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Although sulfur cycling in acid mine drainage (AMD)-contaminated rice paddy soils is critical to understanding and mitigating the environmental consequences of AMD, potential sources and transformations of organosulfur compounds in such soils are poorly understood. We used sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy to quantify organosulfur compounds in paddy soils from five AMD-contaminated sites and one AMD-uncontaminated reference site near the Dabaoshan sulfide mining area in South China. We also determined the sulfur stable isotope compositions of water-soluble sulfate (δ 34 S WS ), adsorbed sulfate (δ 34 S AS ), fulvic acid sulfur (δ 34 S FAS ), and humic acid sulfur (δ 34 S HAS ) in these samples. Organosulfate was the dominant functional group in humic acid sulfur (HAS) in both AMD-contaminated (46%) and AMD-uncontaminated paddy soils (42%). Thiol/organic monosulfide contributed a significantly lower proportion of HAS in AMD-contaminated paddy soils (8%) compared to that in AMD-uncontaminated paddy soils (21%). Within contaminated soils, the concentration of thiol/organic monosulfide was positively correlated with cation exchange capacity (CEC), moisture content (MC), and total Fe (TFe). δ 34 S FAS ranged from -6.3 to 2.7‰, similar to δ 34 S WS (-6.9 to 8.9‰), indicating that fulvic acid sulfur (FAS) was mainly derived from biogenic S-bearing organic compounds produced by assimilatory sulfate reduction. δ 34 S HAS (-11.0 to -1.6‰) were more negative compared to δ 34 S WS , indicating that dissimilatory sulfate reduction and abiotic sulfurization of organic matter were the main processes in the formation of HAS.

Although it has been established that electron mediators substantially promote extracellular electron transfer (EET), electron shuttling pathways are not fully understood. Here, a new electron shuttling pathway was found in the EET process by Shewanella oneidensis MR-1 with resazurin, a lipophilic electron mediator. With resazurin, the genes encoding outer-membrane cytochromes ( mtrCBA and omcA ) were downregulated. Although cytochrome deletion substantially reduced biocurrent generation to 1-12% of that of wild-type (WT) cells, the presence of resazurin restored biocurrent generation to 168 μA·cm -2 (Δ mtrA / omcA / mtrC ), nearly equivalent to that of WT cells (194 μA·cm -2 ), indicating that resazurin-mediated electron transfer was not dependent on the Mtr pathway. Biocurrent generation by resazurin was much lower in Δ cymA and Δ mtrA / omcA / mtrC / fccA / cctA mutants (4 and 6 μA·cm -2 ) than in WT cells, indicating a key role of FccA, CctA, and CymA in this process. The effectiveness of resazurin in EET of Mtr cytochrome mutants is also supported by cyclic voltammetry, resazurin reduction kinetics, and in situ c -type cytochrome spectroscopy results. The findings demonstrated that low molecular weight, lipophilic electron acceptors, such as phenoxazine and phenazine, may facilitate electron transfer directly from periplasmic and inner membrane proteins, thus providing new insight into the roles of exogenous electron mediators in electron shuttling in natural and engineered biogeochemical systems.

Grass shrimp ( Palaemonetes pugio ) represent a potential link in the transfer of methylmercury (MeHg) from salt marsh sediments to transient young-of-the-year (YOY) fish. Across six salt marshes subject to varying degrees of Hg contamination, MeHg concentration in grass shrimp was significantly correlated with MeHg in sediment ( p < 0.05, R 2 = 0.81). Bioenergetic models show that grass shrimp alone account for 12-90% of MeHg observed in YOY striped bass and 6-22% of MeHg in YOY summer flounder. Direct accumulation of MeHg from grass shrimp to YOY fish increased with MeHg levels in grass shrimp and sediment. However, in the most contaminated salt marshes with the highest levels of MeHg in grass shrimp and sediment, indirect accumulation of MeHg from grass shrimp by YOY summer flounder, whose diet is dominated by benthic forage fish (mummichog), is predicted to plateau because higher concentrations of MeHg in grass shrimp are offset by a lower proportion of grass shrimp in the mummichog diet. Our results demonstrate that grass shrimp are an important trophic link in the bioaccumulation of MeHg in salt marsh food webs and that MeHg accumulation in YOY fish varies with both the concentration of MeHg in salt marsh sediments and benthic food web structure.

