Zinc Supply Affects Cadmium Uptake and Translocation in the Hyperaccumulator Sedum Plumbizincicola as Evidenced by Isotope Fractionation.

This study employs stable isotope analysis to investigate the mechanisms of cadmium (Cd) and zinc (Zn) interaction in the metal hyperaccumulating plant species Sedum plumbizincicola. To this end, the Cd and Zn isotope compositions of root, stem, leaf, and xylem sap samples were determined during metal uptake and translocation at different Cd and Zn concentrations. The enrichment of light isotopes of both elements in plants during uptake was less pronounced at low metal supply levels, likely reflecting the switch from a low-affinity to a high-affinity transport system at lower levels of external metal supply. The lower δ114/110Cd values of xylem sap when treated with a metabolic inhibitor decreasing the active Cd uptake further supports the preference of heavier Cd isotopes during high-affinity transport. The Δ66Znplant-initial solution or Δ66Znplant-final solution values were similar at different Cd concentrations, indicating negligible interaction of Cd in the Zn uptake process. However, decreasing Zn supply levels significantly increased the enrichment of light Cd isotopes in plants (Δ114/110Cd = -0.08‰) in low-Cd treatments but reduced the enrichment of light Cd isotopes in plants (Δ114/110Cd = 0.08‰) under high Cd conditions. A systematic enrichment of heavy Cd and light Zn isotopes was found in root-to-shoot translocation of the metals. The Cd concentrations of the growth solutions thereby had no significant impact on Zn isotope fractionation during root-to-shoot translocation. However, the Δ114/110Cdtranslocation values hint at possible competition between Cd and Zn for transporters during root-to-shoot transfer and this may impact the transport pathway of Cd. The stable isotope data demonstrate that the interactions between the two metals influenced the uptake and transport mechanisms of Cd in S. plumbizincicola but had little effect on those of Zn.

An investigation of zinc isotope fractionation in cacao (Theobroma cacao L.) and comparison of zinc and cadmium isotope compositions in hydroponic plant systems under high cadmium stress.

This study aims to establish whether zinc (Zn) and cadmium (Cd) share similar physiological mechanisms for uptake and translocation in cacao plants (Theobroma cacao L.). Multiple-collector ICP-MS was used to determine the Zn stable isotope compositions in the roots, stems and leaves of 19 diverse cacao genotypes grown in hydroponics with 20 µmol L-1 CdCl2. Additional plants of one genotype were grown in hydroponic solutions containing lower Cd concentrations (0 and 5 µmol L-1 added CdCl2). Regardless of the Cd concentration used in the exposures, the Zn stable isotope compositions show the same systematic patterns in plant organs, with δ66Znroot > δ66Znstem > δ66Znleaf (δ66Zn denotes relative differences in 66Zn/64Zn ratios in parts per thousand). The mean Zn stable isotope fractionation between the plants and the hydroponic solutions was ε66Znuptake = -1.15 ± 0.36‰ (2SD), indicating preferential uptake of isotopically light Zn by plants from the hydroponic solution. The mean  stable isotope fractionation factor associated with translocation of Zn from roots to shoots, ε66Znseq-mob = + 0.52 ± 0.36‰ (2SD), shows that isotopically heavy Zn is preferentially sequestered in the cacao roots, whilst isotopically light Zn is mobilised to the leaves. A comparison with the Cd stable isotope compositions of the same plants shows that both isotopically light Zn and Cd are preferentially taken up by cacao plants. In contrast to Zn, however, the cacao roots retain isotopically light Cd and transfer isotopically heavy Cd to the leaves.

Nucleosynthetic isotope anomalies of zinc in meteorites constrain the origin of Earth's volatiles.

Material inherited from different nucleosynthesis sources imparts distinct isotopic signatures to meteorites and terrestrial planets. These nucleosynthetic isotope anomalies have been used to constrain the origins of material that formed Earth. However, anomalies have only been identified for elements with high condensation temperatures, leaving the origin of Earth's volatile elements unconstrained. We determined the isotope composition of the moderately volatile element zinc in 18 bulk meteorites and identified nucleosynthetic zinc isotope anomalies. Using a mass-balance model, we find that carbonaceous bodies, which likely formed beyond the orbit of Jupiter, delivered about half of Earth's zinc inventory. Combined with previous constraints obtained from studies of other elements, these results indicate that ~10% of Earth's mass was provided by carbonaceous material.

