Field sampling and flow injection strategies for trace analysis and element speciation.

Over the last two decades research has shown that the different forms of trace elements in the environment can cause a variety of health concerns as a result of differences in toxicity. The need to establish efficient, effective and reliable speciation methods has become paramount. A basic aim of this work has been to advance speciation measurement capability for key trace elements (mercury, lead and chromium) by devising an integrated analytical approach that links the sample collection, sample preservation and laboratory measurements in an unified manner.An introductory chapter first reviews the occurrence of organometallic compounds in the environment and focuses on the identification of the "environmental compartments" where transformations of such species can take place. Speciation studies also assist in understanding the biogeochemical cycling of trace elements. Moreover, a review of the various methodologies used for trace element speciation measurements including hyphenated techniques and/or a variety of chemical/physical pretreatments in combination with flow injection (FI) is discussed.Chapter 2 describes mercury speciation experiments utilising gas chromatography-microwave induced plasma-atomic emission spectrometry (GC-MIP-AES) and FI. The approach was based on the preconcentration of mercury on sulphydryl cotton and after elution from the microcolumn, separation and quantitation of methyl-, ethyl- and inorganic mercury species. Method development experiments were performed using a derivatisation technique which gave low contamination and allowed rapid analysis of samples. The microcolumn technique was transferred to the field and speciation of mercury in surface waters of the Manchester Ship Canal was undertaken and high methylmercury concentrations (0.052-0.182 ug 1 -1, as Hg) were detected. In so doing the new approach offered the preservation of the natural speciation state of the water sample directly at the sampling site and during the interval between collection and analysis.In chapter 3 lead studies are centred on the development of a rapid speciation scheme for neutral and cationic (organic and inorganic) lead species based on activated alumina microcolumn separation in combination with ICP-MS and FI. The approach permitted rapid assessment of the nature of lead contamination in environmental waters. Speciation of lead in surface waters of the Manchester Ship Canal was also undertaken using the field sampling approach in an attempt to confirm a transmethyllation reaction between organolead and inorganic mercury.A further application for microcolumns, in the context of speciation measurement, is their use as external calibrants and certified reference materials (CRMs) and this is discussed in the penultimate chapter. Key elements were mercury and chromium. After immobilisation of mercury species on SCF microcolumns it was found that recoveries for methyl- and inorganic mercury were quantitative over 4 months in contrast to ethylmercury which was 2 months. Similar studies for chromium species indicated ineffective elution and more vigorous conditions (microwave assisted digestion) for the elution step were used.A final chapter reviews progress and recommendations are given concerning future research and application for microcolumn field sampling in combination with instrumental analytical techniques.