Soot and mercury (Hg) are two notorious air pollutants, and the fate and transport of Hg may be affected by soot at various scales in the environment as soot may be both a carrier and a reactant for active Hg species. This study was designed to quantify photoreduction of Hg(II) in the presence of soot and the associated Hg isotope fractionation under both atmospheric aerosol and aqueous conditions (water-saturated). Photoreduction experiments were conducted with diesel soot particulate matter under controlled temperature and relative humidity (RH) conditions using a flow-through semibatch reactor system. Mass-dependent fractionation resulted in the enrichment of heavier Hg isotopes in the remaining Hg(II) with enrichment factors (ε 202 Hg) of 1.48 ± 0.02‰ (±2 standard deviation) to 1.75 ± 0.05‰ for aerosol-phase reactions (RH 28-68%) and from 1.26 ± 0.11 to 1.50 ± 0.04‰ for aqueous-phase reactions. Positive odd mass-independent fractionation (MIF) was observed in aqueous-phase reactions, resulting in Δ 199 Hg values for reactant Hg(II) as high as 5.29‰, but negative odd-MIF occurred in aerosol-phase reactions, in which Δ 199 Hg values of reactant Hg(II) varied from -1.02 to 0‰. The average ratio of Δ 199 Hg/Δ 201 Hg (1.1) indicated that under all conditions, MIF was dominated by magnetic isotope effects during photoreduction of Hg(II). Increasing RH resulted in higher reduction rates but lower extents of negative MIF in the aerosol-phase experiments, suggesting that the reduction of soot particle-bound Hg(II) was responsible for the observed negative odd-MIF. Our results suggest that mass-independent Hg isotope fractionation during Hg(II) photoreduction varies with soot aerosol water content and that Hg-stable isotope ratios may be used to understand the transformational histories of aerosol-bound Hg(II) in the environment.

How metal-reducing bacteria transfer electrons during dissimilatory energy generation under electron acceptor-limited conditions is poorly understood. Here, we incubated the iron and manganese-reducing bacterium Shewanella oneidensis MR-1 without electron acceptors. Removal of soluble extracellular organic compounds (EOCs) dramatically retarded transfer of electrons to an experimental electron acceptor, Cr(VI), by MR-1. However, the return of either high MW (>3000 Da) or low MW (<3000 Da) soluble EOCs produced by MR-1 to washed cells restored Cr(VI) reduction though Cr(VI) reduction was fastest when both size fractions were added together. Spectral and electrochemical characterization of EOCs indicated the presence of flavins and c -type cytochromes ( c -Cyts). A model of the kinetics of individual elementary reactions between cells, flavins, released c -Cyts, and Cr(VI), including the direct reduction of flavins, released c -Cyts, and Cr(VI) by cells and the indirect reduction of Cr(VI) by reduced forms of flavins and released c -Cyts, was developed. Model results suggest that released c -Cyts could act as electron mediators to accelerate electron transfer from cells to Cr(VI), and the relative contribution of this pathway was higher than that mediated by flavins. Hence, extracellular c -Cyts produced by MR-1 likely play a role in extracellular electron transfer under electron acceptor-limited conditions. These findings provide new insights into extracellular electron shuttling and the metabolic strategy of metal-reducing bacteria under electron acceptor-limited conditions.

The photochemical reduction of Hg(II) is an important pathway in the environmental Hg cycle because it competes with Hg methylation and potentially limits the formation of bioaccumulative methylmercury. Hg stable isotope systematics have proven to be an effective tool for investigating the transport, transformation, and bioaccumulation of Hg. The dominant cause of mass independent isotope fractionation (MIF) of Hg in nature is the photochemical reduction of various species of Hg(II). However, it is difficult to fully interpret Hg stable isotope signatures due to the lack of mechanistic information about which Hg compounds are susceptible to MIF and why. This study investigates Hg isotope fractionation during the photochemical reduction of Hg(II) complexed to organic ligands, which are representative of the available binding sites in natural dissolved organic matter. The photochemical reduction of Hg(II) in the presence of cysteine resulted in both negative and positive MIF in residual Hg(II), where the sign depended on pH and dissolved oxygen level. In the presence of serine, either nuclear volume or magnetic isotope effects were observed depending on the wavelength of light and the extent of Hg(II) complexation by serine. In the presence of ethylenediamine, MIF was negative. Our Hg stable isotope results suggest that MDF and MIF are induced at different steps in the overall photochemical reduction reaction and that MIF does not depend on the rate-determining step but instead depends on photophysical aspects of the reaction such as intersystem crossing and hyperfine coupling. The behavior of Hg isotopes reported here will allow for a better understanding of the underlying reaction mechanisms controlling the Hg isotope signatures recorded in natural samples.

