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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-CH 4 /y and 25.2 (20.8-29.5) Tg C-CO 2 /y from reservoirs and lakes. Chinese lakes and reservoirs emit 175.0 (134.7-215.3) Tg CO 2 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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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 (HCO 3 - ) 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 HCO 3 - , Na + , Chl-a, TDS, TN, TP and the ratio TN:TP had inverse trends. Stoichiometric ratios of DSi:HCO 3 - , DSi:Na + and HCO 3 - :Na + were significantly lower in the drought period. DSi exhibited significantly negative relationships with HCO 3 - , and DSi:Na + was strongly correlated with HCO 3 - :Na + in both drought and post-drought periods. The backward stepwise regression analysis that could avoid multicollinearity suggested that DSi:HCO 3 - 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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)

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.

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.

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., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

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).

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., (Copyright © 2013 Elsevier B.V. All rights reserved.)

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., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

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.

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.

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.

Benthic sediments in coastal acid sulfate soil (CASS) drains can contain high concentrations (~1-5%) of acid volatile sulfide (AVS) as nano-particulate mackinawite. These sediments can sequester substantial quantities of trace metals. Because of their low elevation and the connectivity of drains to estuarine channels, these benthic sediments are vulnerable to rapid increases in ionic strength from seawater incursion by floodgate opening, floodgate failure, storm surge and seasonal migration of the estuarine salt wedge. This study examines the effect of increasing seawater concentration on trace metal mobilization from mackinawite-rich drain sediments (210-550 μmol g⁻¹ AVS) collected along an estuarine salinity gradient. Linear combination fitting of S K-edge XANES indicated mackinawite comprised 88-96% of sediment-bound S. Anoxic sediment suspensions were conducted with seawater concentrations ranging from 0% to 100%. We found that mobilization of some metals increased markedly with increasing ionic strength (Cu, Fe, Mn, Ni) whereas Al mobilization decreased. The largest proportion of metals mobilized from the labile metal pool, operationally defined as Σexchangeable + acid-extractable + organically-bound metals, occurred in sediments from relatively fresh upstream sites (up to 39% mobilized) compared to sediments sourced from brackish downstream sites (0-11% mobilized). The extent of relative trace metal desorption generally followed the sequence Mn > Ni ≈ Cu > Zn > Fe > Al. Trace metal mobilization from these mackinawite-rich sediments was attributed primarily to desorption of weakly-bound metals via competitive exchange with marine-derived cations and enhanced complexation with Cl⁻ and dissolved organic ligands. These results have important implications for trace metal mobilization from these sediments at near-neutral pH under current predicted sea-level rise and climate change scenarios., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Episodic hypoxic events can occur following summer floods in sub-tropical estuaries of eastern Australia. These events can cause deoxygenation of waterways and extensive fish mortality. Here, we present a conceptual model that links key landscape drivers and biogeochemical processes which contribute to post-flood hypoxic events. The model provides a framework for examining the nature of anthropogenic forcing. Modification of estuarine floodplain surface hydrology through the construction of extensive drainage networks emerges as a major contributing factor to increasing the frequency, magnitude and duration of hypoxic events. Forcing occurs in two main ways. Firstly, artificial drainage of backswamp wetlands initiates drier conditions which cause a shift in vegetation assemblages from wetland-dominant species to dryland-dominant species. These species, which