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    Replacement and authigenic mineralogy of metal contaminants in stream and estuarine sediments at Newtownards, Northern Ireland
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    Abstract:
    Tidal mudflats are locally enriched in heavy metals at the head of Strangford Lough in Northern Ireland, where drainage from the hinterland enters the sea lough via a tidal canal in an urban area. To characterize the metallic contaminants and investigate their provenance, heavy particles separated from stream, canal and estuarine sediments were analysed by electron microprobe and laser Raman microspectroscopic methods. Potential metal sources are mineralization in the catchment area and industrial or domestic pollution. Anthropogenic particles include metallic grains, alloys and compounds of Pb, Zn, Cu, Fe, Cr and Sn. Alteration of metallic particles includes de-zincification of brass in freshwater sediment and replacement of Cu wire by covellite in brackish to marine sediment. Mobility of Cu, Fe and S in canal and estuarine sediments is indicated by the authigenic growth of framboidal Fe sulphide on oxide substrates and of chalcopyrite rims on covellite. Intricate colloform and platy crystalline textures suggest a cyclical deposition of covellite and chalcopyrite under conditions of varying redox and salinity. Lead and Cr mobility in the contaminated estuarine sediment is shown by the authigenic formation on Pb-rich substrates of heterogeneous Pb- and Cr-rich sulphate-phosphate compounds and Pb-oxychlorides.
    Keywords:
    Authigenic
    Covellite
    Abstract Acid volatile sulfide (AVS) is a component of sediments that complexes some cationic metals and thereby influences the toxicity of these metals to benthic organisms. Experimental manipulation of AVS in metal-contaminated sediments may provide a means to neutralize toxicity due to metals and thereby help assess the cause of sediment toxicity. This study evaluated the effect of spiking FeS, Na2S, and Na2S/FeSO4 combined on the concentration of AVS, simultaneously extracted metals (SEM), and pore-water metals in uncontaminated and metal-enriched sediments. Experiments with solid FeS showed comparatively low effectiveness in increasing AVS. Spiking with either Na2S or Na2 S/FeSO4 combined increased AVS and/or reduced SEM metal in Cd-, Zn-, and Ni-spiked sediments and in a Cu-contaminated sediment collected from the field. Spiking with Na2S/FeSO4 caused marked reductions in dissolved metal concentrations in the pore waters of these sediments; spiking with Na2S alone caused an apparent elevation in pore-water (Cu) metal that we believe is an artifact of metal sulfide formation in the filtered pore water. When the Na2S/FeSO4 treatment was evaluated under conditions simulating those in sediment toxicity tests, alterations of AVS/SEM were nearly quantitative, except for Ni-spiked sediment, which showed lower efficiency than the Cd, Zn, or Cu sediments. It appears that AVS spiking holds promise for the experimental manipulation of metal toxicity in sediments.
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    Acid volatile sulfide (AVS) is a component of sediments that complexes some cationic metals and thereby influences the toxicity of these metals to benthic organisms. Experimental manipulation of AVS in metal-contaminated sediments may provide a means to neutralize toxicity due to metals and thereby help assess the cause of sediment toxicity. This study evaluated the effect of spiking FeS, Na2S, and Na2S/FeSO4 combined on the concentration of AVS, simultaneously extracted metals (SEM), and pore-water metals in uncontaminated and metal-enriched sediments. Experiments with solid FeS showed comparatively low effectiveness in increasing AVS. Spiking with either Na2S or Na2 S/FeSO4 combined increased AVS and/or reduced SEM metal in Cd-, Zn-, and Ni-spiked sediments and in a Cu-contaminated sediment collected from the field. Spiking with Na2S/FeSO4 caused marked reductions in dissolved metal concentrations in the pore waters of these sediments; spiking with Na2S alone caused an apparent elevation in pore-water (Cu) metal that we believe is an artifact of metal sulfide formation in the filtered pore water. When the Na2S/FeSO4 treatment was evaluated under conditions simulating those in sediment toxicity tests, alterations of AVS/SEM were nearly quantitative, except for Ni-spiked sediment, which showed lower efficiency than the Cd, Zn, or Cu sediments. It appears that AVS spiking holds promise for the experimental manipulation of metal toxicity in sediments.
    Metal Toxicity