Distinct spatiotemporal distributions of sea surface dissolved elemental mercury (DEM) and its air-sea exchange flux were observed in the river-dominated and monsoon-influenced East China Sea (ECS). Spatially, DEM concentrations were higher in the nearshore Changjiang diluted water (90 ± 20 to 260 ± 40 fM) than in the offshore Kuroshio water (60 ± 10 to 160 ± 40 fM) and correlated with salinity and total Hg concentrations, suggesting that the total Hg discharged from the Changjiang river is a controlling factor. In summer, monsoon-driven coastal upwelling formed a transient nearshore water mass with very elevated DEM concentrations (290 ± 20 to 320 ± 70 fM). Seasonally, DEM concentrations in all water masses were the highest in summer (120 ± 30 to 320 ± 70 fM). Estimated rate coefficients for DEM production varied seasonally and strongly correlated with sea surface temperature (SST). Hg 0 evasion fluxes also peaked in summer (670 ± 380 pmol m -2 day -1 ), while in winter, DEM was close to equilibrium with gaseous elemental mercury in the atmosphere. Based on the air-sea Hg fluxes for all four seasons from this study and regional atmospheric deposition fluxes from others, we conclude that the ECS is a net sink of Hg annually, but it is a source of Hg to the atmosphere in summer. Moreover, the contribution of the ECS to Hg evasion may increase as a result of flood-associated high Changjiang discharge and rising SST.

The biological production of monomethylmercury (MeHg) in soils and sediments is an important factor controlling mercury (Hg) accumulation in aquatic and terrestrial food webs. In this study we examined the fractionation of Hg stable isotopes during Hg methylation in nongrowing cultures of the anaerobic bacteria Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132. Both organisms showed mass-dependent, but no mass-independent fractionation of Hg stable isotopes during Hg methylation. Despite differences in methylation rates, the two bacteria had similar Hg fractionation factors (αr/p = 1.0009 and 1.0011, respectively). Unexpectedly, δ(202)Hg values of MeHg for both organisms were 0.4‰ higher than the value of initial inorganic Hg after about 35% of inorganic Hg had been methylated. These results indicate that a (202)Hg-enriched pool of inorganic Hg was preferentially utilized as a substrate for methylation by these organisms, but that multiple intra- and/or extracellular pools supplied inorganic Hg for biological methylation. Understanding the controls of the Hg stable isotopic composition of microbially produced MeHg is important to identifying bioavailable Hg in natural systems and the interpretation of Hg stable isotopes in aquatic food webs.

Analysis of arsenic concentrations in New Jersey well water from the Newark Basin showed up to 15% of the wells exceed 10 microg L(-1), with a maximum of 215 microg L(-1). In some geologic settings in the basin, this mobile arsenic could be from the weathering of pyrite (FeS2) found in black shale that contains up to 4% arsenic by weight. We hypothesized that under oxic conditions at circumneutral pH, the microbially mediated oxidation of sulfide in the pyrite lattice would lead to the release of pyrite-bound arsenic. Moreover, the oxidation of aqueous As(III) to As(V) by aerobic microorganisms could further enhance arsenic mobilization from the solid phase. Enrichment cultures under aerobic, As(III)-oxidizing conditions were established under circumneutral pH with weathered black shale from the Newark Basin as the inoculum source. Strain WAO, an autotrophic inorganic-sulfur and As(III)-oxidizer, was isolated and phylogenetically and physiologically characterized. Arsenic mobilization studies from arsenopyrite (FeAsS) mineral, conducted with strain WAO at circumneutral pH, showed microbially enhanced mobilization of arsenic and complete oxidation of released arsenic and sulfur to stoichiometric amounts of arsenate and sulfate. In addition, WAO preferentially colonized pyrite on the surface of arsenic-bearing, black shale thick sections. These findings support the hypothesis that microorganisms can directly mobilize and transform arsenic bound in mineral form at circumneutral pH and suggest that the microbial mobilization of arsenic into groundwater may be important in other arsenic-impacted aquifers.