Zinc stable isotope analysis reveals Zn dyshomeostasis in benign tumours, breast cancer, and adjacent histologically normal tissue.

The disruption of Zn homeostasis has been linked with breast cancer development and progression. To enhance our understanding of changes in Zn homeostasis both inside and around the tumour microenvironment, Zn concentrations and isotopic compositions (δ66Zn) were determined in benign (BT) and malignant (MT) tumours, healthy tissue from reduction mammoplasty (HT), and histologically normal tissue adjacent to benign (NAT(BT)) and malignant tumours (NAT(MT)). Mean Zn concentrations in NAT(BT) are 5.5 µg g-1 greater than in NAT(MT) (p = 0.00056) and 5.1 µg g-1 greater than in HT (p = 0.0026). Zinc concentrations in MT are 12.9 µg g-1 greater than in HT (p = 0.00012) and 13.3 µg g-1 greater than in NAT(MT) (p < 0.0001), whereas δ66Zn is 0.17‰ lower in MT than HT (p = 0.017). Benign tumour Zn concentrations are also elevated compared to HT (p = 0.00013), but are not significantly elevated compared to NAT(BT) (p = 0.32). The δ66Zn of BT is 0.15‰ lower than in NAT(BT) (p = 0.045). The similar light δ66Zn of BT and MT compared to HT and NAT may be related to the isotopic compensation of increased metallothionein (64Zn-rich) expression by activated matrix metalloproteinase (66Zn-rich) in MT, and indicates a resultant 66Zn-rich reservoir may exist in patients with breast tumours. Zinc isotopic compositions thus show promise as a potential diagnostic tool for the detection of breast tumours. The revealed differences of Zn accumulation in healthy and tumour-adjacent tissues require additional investigation.

Characterisation and chemometric evaluation of 17 elements in ten seaweed species from Greenland.

Several Greenland seaweed species have potential as foods or food ingredients, both for local consumption and export. However, knowledge regarding their content of beneficial and deleterious elements on a species specific and geographical basis is lacking. This study investigated the content of 17 elements (As, Ca, Cd, Cr, Cu, Fe, Hg, I, K, Mg, Mn, Na, Ni, P, Pb, Se and Zn) in 77 samples of ten species (Agarum clathratum, Alaria esculenta, Ascophyllum nodosum, Fucus distichus, Fucus vesiculosus, Hedophyllum nigripes, Laminaria solidungula, Palmaria palmata, Saccharina latissima and Saccharina longicruris). Element profiles differed between species but showed similar patterns within the same family. For five species, different thallus parts were investigated separately, and showed different element profiles. A geographic origin comparison of Fucus species indicated regional differences. The seaweeds investigated were especially good sources of macrominerals (K > Na > Ca > Mg) and trace minerals, such as Fe. Iodine contents were high, especially in macroalgae of the family Laminariaceae. None of the samples exceeded the EU maximum levels for Cd, Hg or Pb, but some exceeded the stricter French regulations, especially for Cd and I. In conclusion, these ten species are promising food items.

Evaluation of Optimized Procedures for High-Precision Lead Isotope Analyses of Seawater by Multiple Collector Inductively Coupled Plasma Mass Spectrometry.

The application of Pb isotopes to marine geochemistry is currently hindered by challenges associated with the analysis of Pb isotopes in seawater. The current study evaluates the performance of multiple collector inductively coupled plasma mass spectrometry (MC-ICP-MS) measurements of seawater Pb isotope compositions following Pb separation by either solid-phase extraction with Nobias Chelate PA-1 resin or coprecipitation with Mg(OH)2 and using either a Pb double spike or external normalization to Tl for mass bias correction. The four analytical combinations achieve results of similar quality when measuring 1-7 ng of seawater Pb, with reproducibilities (two standard deviations, 2SD) of 100-1200 ppm for 206Pb/207Pb and 208Pb/207Pb and 300-1700 ppm for ratios involving the minor 204Pb isotope. All four procedures enable significantly improved sample throughput compared to an established thermal ionization mass spectrometry (TIMS) double-spike method and produce unbiased seawater Pb isotope compositions with similar or improved precision. Nobias extraction is preferable to coprecipitation due to its greater analytical throughput and suitability for analyses of large seawater samples with high Si(OH)4 contents. The most accurate Pb isotope data are produced following Nobias extraction and double-spike correction as such analyses are least susceptible to matrix effects. However, Nobias extraction with Tl normalization constitutes an attractive alternative as, unlike the double-spike procedure, only a single mass spectrometric measurement is required, which improves analytical throughput and optimizes Pb consumption for analysis. Despite the advantages of solid-phase extraction, coprecipitation represents a useful Pb separation technique for samples with low to moderate Si contents as it is inexpensive, simple to implement, and the data are only marginally less accurate, especially when combined with a Pb double spike for mass bias correction.

