Katharina Kreissig

A new separation procedure for Cu prior to stable isotope analysis by MC-ICP-MS

A novel ion exchange chromatography was developed for the separation of Cu from biological samples prior to stable isotope analyses. In contrast to previous methods, the new technique makes use of the different distribution coefficients of Cu(I) and Cu(II) to anion exchange resin and this helps to significantly improve the purity of the Cu separates obtained from biological samples, whilst maintaining crucial quantitative yields. Careful method validation confirmed that the procedure yields sufficiently pure Cu fractions after a single pass through the anion exchange columns, with a recovery of 100 ± 2%. Subsequent isotopic analyses of the Cu by multi-collector inductively coupled plasma mass spectrometry, using admixed Ni for mass bias correction, produced accurate Cu stable isotope data with a reproducibility of ±0.04‰ for pure standard solutions and of ±0.15‰ for samples of biological origin.

Tracing anthropogenic thallium in soil using stable isotope compositions

Thallium stable isotope data are used in this study, for the first time, to apportion Tl contamination in soils. In the late 1970s, a cement plant near Lengerich, Germany, emitted cement kiln dust (CKD) with high Tl contents, due to cocombustion of Tl-enriched pyrite roasting waste. Locally contaminated soil profiles were obtained down to 1 m depth and the samples are in accord with a binary mixing relationship in a diagram of Tl isotope compositions (expressed as ε(205)Tl, the deviation of the (205)Tl/(203)Tl ratio of a sample from the NIST SRM 997 Tl isotope standard in parts per 10(4)) versus 1/[Tl]. The inferred mixing endmembers are the geogenic background, as defined by isotopically light soils at depth (ε(205)Tl ≈ -4), and the Tl emissions, which produce Tl-enriched topsoils with ε(205)Tl as high as ±0. The latter interpretation is supported by analyses of the CKD, which is also characterized by ε(205)Tl ≈ ± 0, and the same ε(205)Tl value was found for a pyrite from the deposit that produced the cocombusted pyrite roasting waste. Additional measurements for samples from a locality in China, with outcrops of Tl sulfide mineralization and associated high natural Tl backgrounds, reveal significant isotope fractionation between soils (ε(205)Tl ≈ +0.4) and locally grown green cabbage (ε(205)Tl between -2.5 and -5.4). This demonstrates that biological isotope fractionation cannot explain the isotopically heavy Tl in the Lengerich topsoils and the latter are therefore clearly due to anthropogenic Tl emissions from cement processing. Our results thus establish that isotopic data can reinforce receptor modeling for the toxic trace metal Tl.

Stable isotope ratio measurements of Cu and Zn in mineral dust (bulk and size fractions) from the Taklimakan Desert and the Sahel and in aerosols from the eastern tropical North Atlantic Ocean

Accurate characterization of the stable isotope composition of Cu and Zn in major global mineral dust sources and in aerosols is central to the application of these isotope systems to the studies of global geochemical processes and cycles. We test here for the first time Cu and Zn isotope ratios within a well-defined source-receptor setting on the continent-ocean interface and determine the isotope composition of (i) bulk surface soil dust samples from the Sahel region, (ii) individual size fractions of surface dust samples from the Taklimakan Desert, and (iii) aerosols collected in the equatorial eastern North Atlantic region. This is achieved reducing the blank contribution during the ion exchange step using small resin and acid volumes and using a second ion exchange passage to purify the Cu fraction. We find no significant correlation between size fractions and isotope ratios in the two samples analyzed from the Taklimakan Desert. Mass balance calculations suggest that isotope ratios of bulk samples are within the analytical precision of the <4 μm size fraction and can be used to characterize atmospheric long range transport of Cu and Zn in mineral dust from the Taklimakan Desert. The <1 µm size fractions of two aerosol samples collected over the equatorial eastern North Atlantic region have Cu and Zn isotope ratios that are different to Sahel surface soil dust suggesting important non-crustal sources, in line with calculated enrichment factors, and possibly of anthropogenic origin. Using previously reported δ(66)Zn values for anthropogenic emission from Europe, preliminary calculations suggest that up to 55% of Zn arriving at the sampling points in the equatorial eastern North Atlantic region could be of anthropogenic origin.