Speciation and reactivity of mercury were examined in Berry's Creek estuary downstream of a highly mercury-contaminated U.S. EPA Superfund site during the summers of 2002 and 2003. Surface water samples from Berry's Creek estuary, its confluence with the Hackensack River, and upstream of that confluence were analyzed for total (THg), particulate (PHgT), and dissolved (DHg) mercury, total and particulate monomethylmercury (MeHg), dissolved gaseous mercury (DGM), and bacterial merA gene and transcript abundances. Surface water concentrations of THg in Berry's Creek estuary (210-6800 pM) are among the highest in North America. A downstream gradient of Hg contamination is a permanent feature of Berry's Creek estuary, and the upper estuary appears to be a perennial source of Hg to the lower estuary and the Hackensack River. MeHg concentrations in Berry's Creek surface waters ranged from 2 to 14 pM, with the highest concentrations occurring at a midestuary site 2 km downstream of the tide gate. The suspended particle phase dominated Hg and MeHg speciation throughout this system, accounting for > 90% of THg in Berry's Creek estuary and 35-94% of THg in the Hackensack River. Concentrations of DGM in Berry's Creek estuary (0.1-1.0 pM) are similar to levels of DGM in other much less contaminated estuaries (0.04-0.75 pM). In addition, expression levels of the bacterial mercuric reductase gene, merA, a gene of the inorganic Hg(II)-regulated, mercury resistance (mer) operon, were low throughout Berry's Creek estuary. Thus, despite very high concentrations of mercury in Berry's Creek estuary, relatively low concentrations of DGM and merA gene expression levels indicate limited bioavailability of inorganic Hg in the estuary's surface waters. A system-wide limitation on the bioavailability of inorganic Hg, together with bacterial demethylation activity, may account for observed MeHg concentrations that, although elevated, are lower than expected given the concentrations of THg in this estuary.

Upland placement of dredged materials from navigation channels in the New York/New Jersey Harbor is currently being used to manage sediments deemed inappropriate for open water disposal. Although upland placement sites are equipped with engineering controls (leachate collection and/or barrier walls), little is known of the potential impacts of this approach to air quality. The aim of this study was to estimate the flux of mercury to the atmosphere from New York/New Jersey Harbor stabilized dredged material (SDM) that was used for land reclamation at a site in northeastern New Jersey. Total gaseous mercury (TGM) was measured at a site receiving SDM in August and October 2001 and May and November 2002. TGM was also monitored at an urban reference site 3.5 km west of the SDM site in September 2001 and from February 2002 to July 2002 and from October 2002 to February 2003. The concentration of TGM at the urban reference site averaged 2.2 +/- 1.1 ng m(-3), indicating some local contribution to the Northern Hemisphere background. TGM concentrations exhibited seasonality with the highest values in summer (3.3 +/- 2.1 ng m(-3) in June 2002) and the lowest in winter (1.7 +/- 0.6 ng m(-3) in January 2003). TGM concentrations at the SDM placement site ranged from 2 to 7 ng m(-3) and were significantly higher (p < 0.001) than those at the urban reference site. Sediment-air fluxes of Hg at the SDM placement site estimated by the micrometeorological technique ranged from -13 to 1040 ng m(-2) h(-1) (sediment to air fluxes being positive) and were significantly correlated to solar radiation (r2 = 0.81). The estimated contribution of Hg emissions from land-applied SDM to local TGM concentrations was found to be negligible (<4%). However, the estimated annual volatilization rate of TGM atthe SDM site (130 kg y(-1))was comparable to those of other industrial sources in New Jersey (140-450 kg y(-1)).

Atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured at urban/industrial, suburban, coastal, and rural areas in New Jersey as part of the New Jersey Atmospheric Deposition Network. Concentrations of 36 PAH compounds were measured in the gas and particle phases in air and in precipitation at nine sites at regular intervals from October 1997 through May 2001. Gas-phase and particle-phase sigma36PAH concentrations ranged from 0.45 to 118 ng m(-3) and from 0.046 to 172 ng m(-3), respectively, and precipitation concentrations ranged from 11 to 16200 ng L(-1). PAH concentrations vary spatially across the region, with the highest concentrations occurring at the most heavily urban and industrial locations. Average gas absorption deposition ranged from 0.004 (naphthacene) to 5040 (methylphenanthrenes) ng m(-2) d(-1), and dry particle deposition PAH fluxes ranged from 0.11 (naphthacene) to 300 (benzo[b+k]fluoranthene) ng m(-2) d(-1) at the nine sites. Average atmospheric wet deposition PAH fluxes at the seven sites ranged from 0.40 (cyclopenta[cd]pyrene) to 140 (methylphenanthrenes) ng m(-2) d(-1). These represent the first comprehensive estimates of PAH deposition to New Jersey and the Mid-Atlantic East Coast.

