Reduced bioavailability of Au and isotopically enriched 109Ag nanoparticles transformed through a pilot wastewater treatment plant in Hyallela azteca under environmentally relevant exposure scenarios.

Wastewater Treatment Plants (WWTP) are a major repository and entrance path of nanoparticles (NP) in the environment and hence play a major role in the final fate and toxicity to biota of NP in the aquatic environment. Studies on silver nanoparticles (AgNP) transport via the WWTP system and uptake by aquatic biota have so far been carried out using unrealistically high AgNP concentrations, unlikely to be encountered in the aquatic environment. The use of high AgNP concentrations is necessitated by both the low sensitivity of the detection methods used and the need to distinguish background Ag from spiked AgNP. In this study, isotopically enriched 109AgNP were synthesized to overcome these shortcomings and characterized by a broad range of methods including transmission electron microscopy, dynamic and electrophoretic light scattering. 109AgNP and gold NP (AuNP) were spiked to a pilot wastewater treatment plant fed with municipal wastewater for up to 21 days. AuNP were used as chemically less reactive tracer. The uptake of the pristine and transformed NP present in the effluent was assessed using the benthic amphipod Hyalella azteca in fresh- and brackish water exposures at environmentally relevant concentrations of 30 to 500 ng Au/L and 39 to 260 ng Ag/L. The unique isotopic signature of the 109AgNP allowed to detect the material at environmentally relevant concentrations in the presence of a much higher natural Ag background. The results show that the transformations reduce the NP uptake at environmentally relevant exposure concentrations. For 109Ag, lower accumulation factors (AF) were obtained after exposure to transformed NP (250-350) compared to the AF values obtained for pristine 109AgNP (750-840). The reduced AF values observed for H. azteca exposed to effluent from the AuNP-spiked WWTP indicate that biological transformation processes (e.g. eco-corona formation) seem to be involved in addition to chemical transformation.

Stable Isotope Analyses Reveal Impact of Fe and Zn on Cd Uptake and Translocation by Theobroma cacao.

High concentrations of toxic cadmium (Cd) in soils are problematic as the element accumulates in food crops such as rice and cacao. A mitigation strategy to minimise Cd accumulation is to enhance the competitive uptake of plant-essential metals. Theobroma cacao seedlings were grown hydroponically with added Cd. Eight different treatments were used, which included/excluded hydroponic or foliar zinc (Zn) and/or iron (Fe) for the final growth period. Analyses of Cd concentrations and natural stable isotope compositions by multiple collector ICP-MS were conducted. Cadmium uptake and translocation decreased when Fe was removed from the hydroponic solutions, while the application of foliar Zn-EDTA may enhance Cd translocation. No significant differences in isotope fractionation during uptake were found between treatments. Data from all treatments fit a single Cd isotope fractionation model associated with sequestration (seq) of isotopically light Cd in roots and unidirectional mobilisation (mob) of isotopically heavier Cd to the leaves (ε114Cdseq-mob = -0.13‱). This result is in excellent agreement with data from an investigation of 19 genetically diverse cacao clones. The different Cd dynamics exhibited by the clones and seen in response to different Fe availability may be linked to similar physiological processes, such as the regulation of specific transporter proteins.

Decline of anthropogenic lead in South Atlantic Ocean surface waters from 1990 to 2011: New constraints from concentration and isotope data.

Anthropogenic emissions have severely perturbed the marine biogeochemical cycle of lead (Pb). Here, we present new Pb concentration and isotope data for surface seawater from GEOTRACES section GA02, sampled in the western South Atlantic in 2011. The South Atlantic is divided into three hydrographic zones: equatorial (0-20°S), subtropical (20-40°S), and subantarctic (40-60°S). The equatorial zone is dominated by previously deposited Pb transported by surface currents. The subtropical zone largely reflects anthropogenic Pb emissions from South America, whilst the subantarctic zone presents a mixture of South American anthropogenic Pb and natural Pb from Patagonian dust. The mean Pb concentration of 16.7 ± 3.8 pmol/kg is 34 % lower than in the 1990s, mostly driven by changes in the subtropical zone, with the fraction of natural Pb increasing from 24 % to 36 % between 1996 and 2011. Although anthropogenic Pb remains predominant, these findings demonstrate the effectiveness of policies that banned leaded gasoline.

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.

ZnO Nanomaterials and Ionic Zn Partition within Wastewater Sludge Investigated by Isotopic Labeling.

The increasing commercial use of engineered zinc oxide nanomaterials necessitates a thorough understanding of their behavior following their release into wastewater. Herein, the fates of zinc oxide nanoparticles (ZnO NPs) and ionic Zn in a real primary sludge collected from a municipal wastewater system are studied via stable isotope tracing at an environmentally relevant spiking concentration of 15.2 µg g-1. Due to rapid dissolution, nanoparticulate ZnO does not impart particle-specific effects, and the Zn ions from NP dissolution and ionic Zn display indistinguishable behavior as they partition equally between the solid, liquid, and ultrafiltrate phases of the sludge over a 4-h incubation period. This work provides important constraints on the behavior of engineered ZnO nanomaterials in primary sludge-the first barrier in a wastewater treatment plant-at low, realistic concentrations. As the calculated solid-liquid partition coefficients are significantly lower than those reported in prior studies that employ unreasonably high spiking concentrations, this work highlights the importance of using low, environmentally relevant doses of engineered nanomaterials in experiments to obtain accurate risk assessments.

