Publications
37 results found
Griffiths A, Lambelet M, Crocket K, et al., 2024, Neodymium isotope composition and rare earth element distribution of East Antarctic continental shelf and deep waters, Chemical Geology, Vol: 653, ISSN: 0009-2541
Circumpolar Deep Water (CDW) and Antarctic Bottom Water (AABW) play key roles in the Earth's climate system. Both water masses form critical components of the Antarctic Circumpolar Current and Meridional Overturning Circulation and therefore directly influence the large-scale redistribution of heat, nutrients and carbon. Reconstruction of past CDW transport and AABW production and export has been a key target in palaeoceanography. One promising proxy to achieve this has been the neodymium (Nd) isotope composition of seawater. The biogeochemical processes controlling Nd in the ocean, however, remain underconstrained, and modern observations of Nd isotopes in the Southern Ocean are still geographically limited.To overcome this limitation, 61 seawater samples were collected for Nd isotope and rare earth element (REE) analysis at nine stations along the Wilkes Land continental margin and in the Australian-Antarctic Basin (65°S 125°E) near East Antarctica. The results show that the different water masses have the following Nd isotope characteristics: Antarctic Surface Water (AASW), εNd = −9.0 ± 1.0 (2SD; n = 22); Modified CDW (MCDW), εNd = −8.8 ± 0.8 (2SD; n = 22); AABW, εNd = −8.3 ± 0.5 (2SD; n = 17).There is no evidence of continental REE inputs to surface waters on the Wilkes Land margin. Observed zonal variability of Nd isotope composition in AASW can be attributed to seasonal competition between the poleward flow of warm AASW from the AAG and the westward export of cold surface shelf waters by the Antarctic Slope Current.In terms of deep and bottom waters, mixing of upwelled CDW with AASW and AABW exclusively controls the Nd isotope composition of MCDW, with no indication of boundary processes modifying the Nd isotope composition of MCDW as it encroaches the shelf or slope. The regional Nd isotope signature for AABW is intermediate between published data for the Atlantic sector AABW (εNd
Evangelinos D, Etourneau J, van de Flierdt T, et al., 2024, Late Miocene onset of the modern Antarctic Circumpolar Current, Nature Geoscience, Vol: 17, Pages: 165-170, ISSN: 1752-0894
The Antarctic Circumpolar Current plays a pivotal role in global climate through its strong influence on the global overturning circulation, ocean heat and CO2 uptake. However, when and how the Antarctic Circumpolar Current reached its modern-like characteristics remains disputed. Here we present neodymium isotope and sortable silt records from sediment cores in the Southwest Pacific and South Indian oceans spanning the past 31 million years. Our data indicate that a circumpolar current like that of today did not exist before the late Miocene cooling. These findings suggest that the emergence of a homogeneous and deep-reaching strong Antarctic Circumpolar Current was not linked solely to the opening and deepening of Southern Ocean Gateways triggering continental-scale Antarctic Ice Sheet expansion during the Eocene–Oligocene Transition (∼34 Ma). Instead, we find that besides tectonic pre-conditioning, the expansion of the Antarctic Ice Sheet and sea ice since the middle Miocene Climate Transition (∼14 Ma) played a crucial role. This led to stronger density contrast and intensified Southern Westerly Winds across the Southern Ocean, establishing a vigorous deep-reaching circumpolar flow and an enhanced global overturning circulation, which amplified the late Cenozoic global cooling.
Zhou J, Moore RET, Rehkämper M, et al., 2024, Cadmium and zinc isotope compositions indicate metal sources and retention mechanisms in different soil particle size fractions, Journal of Hazardous Materials, Vol: 461, ISSN: 0304-3894
Soil particle size may significantly affect metal distribution and stable isotopic behavior. Here, two soils were separated into four particle size fractions, namely fine sand, silt, fine silt, and colloidal particles and used to determine cadmium (Cd) and zinc (Zn) concentrations and isotope compositions. Concentrations of Cd and Zn were generally enriched in the finer particles and positively correlated with the iron (Fe) and manganese (Mn) oxide contents. However, Cd concentration in the fine sand was higher than in the silt fraction due to the higher soil organic matter contents in the former particle fraction. The maximum δ114/110Cd value was found in the colloidal particles (−0.02 and 0.01‰) of both soils while the minimum was in the silt particles (−0.12 and single bond0.06‰). Incorporation into the mineral lattice of Fe and Mn oxides is suggested to explain the slight enrichment of heavy Cd isotopes in the colloidal fraction. The similar δ66Zn values of the four particle fractions (0.20–0.29‰ with a mean of 0.25‰) indicate similar Zn sources in different particle sizes. Metal isotopic fingerprint of different soil particle size fractions provides further insight into underlying metal retention mechanisms within soil micro-zones and helps in tracing metal sources and biogeochemical processes.