Cadmium isotope fractionation in the soil - cacao systems of Ecuador: a pilot field study.

The often high Cd concentrations of cacao beans are a serious concern for producers in Latin America due to the implementation of stricter Cd limits for cocoa products by the European Union in 2019. This is the first investigation to employ coupled Cd isotope and concentration measurements to study soil - cacao systems. Analyses were carried out for 29 samples of soils, soil amendments and cacao tree organs from organic farms in Ecuador that harvest three distinct cacao cultivars. The majority of soils from 0-80 cm depth have very similar δ114/110Cd of about -0.1‰ to 0‰. Two 0-5 cm topsoils, however, have high Cd concentrations coupled with heavy Cd isotope compositions of δ114/110Cd ≈ 0.2%, possibly indicating Cd additions from the tree litter used as organic fertilizer. Whilst cacao leaves, pods and beans are ubiquitously enriched in Cd relative to soils there are distinct Cd isotope signatures. The leaves and pods are isotopically heavier than the soils, with similar Δ114/110Cdleaf-soil values of 0.22 ± 0.07‰ to 0.41 ± 0.09‰. In contrast, the data reveal differences in Δ114/110Cdbean-leaf that may be linked to distinct cacao cultivars. In detail, Δ114/110Cdbean-leaf values of -0.34‰ to -0.40‰ were obtained for Nacional cacao from two farms, whilst CCN-51 hybrid cacao from a third farm showed no fractionation within error (-0.08 ± 0.13‰). As such, further work to investigate whether Cd isotopes are indeed useful for tracing sources of Cd enrichments in soils and to inform genetic efforts to reduce the Cd burden of cocoa is indicated.

Towards an understanding of the Cd isotope fractionation during transfer from the soil to the cereal grain.

Cd in soils might be taken up by plants, enter the food chain and endanger human health. This study investigates the isotopic fractionation of major processes during the Cd transfer from soils to cereal grains. Thereto, soil, soil solution, wheat and barley plants (roots, straw and grains) were sampled in the field at three study sites during two vegetation periods. Cd concentrations and δ114/110Cd values were determined in all samples. The composition of the soil solution was analyzed and the speciation of the dissolved Cd was modelled. Isotopic fractionation between soils and soil solutions (Δ114/110Cd20-50cm-soil solution = -0.61 to -0.68‰) was nearly constant among the three soils. Cd isotope compositions in plants were heavier than in soils (Δ114/110Cd0-20cm-plants = -0.55 to -0.31‰) but lighter than in soil solutions (Δ114/110Cdsoil solution-plants = 0.06-0.36‰) and these differences correlated with Cd plant-uptake rates. In a conceptual model, desorption from soil, soil solution speciation, adsorption on root surfaces, diffusion, and plant uptake were identified as the responsible processes for the Cd isotope fractionation between soil, soil solution and plants whereas the first two processes dominated over the last three processes. Within plants, compartments with lower Cd concentrations were enriched in light isotopes which might be a consequence of Cd retention mechanisms, following a Rayleigh fractionation, in which barley cultivars were more efficient than wheat cultivars.

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.

Determination of major and trace element variability in healthy human urine by ICP-QMS and specific gravity normalisation.

