Bioaccumulation and trophic transfer of methylmercury in Long Island Sound

Author Posting. © Springer, 2006. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Archives of Environmental Contamination and Toxicology 51 (2006): 416-424, doi:10.1007/s00244-005-0265-7.Humans are exposed to methylmercury (MeHg) principally by consumption of marine fish. The coastal zone supports the majority of marine fish production, and may therefore be an important source of MeHg to humans; however, little is known about the bioaccumulation or MeHg in near-shore marine ecosystems. We examined MeHg in microseston, zooplankton, a decapod crustacean and four representative species of finfish that differ in trophic status and/or prey selection in Long Island Sound (LIS), a large coastal embayment in the northeastern United States. MeHg biomagnifies in LIS; levels in microseston were 104.2 greater than those in water and 2.3-fold less than zooplankton. MeHg concentrations were related positively to fish length for each species, but often varied considerably among larger individuals. This may be due to differences in the past dietary MeHg exposure of these fish, some of which are migratory. Sedimentary production and mobilization can account for most of the MeHg in microseston of LIS, and by extension, other near-shore locations. Hence, much of the MeHg in higher trophic levels of coastal marine ecosystems, including fishes destined for human consumption, may be attributed to net sedimentary production and dietary bioaccumulation.This study was supported by a STAR grant (R827635) and graduate student fellowship (U91591801) from the U.S. EPA, and the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution, with funding provided by the Doherty Foundation

Converting sporting capacity to entrepreneurial capacity: A process perspective

Managing a personal sporting career and conducting an entrepreneurial initiative are two vitally connected processes. Most athletes require a second career and many engage in entrepreneurship. Research on the similarities and differences of the sports career management process and entrepreneurial process with a special emphasis on the necessary capacities will have a ready audience among practitioners. This study begins the task of closing a surprising gap. In entrepreneurship literature, there is (1) growing research on entrepreneurial process and entrepreneurial capacity as the key driver; (2) strong work in generic, descriptive and explanatory modelling of process as a whole and capacity as a sub-process; and (3) the presence of a generic model of entrepreneurial process based of what distinguishes entrepreneurial capacity from other human capacities. In sports management literature, these research strands are virtually absent. The study indicates how the deficiency might be remedied

Methylmercury cycling in sediments on the continental shelf of southern New England

Author Posting. © The Authors, 2005. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 70 (2006): 918-930, doi:10.1016/j.gca.2005.10.020.Exposure of humans to monomethylmercury (MMHg) occurs primarily through consumption of marine fish, yet there is limited understanding concerning the bioaccumulation and biogeochemistry of MMHg in the biologically productive coastal ocean. We examined the cycling of MMHg in sediments at three locations on the continental shelf of southern New England in September 2003. MMHg in surface sediments is related positively to inorganic Hg (Hg(II)=total Hg-MMHg), the geographical distribution of which is influenced by organic material. Organic matter also largely controls the sediment-water partitioning of Hg species and governs the availability of dissolved Hg(II) for methylation. Potential gross rates of MMHg production, assayed by experimental addition of 200Hg to intact sediment cores, are correlated inversely with the distribution coefficient (KD) of Hg(II) and positively with the concentration of Hg(II), most probably as HgS0, in 0.2-µm filtered pore water of these low-sulfide deposits. Moreover, the efflux of dissolved MMHg to overlying water (i.e., net production at steady state) is correlated with the gross potential rate of MMHg production in surface sediments. These results suggest that the production and efflux of MMHg from coastal marine sediments is limited by Hg(II), loadings of which presumably are principally from atmospheric deposition to this region of the continental shelf. The estimated diffusive flux of MMHg from the shelf sediments averages 9 pmol m-2 d-1. This flux is comparable to that required to sustain the current rate of MMHg accumulation by marine fish, and may be enhanced by the efflux of MMHg from near-shore deposits contaminated more substantially with anthropogenic Hg. Hence, production and subsequent mobilization of MMHg from sediments in the coastal zone may be a major source of MMHg to the ocean and marine biota, including fishes consumed by humans.This research was supported by a STAR student fellowship (U91591801) and grant (R827635) from the U.S. Environmental Protection Agency, a graduate student fellowship and grant from the Hudson River Foundation for Environmental Research, and the Postdoctoral Scholar Program at the Woods Hole Oceanographic Institution, with funding provided by the Doherty Foundation

Mercury contamination and cycling in the coastal zone

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Contribution of the Infection-Associated Complement Regulator-Acquiring Surface Protein 4 (ErpC) to Complement Resistance of \u3cem\u3eBorrelia Burgdorferi\u3c/em\u3e