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.

Zinc stable isotopes in urine as diagnostic for cancer of secretory organs.

Breast, prostate, and pancreatic cancers alter the zinc (Zn) metabolism. Combined analyses of urinary Zn concentrations [Zn] and Zn stable isotope compositions (δ66Zn) may provide a non-invasive approach for tracing malignancy-induced Zn dyshomeostasis. In this study, we measured [Zn] and δ66Zn in urine from prostate (n = 22), breast (n = 16), and from women with benign breast disease (n = 14) and compared those with age-matched healthy controls (22-49 years or 50+ years) and published data for pancreatic cancer (n = 17). Our results show that cancer-induced changes are reflected in higher urinary [Zn] and lower urinary δ66Zn for pancreatic and prostate cancer and benign breast disease when compared with healthy controls. For prostate cancer, the progression of low [Zn] and high δ66Zn for patients of low-risk disease toward high [Zn] and low δ66Zn for the higher risk patients demonstrates that [Zn] and δ66Zn in urine could serve as a reliable prognostic tool. Urinary excretion of isotopically light Zn by patients with prostatic and pancreatic cancer is probably the result of increased reactive oxygen species in cancerous cells, which limits the scavenging of hydroxyl radicals and thus facilitates the oxidation of metalloproteins with sulfur-rich ligands. Urine from breast cancer patients shows undistinguishable δ66Zn to healthy controls, implying that the expression of metalloproteins with sulfur-rich ligands is stronger in breast cancer tissues. In conclusion, urinary δ66Zn may provide a non-invasive diagnostic tool for pancreatic cancer and support disease prognosis for prostate cancer. These findings should translate to comprehensive transverse and longitudinal cohort studies in future.

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.

Postprandial zinc stable isotope response in human blood serum.

In recent years, considerable advances have been made in the field of medical isotope metallomics, but numerous fundamental physiological processes remain to be investigated. Past studies report that blood serum Zn concentrations decrease by between about 10 and 25%, depending on the size of meal, approximately three hours postprandially (i.e. after eating), before returning to baseline values if no meals are consumed over the following four to five hours. Nine participants were recruited for this study to investigate whether this postprandial Zn concentration decrease is accompanied by a stable isotope response. A baseline serum sample was collected from participants in the morning after overnight fasting. A 576 kcal meal was then provided and additional serum samples were taken 90 and 180 minutes post-meal to coincide with the postprandial response. Serum Zn concentrations decreased postprandially by an average of 21 ± 9% (1SD), but this was not accompanied by a change in stable Zn isotope composition (mean Δ66Zn180-minute-baseline = 0.01 ± 0.09‰, 2SD). We propose that hemodilution and the rapid, efficient postprandial transfer of albumin-bound Zn from serum to the liver and pancreas is responsible for the lack of postprandial serum Zn isotopic response. These results indicate that studies examining solely the distribution of Zn isotopes in serum may obtain samples without considering timing of the most recent meal. However, future studies seeking to compare serum Zn concentrations with δ66Zn values should draw blood samples in the morning after overnight fasting.

Cadmium isotope fractionation reveals genetic variation in Cd uptake and translocation by Theobroma cacao and role of natural resistance-associated macrophage protein 5 and heavy metal ATPase-family transporters.

In response to new European Union regulations, studies are underway to mitigate accumulation of toxic cadmium (Cd) in cacao (Theobroma cacao, Tc). This study advances such research with Cd isotope analyses of 19 genetically diverse cacao clones and yeast transformed to express cacao natural resistance-associated macrophage protein (NRAMP5) and heavy metal ATPases (HMAs). The plants were enriched in light Cd isotopes relative to the hydroponic solution with Δ114/110Cdtot-sol = -0.22 ± 0.08‰. Leaves show a systematic enrichment of isotopically heavy Cd relative to total plants, in accord with closed-system isotope fractionation of Δ114/110Cdseq-mob = -0.13‰, by sequestering isotopically light Cd in roots/stems and mobilisation of remaining Cd to leaves. The findings demonstrate that (i) transfer of Cd between roots and leaves is primarily unidirectional; (ii) different clones utilise similar pathways for Cd sequestration, which differ from those of other studied plants; (iii) clones differ in their efficiency of Cd sequestration. Transgenic yeast that expresses TcNRAMP5 (T. cacao natural resistance-associated macrophage gene) had isotopically lighter Cd than did cacao. This suggests that NRAMP5 transporters constitute an important pathway for uptake of Cd by cacao. Cd isotope signatures of transgenic yeast expressing HMA-family proteins suggest that they may contribute to Cd sequestration. The data are the first to record isotope fractionation induced by transporter proteins in vivo.

