MC ICP-MS δ(34)S(VCDT) measurement of dissolved sulfate in environmental aqueous samples after matrix separation by means of an anion exchange membrane.

Analysis of (34)S/(32)S of sulfate in rainwater and soil solutions can be seen as a powerful tool for the study of the sulfur cycle. Therefore, it is considered as a useful means, e.g., for amelioration and calibration of ecological or biogeochemical models. Due to several analytical limitations, mainly caused by low sulfate concentration in rainwater, complex matrix of soil solutions, limited sample volume, and high number of samples in ecosystem studies, a straightforward analytical protocol is required to provide accurate S isotopic data on a large set of diverse samples. Therefore, sulfate separation by anion exchange membrane was combined with precise isotopic measurement by multicollector inductively coupled plasma mass spectrometry (MC ICP-MS). The separation method proved to be able to remove quantitatively sulfate from matrix cations (Ca, K, Na, or Li) which is a precondition in order to avoid a matrix-induced analytical bias in the mass spectrometer. Moreover, sulfate exchange on the resin is capable of preconcentrating sulfate from low concentrated solutions (to factor 3 in our protocol). No significant sulfur isotope fractionation was observed during separation and preconcentration. MC ICP-MS operated at edge mass resolution has enabled the direct (34)S/(32)S analysis of sulfate eluted from the membrane, with an expanded uncertainty U (k = 2) down to 0.3 ‰ (a single measurement). The protocol was optimized and validated using different sulfate solutions and different matrix compositions. The optimized method was applied in a study on solute samples retrieved in a beech (Fagus sylvatica) forest in the Vienna Woods. Both rainwater (precipitation and tree throughfall) and soil solution δ (34)SVCDT ranged between 4 and 6 ‰, the ratio in soil solution being slightly lower. The lower ratio indicates that a considerable portion of the atmospherically deposited sulfate is cycled through the organic S pool before being released to the soil solution. Nearly the same trends and variations were observed in soil solution and rainwater δ (34)SVCDT values showing that sulfate adsorption/desorption are not important processes in the studied soil.

Diffusive gradients in thin films measurement of sulfur stable isotope variations in labile soil sulfate.

A diffusive gradient in thin films (DGT) technique, based on a strongly basic anion exchange resin (Amberlite IRA-400), was successfully tested for 34S/32S analysis in labile soil sulfate. Separation of matrix elements (Na, K, and Ca) that potentially cause non-spectral interferences in 34S/32S analysis by MC ICP-MS (multi-collector inductively coupled plasma-mass spectrometry) during sampling of sulfate was demonstrated. No isotopic fractionation caused by diffusion or elution of sulfate was observed below a resin gel disc loading of ≤79 µg S. Above this threshold, fractionation towards 34S was observed. The method was applied to 11 different topsoils and one mineral soil profile (0-100 cm depth) and compared with soil sulfate extraction by water. The S amount and isotopic ratio in DGT-S and water-extractable sulfate correlated significantly (r 2 = 0.89 and r 2 = 0.74 for the 11 topsoils, respectively). The systematically lower 34S/32S isotope ratios of the DGT-S were ascribed to mineralization of organic S.

Novel diffusive gradients in thin films technique to assess labile sulfate in soil.

A novel diffusive gradients in thin films (DGT) technique for sampling labile soil sulfate was developed, based on a strong basic anion exchange resin (Amberlite IRA-400) for sulfate immobilization on the binding gel. For reducing the sulfate background on the resin gels, photopolymerization was applied instead of ammonium persulfate-induced polymerization. Agarose cross-linked polyacrylamide (APA) hydrogels were used as diffusive layer. The sulfate diffusion coefficient in APA gel was determined as 9.83 × 10(-6) ± 0.35 × 10(-6) cm(2) s(-1) at 25 °C. The accumulated sulfate was eluted in 1 mol L(-1) HNO3 with a recovery of 90.9 ± 1.6 %. The developed method was tested against two standard extraction methods for soil sulfate measurement. The obtained low correlation coefficients indicate that DGT and conventional soil test methods assess differential soil sulfate pools, rendering DGT a potentially important tool for measuring labile soil sulfate.

Fractionation of sulfur (S) in beech (Fagus sylvatica) forest soils in relation to distance from the stem base as useful tool for modeling S biogeochemistry.

The investigation of the fractionation of S compounds in forest soils is a powerful tool for interpreting S dynamics and S biogeochemistry in forest ecosystems. Beech stands on high pH (nutrient-rich) sites on Flysch and on low pH (nutrient-poor) sites on Molasse were selected for testing the influence of stemflow, which represents a high input of water and dissolved elements to the soil, on spatial patterns of sulfur (S) fractions. Soil cores were taken at six distances from a beech stem per site at 55 cm uphill and at 27, 55, 100, 150 and 300 cm downhill from the stem. The cores were divided into the mineral soil horizons 0-3, 3-10, 10-20, 20-30 and 30-50 cm. Soil samples were characterized for pH, Corg, pedogenic Al and Fe oxides and S fractions. Sequential extraction by NH4Cl, NH4H2PO4 and HCl yielded readily available sulfate-S (RAS), adsorbed sulfate-S (AS) and HCl-soluble sulfate-S (HCS). Organic sulfur (OS) was estimated as the difference between total sulfur (ToS) and inorganic sulfur (RAS + AS + HCS). Organic sulfur was further divided into ester sulfate-S (ES, HI-reduction) and carbon bonded sulfur (CS). On Flysch, RAS represented 3-6%, AS 2-12%, HCS 0-8% and OS 81-95% of ToS. On Molasse, RAS amounted 1-6%, AS 1-60%, HCS 0-8% and OS 37-95% of ToS. Spatial S distribution patterns with respect to the distance from the tree stem base could be clearly observed at all investigated sites. The presented data is a contribution to current reports on negative input-output S budgets of forest watersheds, suggesting that mineralization of OS on nutrient rich soils and desorption of historic AS on nutrient-poor soils are the dominant S sources, which have to be considered in future modeling of sulfur.

The performance of single and multi-collector ICP-MS instruments for fast and reliable 34S/32S isotope ratio measurements.

The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3-0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%).