Cadmium Isotope Fractionation in Soil–Wheat Systems

Analyses of stable metal isotope ratios constitute a novel tool in order to improve our understanding of biogeochemical processes in soil-plant systems. In this study, we used such measurements to assess Cd uptake and transport in wheat grown on three agricultural soils under controlled conditions. Isotope ratios of Cd were determined in the bulk C and A horizons, in the Ca(NO3)2-extractable Cd soil pool, and in roots, straw, and grains. The Ca(NO3)2-extractable Cd was isotopically heavier than the Cd in the bulk A horizon (Δ(114/110)Cdextract-Ahorizon = 0.16 to 0.45‰). The wheat plants were slightly enriched in light isotopes relative to the Ca(NO3)2-extractable Cd or showed no significant difference (Δ(114/110)Cdwheat-extract = -0.21 to 0.03‰). Among the plant parts, Cd isotopes were markedly fractionated: straw was isotopically heavier than roots (Δ(114/110)Cdstraw-root = 0.21 to 0.41‰), and grains were heavier than straw (Δ(114/110)Cdgrain-straw = 0.10 to 0.51‰). We suggest that the enrichment of heavy isotopes in the wheat grains was caused by mechanisms avoiding the accumulation of Cd in grains, such as the chelation of light Cd isotopes by thiol-containing peptides in roots and straw. These results demonstrate that Cd isotopes are significantly and systematically fractionated in soil-wheat systems, and the fractionation patterns provide information on the biogeochemical processes in these systems.

Improvements in Cd stable isotope analysis achieved through use of liquid–liquid extraction to remove organic residues from Cd separates obtained by extraction chromatography

During isotopic analysis of Cd by MC-ICP-MS, organic resin residue can perturb instrumental mass fractionation. These organic compounds can be removed by a liquid–liquid extraction procedure using heptane.

Thallium geochemistry in the metamorphic Lengenbach sulfide deposit, Switzerland: Thallium-isotope fractionation in a sulfide melt

Abstract The Lengenbach (Switzerland) Pb-As-Tl-Zn deposit was formed from a sulfide melt at about 500 °C during Alpine metamorphism, but details on its formation and especially the source of the metals are still under debate. In this study we present two sample sets to address these questions: (1) MC-ICP-MS analyses of thallium isotopes in sulfides, sulfosalts, and melt inclusions from the Alpine metamorphic Lengenbach deposit in the Binn Valley of Switzerland, the non-metamorphic Wiesloch Mississippi Valley-type deposit in Southern Germany, and the Cu- and As-rich mineralization at Pizzo Cervandone about 2 km SW of the Lengenbach deposit, which has been discussed as potential source of the Lengenbach metals. (2) LA-ICP-MS analyses of micas from the Lengenbach deposit and surrounding country rocks between the deposit and the Pizzo Cervandone to trace potential metal-bearing fluid pathways. We found that Tl isotope compositions expressed as ε205Tl values in all investigated samples range from -4.1 ± 0.5 to +1.9 ± 0.5. The whole variation can be seen in the Lengenbach deposit alone, which hence records considerable fractionation even during high-temperature processes involving a sulfide melt. This large range of ε205Tl is thought to be caused by nuclear volume-dependent fractionation. Interestingly, the common fahlores at Lengenbach behave differently from all other investigated sulfosalts: based on their heavy isotopic composition together with a low As/S-ratio, they do not seem to be crystallized from the sulfide melt, but are interpreted to have formed from hydrothermal fluids enriched in the heavy Tl isotopes. Although As mobilization in the gneisses and dolomites surrounding the Lengenbach deposit is evident based on secondary arsenites, no traces of such a country rock fluid could be found in fissure micas at Lengenbach. Hence, considerations involving K/Rb, Rb/Tl, As/S, and Pb/Tl ratios in the sulfides and micas imply that the element enrichment in the Lengenbach deposit is either pre-Alpine or related to peak metamorphism, but occurred definitely before mica growth at Lengenbach.

