Fractionation of the stable silicon isotopes analytical method developments and selected applications in geochemistry

Abstract: During the last few decades, variations in the 'natural' isotopic abundances of stable elements (termed 'fractionation') have received considerable interest from the scientific community. Though analytical methods and techniques for the measurement of isotopic abundances with adequate figures of merit have been available for light elements (e.g. B, C, N and O) for some time, and the wealth of data produced has secured maturity status for such applications, relatively modest progress in fractionation studies devoted to high-mass elements has been made until recently, mainly because of constraints of the available analytical techniques. The situation has changed drastically with the advent of multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS), with the number of reports about natural fractionation of Fe, Cu, Zn, Mo, Cd, Sn increasing exponentially during the recent years. In spite of the high Si abundance in nature and the importance of the element in many areas of the Earth sciences (focusing on e.g. weathering, the global Si cycle, paleoclimate studies, paleoceanography, and biological uptake), the available information on Si isotope fractionation remains rather limited due to the laborious and hazardous chemical purification procedures associated with the analyses. The focus of this thesis was the development of analytical methods for the precise and accurate measurements of Si isotope ratios, which is an absolute requirement for meaningful fractionation studies, in various matrices. This work involved detailed studies on sample preparation (including matrix separation) and refining the measurement protocol by using high resolution MC-ICP-MS. In the former stages, quantitative analyte recovery, thorough control of contamination levels and purification efficiency were the major targets, while severe spectral interferences and the need for adequate instrumental mass bias corrections challenged the latter. The performance of the method was tested in the first inter- laboratory performance assessment study of its kind with good results. As limited examples of applications, studies on Si isotope fractionation in aqueous, plant and humus samples were performed utilizing methods developed. The efficient analyte separation, high-resolution capability of the instrument, quantitative Si recovery and accurate mass bias correction using Mg as internal standard, allowed the determination of the Si isotopic composition of natural waters and biological samples with long-term reproducibility, expressed as twice the standard deviation (2σ), equal to or less than 0.10‰ for δ29Si and 0.25‰ for δ30Si. Furthermore, the presence of a challenging spectral interference on 29Si originating from 28SiH+ was revealed during this study, indicating that instrumental resolution in excess of 3500 is required for interference-free Si isotopic analyses. However, despite complete removal of N-, O-, and C-containing interferences appearing on the high-mass side of the Si isotopes, it was found that exact matching of both the acid matrix and the Si concentration are mandatory due to tailing from the abundant 14N16O+ interference on 30Si. This thesis also includes results from the first study of the Si isotopic homogeneity of major biomass components from a defined area in Northern Sweden covered by boreal forest. Since the potential impact of vegetation on the terrestrial biogeochemical cycle has attracted considerable interest, thorough characterization of the Si isotopic composition of the biomass potentially allows the utilization of this isotope system in the assessment of the relative contributions of biogenic and mineral silica in plants, soil solutions and natural waters (including fresh-, brackish- and marine waters). Isotopic analyses of the biological materials yielded a surprisingly homogenous silicon isotopic composition (relative to the NBS28 Si reference material), expressed as δ29Si (2σ), ranging from (- 0.14 ± 0.05)‰ to (0.13 ± 0.04)‰ Furthermore, elemental and isotopic analysis of local airborne particulate matter suggests that vegetation also accumulates silica via incorporation of exogenous Si containing primary and secondary minerals (in addition to root uptake of non-ionic silicic acid), a fact that has been neglected in previously published studies. This strongly indicates that the presence of potential surface contributions must be considered during in situ silicon uptake studies