currently dominate the floodplain, are largely intolerant of inundation and provide abundant labile substrate for decomposition following flood events. Decomposition of this labile carbon pool consumes oxygen in the overlying floodwaters, and results in anoxic conditions and waters with excess deoxygenation potential (DOP). Carbon metabolism can be strongly coupled with microbially-mediated reduction of accumulated Fe and Mn oxides, phases which are common on these coastal floodplain landscapes. Secondly, artificial drainage enhances discharge rates during the flood recession phase. Drains transport deoxygenated high DOP floodwaters rapidly from backswamp wetlands to the main river channel to further consume oxygen. This process effectively displaces the natural carbon metabolism processes from floodplain wetlands to the main channel. Management options to reduce the impacts of post-flood hypoxia include i) remodifying drainage on the floodplain to promote wetter conditions, thereby shifting vegetation assemblages towards inundation-tolerant species, and ii) strategic retention of floodwaters in the backswamp wetlands to reduce the volume and rate during the critical post-flood recession phase., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The oxidation and acidification of sulfidic soil materials results in the re-partitioning of metals, generally to more mobile forms. In this study, we examine the partitioning of Fe, Cr, Cu, Mn, Ni and Zn in the acidified surface soil (0-0.1 m) and the unoxidised sub-soil materials (1.3-1.5 m) of an acid sulfate soil landscape. Metal partitioning at this acidic site was then compared to an adjacent site that was previously acidified, but has since been remediated by tidal re-inundation. Differences in metal partitioning were determined using an optimised six-step sequential extraction procedure which targets the "labile", "acid-soluble", "organic", "crystalline oxide", "pyritic" and "residual" fractions. The surficial soil materials of the acidic site had experienced considerable losses of Cr, Cu, Mn and Ni compared to the underlying parent material due to oxidation and acidification, yet only minor losses of Fe and Zn. In general, the metals most depleted from the acidified surface soil materials exhibited the greatest sequestration in the surface soil materials of the tidally remediated site. An exception to this was iron, which accumulated to highly elevated concentrations in the surficial soil materials of the tidally remediated site. The "acid-soluble", "organic" and "pyritic" fractions displayed the greatest increase in metals following tidal remediation. This study demonstrates that prolonged tidal re-inundation of severely acidified acid sulfate soil landscapes leads to the immobilisation of trace metals through the surficial accumulation of iron oxides, organic material and pyrite., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The accumulation and behavior of arsenic at the redox interface of Fe-rich sediments is strongly influenced by Fe(III) precipitate mineralogy, As speciation, and pH. In this study, we examined the behavior of Fe and As during aeration of natural groundwater from the intertidal fringe of a wetland being remediated by tidal inundation. The groundwater was initially rich in Fe(2+) (32 mmol L(-1)) and As (1.81 μmol L(-1)) with a circum-neutral pH (6.05). We explore changes in the solid/solution partitioning, speciation and mineralogy of Fe and As during long-term continuous groundwater aeration using a combination of chemical extractions, SEM, XRD, and synchrotron XAS. Initial rapid Fe(2+) oxidation led to the formation of As(III)-bearing ferrihydrite and sorption of >95% of the As(aq) within the first 4 h of aeration. Ferrihydrite transformed to schwertmannite within 23 days, although sorbed/coprecipitated As(III) remained unoxidized during this period. Schwertmannite subsequently transformed to jarosite at low pH (2-3), accompanied by oxidation of remaining Fe(2+). This coincided with a repartitioning of some sorbed As back into the aqueous phase as well as oxidation of sorbed/coprecipitated As(III) to As(V). Fe(III) precipitates formed via groundwater aeration were highly prone to reductive dissolution, thereby posing a high risk of mobilizing sorbed/coprecipitated As during any future upward migration of redox boundaries. Longer-term investigations are warranted to examine the potential pathways and magnitude of arsenic mobilization into surface waters in tidally reflooded wetlands.