Borrelia burgdorferi evades complement-mediated killing by interacting with complement regulators through distinct complement regulator-acquiring surface proteins (CRASPs). Here, we extend our analyses to the contribution of CRASP-4 in mediating complement resistance of B. burgdorferi and its interaction with human complement regulators. CRASP-4 (also known as ErpC) was immobilized onto magnetic beads and used to capture proteins from human serum. Following Western blotting, factor H (CFH), CFH-related protein 1 (CFHR1), CFHR2, and CFHR5 were identified as ligands of CRASP-4. To analyze the impact of native CRASP-4 on mediating survival of serum-sensitive cells in human serum, a B. garinii strain was generated that ectopically expresses CRASP-4. CRASP-4-producing bacteria bound CFHR1, CFHR2, and CFHR5 but not CFH. In addition, transformed spirochetes deposited significant amounts of lethal complement components on their surface and were susceptible to human serum, thus indicating that CRASP-4 plays a subordinate role in complement resistance of B. burgdorferi

Contribution of the Infection-Associated Complement Regulator-Acquiring Surface Protein 4 (ErpC) to Complement Resistance of Borrelia burgdorferi

Borrelia burgdorferi evades complement-mediated killing by interacting with complement regulators through distinct complement regulator-acquiring surface proteins (CRASPs). Here, we extend our analyses to the contribution of CRASP-4 in mediating complement resistance of B. burgdorferi and its interaction with human complement regulators. CRASP-4 (also known as ErpC) was immobilized onto magnetic beads and used to capture proteins from human serum. Following Western blotting, factor H (CFH), CFH-related protein 1 (CFHR1), CFHR2, and CFHR5 were identified as ligands of CRASP-4. To analyze the impact of native CRASP-4 on mediating survival of serum-sensitive cells in human serum, a B. garinii strain was generated that ectopically expresses CRASP-4. CRASP-4-producing bacteria bound CFHR1, CFHR2, and CFHR5 but not CFH. In addition, transformed spirochetes deposited significant amounts of lethal complement components on their surface and were susceptible to human serum, thus indicating that CRASP-4 plays a subordinate role in complement resistance of B. burgdorferi

2-Sulfonylpyrimidines as Privileged Warheads for the Development of S. aureus Sortase A Inhibitors

Staphylococcus aureus is one of the most frequent causes of nosocomial and community-acquired infections, with emerging multiresistant isolates causing a significant burden to public health systems. We identified 2-sulfonylpyrimidines as a new class of potent inhibitors against S. aureus sortase A acting by covalent modification of the active site cysteine 184. Series of derivatives were synthesized to derive structure-activity relationship (SAR) with the most potent compounds displaying low micromolar K(I) values. Studies on the inhibition selectivity of homologous cysteine proteases showed that 2-sulfonylpyrimidines reacted efficiently with protonated cysteine residues as found in sortase A, though surprisingly, no reaction occurred with the more nucleophilic cysteine residue from imidazolinium-thiolate dyads of cathepsin-like proteases. By means of enzymatic and chemical kinetics as well as quantum chemical calculations, it could be rationalized that the S ( N )Ar reaction between protonated cysteine residues and 2-sulfonylpyrimidines proceeds in a concerted fashion, and the mechanism involves a ternary transition state with a conjugated base. Molecular docking and enzyme inhibition at variable pH values allowed us to hypothesize that in sortase A this base is represented by the catalytic histidine 120, which could be substantiated by QM model calculation with 4-methylimidazole as histidine analog

Mercury and monomethylmercury in fluids from Sea Cliff submarine hydrothermal field, Gorda Ridge

Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 33 (2006): L17606, doi:10.1029/2006GL026321.Submarine hydrothermal systems are hypothesized to be a potentially important source of monomethylmercury (MMHg) to the ocean, yet the amount of MMHg in vent fluids is unknown. Here, we report total Hg and MMHg concentrations in hydrothermal vent fluids sampled from the Sea Cliff site on the Gorda Ridge. MMHg is the dominant Hg species, and levels of total Hg are enhanced slightly compared to seawater. Hg is enriched in deposits surrounding the site, suggesting near-field deposition from fluid plumes, with rapid MMHg demethylation and scavenging of Hg(II) complexes. Assuming the flux of MMHg from Sea Cliff is representative of global submarine hydrothermal inputs, we estimate a flux of 0.1–0.4 Mmoles y−1, which may be attenuated by scavenging near the vents. However, deep waters are not typically known to be elevated in Hg, and thus we suggest that hydrothermal systems are not significant sources of MMHg to commercial fisheries.WHOI Academic Programs Office, the Penzance Endowed Discretionary Fund, NSF-OCE and EPA-STAR, NOAA-NUR