Sixty five urine samples obtained during one or two non-consecutive days from 10 healthy individuals were analysed for major (Na, Mg, K, Ca) and trace (Co, Cu, Zn, As, Rb, Sr, Mo and Pb) element concentrations. Following microwave digestion, the analyses were carried out using ICP-QMS (inductively coupled plasma quadrupole mass spectrometry) incorporating a collision/reaction cell. Repeat analyses of quality control samples show that the procedure produces unbiased results and is well suited for routine urinalysis of the investigated elements. Concentrations were normalised using specific gravity (SG) and the resultant decrease in variability supports previous conclusions that SG-normalisation appropriately corrects for differences in urine dilution. The elemental concentrations of the individual urine samples show large differences in dispersion. Most variable are As, Co and Zn, with CVs (coefficients of variation) of >75%. The major elements as well as Rb, Sr and Mo display intermediate variability, whilst Cu and Pb have the least elemental dispersion with CV values of about 30%. A detailed assessment shows that the overall elemental variability is governed both by differences between individuals and variations for a single individual over time. Spot urine samples exhibit elemental concentrations that, on average, resemble the daily mean values to within about 30% for all elements except K and Rb. Diet-related changes in urinary element concentration are most prominent for Mg, K, Co, Rb and Pb. The concentrations of Co, As and Rb appear to vary systematically with gender but this may primarily reflect co-variance with specific diets.

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.

Organic compounds released from resins that are commonly employed for trace element separations are known to have a detrimental impact on the quality of isotopic analyses by MC-ICP-MS. A recent study highlighted that such effects can be particularly problematic for Cd stable isotope measurements (M. Gault-Ringold and C. H. Stirling, J. Anal. At. Spectrom., 2012, 27, 449-459). In this case, the final stage of sample purification commonly applies extraction chromatography with Eichrom TRU resin, which employs particles coated with octylphenyl-N,N-di-isobutyl carbamoylphosphine oxide (CMPO) dissolved in tri-n-butyl phosphate (TBP). During chromatography, it appears that some of these compounds are eluted alongside Cd and cannot be removed by evaporation due to their high boiling points. When aliquots of the zero-ε reference material were processed through the purification procedure, refluxed in concentrated HNO3 and analyzed at minimum dilution (in 1 ml 0.1 M HNO3), they yielded Cd isotopic compositions (ε114/110Cd = 4.6 ± 3.4, 2SD, n = 4) that differed significantly from the expected value, despite the use of a double spike technique to correct for instrumental mass fractionation. This result was accompanied by a 35% reduction in instrumental sensitivity for Cd. With increasing dilution of the organic resin residue, both of these effects are reduced and they are insignificant when the eluted Cd is dissolved in ≥3 ml 0.1 M HNO3. Our results, furthermore, indicate that the isotopic artefacts are most likely related to anomalous mass bias behavior. Previous studies have shown that perchloric acid can be effective at avoiding such effects (Gault-Ringold and Stirling, 2012; K. C. Crocket, M. Lambelet, T. van de Flierdt, M. Rehkämper and L. F. Robinson, Chem. Geol., 2014, 374-375, 128-140), presumably by oxidizing the resin-derived organics, but there are numerous disadvantages to its use. Here we show that liquid-liquid extraction with n-heptane removes the organic compounds, dramatically improving quality of the Cd isotope data for samples that are analyzed at or close to minimum dilution factors. This technique is quick, simple and may be of use prior to analysis of other isotope systems where similar resins are employed.

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.

Combined chemical separation of Lu, Hf, Sm, Nd, and Rees from a single rock digest: precise and accurate isotope determinations of Lu-Hf and Sm-Nd using multicollector-ICPMS.

A combined procedure for separating Lu, Hf, Sm, Nd, and rare earth elements (REEs) from a single sample digest is presented. The procedure consists of the following five steps: (1) sample dissolution via sodium peroxide sintering; (2) separation of the high field strength elements from the REEs and other matrix elements by a HF-free anion-exchange column procedure; (3) purification of Hf on a cation-exchange resin; (4) separation of REEs from other matrix elements by cation exchange; (5) Lu, Sm, and Nd separation from the other REEs by reversed-phase ion chromatography. Analytical reproducibilities of Sm-Nd and Lu-Hf isotope systematics are demonstrated for standard solutions and international rock reference materials. Results show overall good reproducibilities for Sm-Nd systematics independent of the rock type analyzed. For the Lu-Hf systematics, the reproducibility of the parent/daughter ratio is much better for JB-1 (basalt) than for two analyzed felsic crustal rocks (DR-N and an Archaean granitoid). It is demonstrated that this poorer reproducibility of the Lu/Hf ratio is truly caused by sample heterogeneity; thus, results are geologically reasonable.