The curious phenomenon of similar levels of methylmercury (MeHg) accumulation in fish from contaminated and pristine environments may be explained by the observation that the proportion of total mercury (HgT) present as MeHg is inversely related to HgT in natural waters. We hypothesize that this "MeHg accumulation paradox" is explained by the quantitative induction of bacterial enzymes that are encoded by the mercury resistance (mer) operon, organomercury lyase (MerB), and mercuric reductase (MerA) by inorganic Hg (Hg[II]). We tested this hypothesis in two ecosystems in New Jersey: Berry's Creek in the Meadowlands (ML) and Pine Barren (PB) lakes. Across all sites, an inverse correlation (r2 = 0.80) between the concentration of HgT (ML, 113-4220 ng L(-1); PB, 0.3-5.4 ng L(-1)) and the proportion of HgT as MeHg (MeHg in ML and PB ranged from 0.08 to 1.6 and from 0.03 to 0.34 ng L(-1), respectively) was observed. The planktonic microbial community in Meadowlands surface waters exhibited adaptation to mercury, the presence of mer genes and mRNA transcripts, and high rates of reductive demethylation (k(deg) = 0.19 day(-1)). In contrast, the microbial community of PB was not adapted to mercury and demonstrated low rates of oxidative demethylation (k(deg) = 0.01 day(-1)). These results strongly support our hypothesis and show that the degradation of MeHg by mer-encoded enzymes by the water column microbiota of contaminated environments can significantly affect the amount of MeHg that is available for entry into the aquatic food web.

The first estimates of atmospheric deposition fluxes of polychlorinated biphenyls (PCBs) to the Hudson River Estuary are presented. Concentrations of PCBs were measured in air, aerosol, and precipitation at nine sites representing a variety of land-use regimes at regular intervals from October 1997 through May 2001. Highest concentrations in the gas phase were observed at urban sites such as Camden and Jersey City (sigmaPCB concentrations averaged 3250 and 1260 pg m(-3), respectively). In great portions of the state encompassing forested, coastal, and suburban environments, gas-phase sigmaPCB concentrations were essentially the same (averaging 150-220 pg m(-3)). This spatial trend suggests that atmospheric PCBs arise from highly localized, urban sources which influence atmospheric concentrations and deposition fluxes over a distance of a few tens of kilometers. Atmospheric sigmaPCB deposition fluxes (gas absorption + dry particle deposition + wet deposition) ranged from 7.3 to 340 microg m(-2) yr(-1) and increased with proximity to urban areas. While the magnitude of the fluxes increased with urbanization,the relative proportions of wet, dry, and gaseous deposition remained largely constant. Because the Hudson River Estuary is adjacent to urban areas such as Jersey City, it is subject to higher depositional fluxes of PCBs. These depositional fluxes are at least 2-10 times those estimated for the Chesapeake Bay and Lake Michigan. Inputs of PCBs to the Hudson River Estuary from the upper Hudson River and from wastewater treatment plants are 8-18 times atmospheric inputs, and volatilization of PCBs from the estuary exceeds atmospheric deposition of low molecular weight PCBs.

Cell surface and intracellular accumulation kinetics of phenanthrene were studied in two coastal marine diatoms. Cell surface uptake and depuration rate constants were two to three times greater in the smaller Thalassiosira pseudonana than in T. weissflogii, reflecting the 2.8-fold difference in surface-area-to-volume ratio (A/V) between the two species. However, cell surface accumulation was faster than most other environmental and biological process, supporting the assumption that cell surfaces are in equilibrium with the water. Intracellular depuration rate constants of phenanthrene were similar (0.56 d(-1), 0.62 d(-1)) for both diatoms and for other hydrophobic organic contaminants (ca 1 d(-1)) with a range of hydrophobicities and chemical structures in other microalgae. Biodilution could be a significant factor in the internal accumulation of phenanthrene, as phenanthrene loss rate constants were on the order of phytoplankton growth rates in the spring and summer (1-3 d(-1)). Organic carbon-normalized phenanthrene bioconcentration factors were not significantly different for the two diatom species. The fraction of phenanthrene in the cell surface compartment at steady-state (x1) was directly related to the A/V of the two diatoms and a Chlorophyte microalga, showing that intracellular partitioning, which may affect phenanthrene trophic transfer, depends on phytoplankton cell size.