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A sorbent L-cysteine grafted silica gel has been evaluated for separation and enrichment of dissolved inorganic i-Hg(II) and methylmercury CH3Hg(I) from surface waters at sub-µg L−1 concentrations. Chemical parameters for mercury species enrichment and separation have been optimized. Analytical schemes for the determination of Hg species, using selective column solid phase extraction (SPE) with continuous flow chemical vapor generation atomic absorption spectrometry (CF-CVG-AAS) or inductively coupled plasma-mass spectrometry (ICP-MS) were developed. Possibilities for on-site SPE enrichment were demonstrated as well. The limits of quantification were 1.5 and 5 ng L−1 for dissolved i-Hg(II) and CH3Hg(I) by CF-CVG-AAS and 1 and 2.5 ng L−1 by ICP-MS with relative standard deviations between 7–12% and 7–14%, respectively. The chemically modified SPE sorbent has demonstrated high regeneration ability, chemical and mechanical stability, acceptable capacity and good enrichment factors. Results for total dissolved mercury were in reasonable agreement with those from independent analyses by direct ICP-MS determinations for river waters and for estuarine water certified reference material. <alternatives> [...] </alternatives>
 European Union Directive 2008/105/EC of the European Parliament and of the Council of 16 December 2008 on environmental quality standards in the field of water policy, amending and subsequently repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/280/EEC and amending Directive 2000/60/EC of the European Parliament and of the Council. OJEU 348, 84 (2008)
 European Union Commission directive 2009/90/EC of 31 July 2009 laying down, pursuant to Directive 2000/60/EC of the European Parliament and of the Council, technical specifications for chemical analysis and monitoring of water status. OJEU 201, 36 (2009)
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