This study examines the abundance of trace elements in surface sediments of a former acid sulfate soil (ASS) wetland subjected to marine tidal inundation. Sediment properties of this highly modified study site are compared with those of an adjacent unmodified, intertidal mangrove forest. Whilst some trace elements (Al, Cd, Mn, Ni and Zn) were clearly depleted due to mobilisation and leaching in the previous oxic-acidic phase, other trace elements (As and Cr) displayed significant enrichment in the tidally inundated ASS. Many trace elements were strongly associated with the reactive Fe and acid volatile sulfide (AVS) fractions, suggesting that trace elements may be adsorbed to abundant reactive Fe phases or sequestered as sulfide minerals. These findings provide an important understanding of the fate and mobility of reactive iron, AVS and trace elements during tidal remediation of a formerly acidified Great Barrier Reef (GBR) catchment., ((c) 2010 Elsevier Ltd. All rights reserved.)

Tidal seawater inundation of coastal acid sulfate soils can generate Fe- and S0(4)-reducing conditions in previously oxic-acidic sediments. This creates potential for mobilization of As during the redox transition. We explore the consequences for As by investigating the hydrology, porewater geochemistry, solid-phase speciation, and mineralogical partitioning of As across two tidal fringe toposequences. Seawater inundation induced a tidally controlled redox gradient Maximum porewater As (~400 μg/L) occurred in the shallow (<1 m), intertidal, redox transition zone between Fe-oxidizing and S0(4)-reducing conditions. Primary mechanisms of As mobilization include the reduction of solid-phase As(V) to As(lll), reductive dissolution of As(V)-bearing secondary Fe(lll) minerals and competitive anion desorption. Porewater As concentrations decreased in the zone of contemporary pyrite reformation. Oscillating hydraulic gradients caused by tidal pumping promote upward advection of As and Fe(2+)-enriched porewater in the intertidal zone, leading to accumulation of As(V)-enriched Fe(lll) (hydr)oxides at the oxic sediment-water interface. While this provides a natural reactive-Fe barrier, it does not completely retard the flux of porewater As to overtopping surface waters. Furthermore, the accumulated Fe minerals may be prone to future reductive dissolution. A conceptual model describing As hydro-geochemical coupling across an intertidal fringe is presented.

In acid-mine drainage and acid-sulfate soil environments, the cycling of Fe and As are often linked to the formation and fate of schwertmannite (Fe(8)O(8)(OH)(8-2x)(SO(4))(x)). When schwertmannite-rich material is subjected to near-neutral Fe(III)-reducing conditions (e.g., in reflooded acid-sulfate soils or mining-lake sediments), the resulting Fe(II) can catalyze transformation of schwertmannite to goethite. This work examines the effects of arsenic(V) and arsenic(III) on the Fe(II)-catalyzed transformation of schwertmannite and investigates the associated consequences of this mineral transformation for arsenic mobilization. A series of 9-day anoxic transformation experiments were conducted with synthetic schwertmannite and various additions of Fe(II), As(III), and As(V). X-ray diffraction (XRD) and Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy demonstrated that, in the absence of Fe(II), schwertmannite persisted as the dominant mineral phase. Under arsenic-free conditions, 10 mM Fe(II) catalyzed rapid and complete transformation of schwertmannite to goethite. However, the magnitude of Fe(II)-catalyzed transformation decreased to 72% in the presence of 1 mM As(III) and to only 6% in the presence of 1 mM As(V). This partial Fe(II)-catalyzed transformation of As(III)-sorbed schwertmannite did not cause considerable As(III) desorption. In contrast, the formation of goethite via partial transformation of As(III)- and As(V)-sorbed schwertmannite significantly decreased arsenic mobilization under Fe(III)-reducing conditions. This implies that the Fe(II)-catalyzed transformation of schwertmannite to goethite may help to stabilize solid-phase arsenic and retard its subsequent release to groundwater.

This study describes the sorption of As(V) and As(III) to schwertmannite as a function of pH and arsenic loading. In general, sorption of As(V) was greatest at low pH, whereas high pH favored the sorption of As(III). The actual pH of equivalent As(V) and As(III) sorption was strongly loading dependent, decreasing from pH approximately 8.0 at loadings <120 mmol(As) mol(Fe)(-1) to pH approximately 4.6 at a loading of 380 mmol(As) mol(Fe)(-1). Sorption isotherms for As(V) were characterized by strong partitioning to the schwertmannite solid-phase at low loadings and sorption capacities of 225-330 mmol(As(V)) mol(Fe)(-1) at high loadings. In contrast, the As(III) isotherms revealed a weak affinity for sorption of As(III) versus As(V) at low loadings yet a greater affinity for As(III) sorption compared with As(V) at high loadings (when pH > 4.6). Sorption of As(V) and As(III) caused significant release of SO(4)(2-) from within the schwertmannite solid-phase, without major degradation of the schwertmannite structure (as evident by X-ray diffraction and Raman spectroscopy). This can be interpreted as arsenic sorption via incorporation into the schwertmannite structure, rather than merely surface complexation at the mineral-water interface. The results of this study have important implications for arsenic mobility in the presence of schwertmannite, such as in areas affected by acid-mine drainage and acid-sulfate soils. In particular, arsenic speciation, arsenic loading, and pH should be considered when predicting and managing arsenic mobility in schwertmannite-rich systems.