Rhenium-Based Complexes and in Vivo Testing: A Brief History.

The success of metal-based anticancer therapeutics in the treatment of cancer is best exemplified by cisplatin. Currently used in 32/78 cancer regimens, metal-based drugs have a clear role in cancer therapy. Despite this, metal-based anticancer therapeutics are not without drawbacks, with issues such as toxic side effects and the development of resistance mechanisms. This has led to investigations of other metal-based drug candidates such as auranofin, a gold-based drug candidate as well as ruthenium-based candidates, NAMI-A, NKP-1339 and TLD-1433. All are currently undergoing clinical trials. Another class of complexes under study are rhenium-based; such complexes have undergone extensive in vitro testing but only nine have been reported to display antitumour in vivo activity, which is a necessary step before entering clinical trials. This review will document, chronologically, the rhenium-based drug candidates that have undergone in vivo testing and the outlook for such complexes.

Stable isotope labeling of metal/metal oxide nanomaterials for environmental and biological tracing.

Engineered nanomaterials (NMs) are often compositionally indistinguishable from their natural counterparts, and thus their tracking in the environment or within the biota requires the development of appropriate labeling tools. Stable isotope labeling has become a well-established such tool, developed to assign 'ownership' or a 'source' to engineered NMs, enabling their tracing and quantification, especially in complex environments. A particular methodological challenge for stable isotope labeling is to ensure that the label is traceable in a range of environmental or biological scenarios but does not induce modification of the properties of the NM or lose its signal, thus retaining realism and relevance. This protocol describes a strategy for stable isotope labeling of several widely used metal and metal oxide NMs, namely ZnO, CuO, Ag, and TiO2, using isotopically enriched precursors, namely 67Zn or 68Zn metal, 65CuCl2, 107Ag or 109Ag metal, and 47TiO2 powder. A complete synthesis requires 1-8 d, depending on the type of NM, the precursors used, and the synthesis methods adopted. The physicochemical properties of the labeled particles are determined by optical, diffraction, and spectroscopic techniques for quality control. The procedures for tracing the labels in aquatic (snail and mussel) and terrestrial (earthworm) organisms and for monitoring the environmental transformation of labeled silver (Ag) NMs are also described. We envision that this labeling strategy will be adopted by industry to facilitate applications such as nanosafety assessments before NMs enter the market and environment, as well as for product authentication and tracking.

Assessment of coupled Zn concentration and natural stable isotope analyses of urine as a novel probe of Zn status.

Zinc is a common trace metal in the human body, present in about 10% of proteins. Despite numerous roles of Zn in health and disease, there is still a need for a robust biomarker of Zn status. Many parameters have been proposed, with varying levels of success, with plasma Zn often favoured. This study investigates if Zn status can be assessed from the natural stable Zn isotope composition of urine. To this end, 60 urine samples were analysed from ten healthy participants. Remarkably, samples with lower Zn concentrations are systematically enriched in heavy Zn isotopes. Most of the low-Zn urine originated from individuals who omitted dairy, meat or both from their diets. When data for blood serum from age-matched, healthy individuals are compared with the urine results, the former plot at the extension of the urine trend at higher Zn concentrations and lighter isotope compositions. The observed co-variation of Zn isotope compositions with concentrations is indicative of an isotope fractionation system where both properties are controlled by the same processes. It is interpreted as arising from filtration and/or reabsorption processes within the kidney, which are associated with absorbed dietary Zn. The data suggest that the Zn in blood serum that is bound to low molecular weight molecules has an isotope composition distinct from total serum, due to the different affinities of molecular Zn-binding residues to heavy and light Zn isotopes. This technique provides additional information into an individual's Zn status compared to urine or plasma Zn levels alone.

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.

Using isotopes to trace freshly applied cadmium through mineral phosphorus fertilization in soil-fertilizer-plant systems.

Applications of mineral phosphorus (P) fertilizer can lead to cadmium (Cd) accumulation in soils and can increase Cd concentrations in edible crop parts. To determine the fate of freshly applied Cd, a Cd source tracing experiment was conducted in three soil-fertilizer-wheat systems by using a mineral P fertilizer labeled with the radio isotope 109Cd and by exploiting natural differences in Cd stable isotope compositions (δ114/110Cd). Source tracing with stable isotopes overestimated the proportion of Cd in plants derived from the P fertilizer, because the isotope ratios of the sources were not sufficiently distinct from those of the soils. Despite indistinguishable extractable Cd pools between control and treatments, the addition of P fertilizer resulted in a more negative apparent isotope fractionation between soil and wheat. Overall, the radio isotope approach provided more robust results and revealed that 6.5 to 15% of the Cd in the shoot derived from the fertilizer. From the introduced Cd, a maximum of 2.2% reached the wheat shoots, whilst 97.8% remained in the roots and soils. The low recoveries of the fertilizer derived Cd suggest that continuous P fertilizer application in the past decades can lead to a build-up of a residual Cd pool in soils.

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.