High precision 142Ce/140Ce stable isotope measurements of purified materials with a focus on CeO2 nanoparticles

Engineered CeO2 nanoparticles (NPs) are becoming increasingly prevalent in consumer products and this has raised concerns about the unknown behaviour and fate of such materials in the environment. Analytical limitations have hampered the detection of CeO2 NPs in natural systems at environmentally relevant levels. This study presents data on the inherent stable isotope composition of commercially available purified Ce materials with a particular focus on CeO2 NPs. The aim of this investigation is to determine whether CeO2 NPs posses a distinct isotopic signature that may be exploited for their detection in natural systems. To achieve this, suitable stable isotope measurement protocols were developed for the precise determination of the 142Ce/140Ce isotope ratio by multiple collector ICP-MS using Ba for external normalisation of the instrumental mass bias. The data presented show that precisions of ±0.01‰ (2se) and ±0.04‰ (2sd) can be routinely achieved with these techniques. The results also demonstrate that commercially available CeO2 NPs do not have a distinct Ce isotope composition that may be exploited for the purpose of stable isotope tracing.

Fate of Cd in Agricultural Soils : A Stable Isotope Approach to Anthropogenic Impact, Soil Formation, and Soil-Plant Cycling

The application of mineral phosphate (P) fertilizers leads to an unintended Cd input into agricultural systems, which might affect soil fertility and quality of crops. The Cd fluxes at three arable sites in Switzerland were determined by a detailed analysis of all inputs (atmospheric deposition, mineral P fertilizers, manure, and weathering) and outputs (seepage water, wheat and barley harvest) during one hydrological year. The most important inputs were mineral P fertilizers (0.49 to 0.57 g Cd ha-1 yr-1) and manure (0.20 to 0.91 g Cd ha-1 yr-1). Mass balances revealed net Cd losses for cultivation of wheat (-0.01 to -0.49 g Cd ha-1 yr-1) but net accumulations for that of barley (+0.18 to +0.71 g Cd ha-1 yr-1). To trace Cd sources and redistribution processes in the soils, we used natural variations in the Cd stable isotope compositions. Cadmium in seepage water (δ114/110Cd = 0.39 to 0.79‰) and plant harvest (0.27 to 0.94‰) was isotopically heavier than in soil (-0.21 to 0.14‰). Consequently, parent material weathering shifted bulk soil isotope compositions to lighter signals following a Rayleigh fractionation process (ε ≈ 0.16). Furthermore, soil-plant cycling extracted isotopically heavy Cd from the subsoil and moved it to the topsoil. These long-term processes and not anthropogenic inputs determined the Cd distribution in our soils.

Neodymium isotope analyses after combined extraction of actinide and lanthanide elements from seawater and deep‐sea coral aragonite

Isotopes of the actinide elements protactinium (Pa), thorium (Th), and uranium (U), and the lanthanide element neodymium (Nd) are often used as complementary tracers of modern and past oceanic processes. The extraction of such elements from low abundance matrices, such as seawater and carbonate, is however labor-intensive and requires significant amounts of sample material. We here present a combined method for the extraction of Pa, Th, and Nd from 5 to 10 L seawater samples, and of U, Th, and Nd from <1 g carbonate samples. Neodymium is collected in the respective wash fractions of Pa-Th and U-Th anion exchange chromatographies. Regardless of the original sample matrix, Nd is extracted during a two-stage ion chromatography, followed by thermal ionization mass spectrometry (TIMS) analysis as NdO+. Using this combined procedure, we obtained results for Nd isotopic compositions on two GEOTRACES consensus samples from Bermuda Atlantic Time Series (BATS), which are within error identical to results for separately sampled and processed dedicated Nd samples (e_(Nd) = −9.20 ± 0.21 and −13.11 ± 0.21 for 15 and 2000 m water depths, respectively; intercalibration results from 14 laboratories: e_(Nd) = −9.19 ± 0.57 and −13.14 ± 0.57). Furthermore, Nd isotope results for an in-house coral reference material are identical within analytical uncertainty for dedicated Nd chemistry and after collection of Nd from U-Th anion exchange chromatography. Our procedure does not require major adaptations to independently used ion exchange chromatographies for U-Pa-Th and Nd, and can hence be readily implemented for a wide range of applications.