The cation-exchange purification technique used here does not remove anions (in our case, mostly Cl-, SO 4 2-and to a lesser extent NO 3-) from solutions. In this case, the addition of a known artificial matrix in excess in both the sample and standard solution can be used to dilute the natural concentration of the contaminant and to homogenize sample and standard matrices (doping method, Georg et al., 2006; Hughes et al., 2011). Indeed, dissimilar matrices will affect differently the plasma and ionization efficiency and will induce artificial bias in the delta measurements, invalidating the use of the standard-sample bracketing technique. In our samples, Cl-originating from seawater can be neglected compared to Cladded as HCl (Merck Suprapur) to dissolve the brucite; and as solutions were analyzed in a HCl matrix largely in excess (up to 0.5 mol L-1) compared to natural Cl-concentration. Similarly, the occurrence of NO 3-in seawater was resolved by the use of HNO 3 (Merck Suprapur, 0.5 mol L-1) as a solvent in both the samples and standards. For Depth Depth (m) (m)

Mercury speciation analysis in soil samples by ion chromatography, post-column cold vapor generation and inductively coupled plasma mass spectrometry

An internal standard (IS) can be used to account for moderate, matrix-related shifts in mass bias using multi-collector inductively coupled plasma mass spectrometry through the empirical, linear relationship between measured isotope abundance ratios for different elements in ln-ln space. Unfortunately, erroneous mass bias corrected isotope abundance ratios may be returned by the model, requiring artificial adjustment of the true isotope abundance ratio of the IS. Although inadequate correction for peak tailing has been convincingly used to explain this problem, our analysis of the literature describing the development of the mass bias correction model using an IS reveals the presence of a source of systematic error. The origin of this error is purely mathematical and is eliminated in the revised model presented, in which mass bias corrected isotope abundance ratios are independent of the isotopic composition of the IS. An expression for computing the total combined uncertainty in the corrected ratio, incorporating contributions from the linear model, the isotopic reference material, and measurements of analyte element and IS in the sample, is also derived.

Changes in the analytical performance of double focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) caused by addition of methane to the argon gas ICP were studied for approximately 100 isotopes of 70 elements. The parameters under consideration included instrumental background, analyte sensitivity, precision and formation of spectral interferences as functions of methane flow added to the sample gas. It was shown that for many analytes the capabilities of ICP-SFMS significantly improve by virtue of enhanced sensitivity and reduction of polyatomic interferences. In contrast to quadrupole-based ICP-MS, these gains in instrumental performance do not compromise multi-element capabilities given that the amount of methane is carefully optimized. The accuracy of the results for the determination of 50 elements in water samples was evaluated using the certified reference materials SLRS-4 and SLEW-2.

Various stages of an analytical method for high-precision cadmium (Cd) isotope ratio measurements by MC-ICP-MS (sample preparation, matrix separation, instrumental analysis and data evaluation) were critically evaluated and optimized for the processing of carbon-rich environmental samples. Overall reproducibility of the method was assessed by replicate preparation and Cd isotope ratio measurements in various environmental matrices (soil, sediment, Fe-Mn nodules, sludge, kidney, liver, leaves) and was found to be better than 0.1& (2s for d 114 Cd/ 110 Cd) for the majority of samples. Cd isotope ratio data for several commercially-available reference materials are presented and compared with previously published results where available. The method was used in a pilot study focusing on the assessment of factors affecting Cd isotope composition in tree leaves. A summary of results obtained for a large number (n > 80) of birch (Betula pubescenes) leaves collected from different locations in Sweden and through the entire growing season is presented and potential reasons for observed variability in Cd isotope composition are discussed. Seasonal dynamics of element concentrations and isotope compositions in leaves were also compared for Os, Pb, Zn and Cd.