This study describes the design, deployment, and application of a modified equilibration dialysis device (peeper) optimized for sampling pore waters in acid sulfate soils (ASS). The modified design overcomes the limitations of traditional-style peepers, when sampling firm ASS materials over relatively large depth intervals. The new peeper device uses removable, individual cells of 25 mL volume housed in a 1.5 m long rigid, high-density polyethylene rod. The rigid housing structure allows the device to be inserted directly into relatively firm soils without requiring a supporting frame. The use of removable cells eliminates the need for a large glove-box after peeper retrieval, thus simplifying physical handling. Removable cells are easily maintained in an inert atmosphere during sample processing and the 25-mL sample volume is sufficient for undertaking multiple analyses. A field evaluation of equilibration times indicates that 32 to 38 d of deployment was necessary. Overall, the modified method is simple and effective and well suited to acquisition and processing of redox-sensitive pore water profiles>1 m deep in acid sulfate soil or any other firm wetland soils.

This study describes iron and sulfur fractionation, and the related extractability of selected trace elements (As, Cd, Cr, Cu, Ni, Pb and Zn) in estuarine sediments. The sediments were sulfidic, with moderately high concentrations of pore-water sulfide (200-600 micromol l(-1)) and acid-volatile sulfide (AVS; 9.9-129 micromol g(-1)). Pyrite-S concentrations increased with depth, with 63-251 micromol g(-1) at site W1 and 312-669 micromol g(-1) at site W2. The degree of sulfidisation was generally high (>80%), indicating that Fe may be limiting pyrite accumulation. The ratios of AVS to pyrite-S increased with sediment depth, as expected for the pyritisation of solid-phase AVS. Cadmium, Pb and Zn extractability in 1M HCl indicated that these elements are not significantly sequestered during pyritisation, whereas sequestration may be important for As, Cu and possibly Ni. Extractability trends for Cr suggest that diagenesis in sulfidic sediments may enhance Cr reactivity. Overall, replacement of AVS by pyrite during diagenesis may enhance the reactivity of Cd, Cr, Pb and Zn, whereas As, Cu and possibly Ni may be rendered less reactive.

The effect of acid-volatile sulfide (AVS) oxidation on Fe-S cycling and water quality in coastal flood plain drains from acid-sulfate soil landscapes was examined using natural sediments and synthetic iron monosulfide. Oxidation of AVS occurred rapidly (half-time < or = 1 h) and produced elemental sulfur (S8(0)(s)) and iron oxyhydroxide (FeOOH(s)). The initial rapid AVS oxidation process occurred without significant acidification or changes to the aqueous-phase composition. Severe acidification (pH < 4) occurred only once S8(0)(s) began to oxidize to SO4 (within 2-3 days of the initial AVS oxidation). Our results demonstrate, for the first time with natural sediments, a significant pH-buffered (near-neutral) AVS oxidation step with the trigger to acidification being the oxidation of S8(0)(s). Acidification resulted in the pH-dependent release of large amounts of Al, Mn, Ni, and Zn even though the sediment metal content was low.

We examined processes regulating reduced inorganic sulfur (RIS) speciation in drain sediments from coastal acid sulfate soil (ASS) landscapes. Pore water sulfide was undetectable or present at low levels (0.6-18.8 microM), consistent with FeS(s) precipitation in the presence of high concentrations of Fe2+ (generally >2 mM). Acid-volatile sulfide (AVS), with concentrations up to 1019 micromol g(-1), comprised a major proportion of RIS. The AVS to pyrite-S ratios were up to 2.6 in sediment profiles containing abundant reactive Fe (up to approximately 4000 micromol g(-1)). Such high AVS:pyrite-S ratios are indicative of inefficient conversion of FeS(s) to pyrite. This may be due to low pore water sulfide levels causing slow rates of pyrite formation via the polysulfide and H2S oxidation pathways. Overall, RIS speciation in ASS-associated drain sediments is unique and is largely regulated by abundant reactive Fe.

The identification of common variants that contribute to the genesis of human inherited disorders remains a significant challenge. Hirschsprung disease (HSCR) is a multifactorial, non-mendelian disorder in which rare high-penetrance coding sequence mutations in the receptor tyrosine kinase RET contribute to risk in combination with mutations at other genes. We have used family-based association studies to identify a disease interval, and integrated this with comparative and functional genomic analysis to prioritize conserved and functional elements within which mutations can be sought. We now show that a common non-coding RET variant within a conserved enhancer-like sequence in intron 1 is significantly associated with HSCR susceptibility and makes a 20-fold greater contribution to risk than rare alleles do. This mutation reduces in vitro enhancer activity markedly, has low penetrance, has different genetic effects in males and females, and explains several features of the complex inheritance pattern of HSCR. Thus, common low-penetrance variants, identified by association studies, can underlie both common and rare diseases.