation. In addition, ∼ 25% to ∼ 65% of the initial schwertmannite was also transformed relatively rapidly to goethite (αFeOOH), with the extent of this transformation being dependent on SO4(2-) concentrations. More specifically, the presence of high SO4(2-) concentrations acted to stabilize schwertmannite, retarding its transformation to goethite and allowing its partial persistence over the 400 day experiment duration. Elevated SO4(2-) also decreased the extent of dissimilatory reduction of Fe(III) and As(V), instead favoring dissimilatory SO4(2-) reduction. In contrast, where SO4(2-) was less available, there was near-complete reduction of schwertmannite- and goethite-derived Fe(III) as well as solid-phase As(V). As a result, under low SO4(2-) conditions, almost no Fe(III) or As(V) remained toward the end of the experiment and arsenic solid-phase partitioning was controlled mainly by sorptive interactions between As(III) and mackinawite. These As(III)-mackinawite interactions led to the formation of an orpiment (As2S3)-like species. Interestingly, this orpiment-like arsenic species did not form under SO4(2-)-rich conditions, despite the prevalence of dissimilatory SO4(2-) reduction. The absence of an arsenic sulfide species under SO4(2-)-rich conditions appears to have been a consequence of schwertmannite persistence, combined with the preferential retention of arsenic oxyanions by schwertmannite. The results highlight the critical role that SO4(2-) availability can play in controlling solid-phase arsenic speciation, particularly arsenic-sulfur interactions, under reducing conditions in soils, sediments, and shallow groundwater systems.