Packmann H, Little SH, Nieto JM, et al., 2023, Tracing acid mine drainage and estuarine Zn attenuation using Cd and Zn isotopes, Geochimica et Cosmochimica Acta, Vol: 360, Pages: 36-56, ISSN: 0016-7037
It has been estimated that the acid mine drainage (AMD) impacted Odiel river basin in southern Spain supplies 0.37% and 15% of the global riverine fluxes of Cd and Zn to the oceans, respectively (Sarmiento et al., 2009). However, the behaviour of Cd and Zn in the Ria of Huelva estuary, which connects the Odiel and Tinto watersheds with the Gulf of Cadiz, has yet to be fully investigated. Furthermore, very few studies have investigated Cd and Zn isotope behaviour in estuaries worldwide. This study presents Cd and Zn concentrations and isotopic compositions for the Ria of Huelva estuary and surrounding watersheds, sampled in 2017 and 2019. Sulfide-rich rock samples extracted from three mines yield Cd and Zn isotope compositions that range from –0.14‰ to +0.07‰ (n = 4) for δ114Cd and –0.01‰ to +0.29‰ (n = 4) for δ66Zn. However, a uniform riverine signal of about +0.02‰ for Cd and +0.17‰ for Zn indicates that tracing of individual mining regions using Cd and Zn isotopes is challenging. Limited variability was observed in dissolved δ114Cd values throughout the watershed, including AMD, the estuary, and the Gulf of Cadiz, with a mean value of ±0.00 ± 0.13‰ (n = 25, 2 SD; excludes one AMD outlier, at +0.48‰), including both 2017 and 2019 data. By contrast, δ66Zn values ranged from –0.12‰ to +0.35‰ (n = 28) for the same geographical and temporal scope. In May 2017, a large spill from an abandoned mine, La Zarza, resulted in a drastic increase in the concentrations of trace metals reaching the estuary compared to 2019, but no impact of this mine spill on Cd or Zn isotope compositions is observed. In 2019, an increase in δ66Zn values in the estuary coincided with high pH values (up to pH = 8.8) and chloride concentrations (2.73%), which may reflect an alkaline anthropogenic input from the active neighbouring industrial complex. Overall, Cd concen
Barati E, Moore RET, Ullah I, et al., 2023, Publisher Correction: 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., Sci Rep, Vol: 13
Morton EM, Kreissig K, Coles BJ, et al., 2023, A new double spike method for the determination of mass-dependent Te isotope compositions of meteorites and terrestrial materials by MC-ICP-MS, Journal of Analytical Atomic Spectrometry, Vol: 38, Pages: 1192-1204, ISSN: 0267-9477
This study presents a new method for the determination of mass-dependent Te isotope compositions. The process encompasses a new column chromatographic procedure which separates Te from chondritic and iron meteorites and diverse terrestrial rocks with high yield and purity, combined with a robust 125Te–128Te double spike and optimised multi collector ICP-MS protocols. This allows for precise (2SD = 0.07‰) determination of the mass-dependent 130Te/125Te isotope ratio using analyte solutions containing as little as 6 ng of natural Te. The efficacy of the method is demonstrated by repeat analyses of terrestrial rock reference materials and meteorites, which show overall good agreement with previous work. In addition, an inter-laboratory cross-calibration of three different Te standard solutions was performed. This inter-laboratory cross-calibration is highly advantageous, as a well-calibrated isotope reference material is not yet available for Te. Isotope mass balance and mixing equations performed in this study show that hypothetical mass-independent Te isotope effects of reasonable magnitude are unlikely to have a significant impact on the measured mass-dependent Te isotope compositions at the current level of analytical precision. Finally, this study presents the first precise mass-dependent Te isotope composition obtained for an iron meteorite, Canyon Diablo, and komatiite reference material KAL-1 using the double spike technique.
Zhou J, Moore RET, Rehkämper M, et al., 2023, Zinc supply affects cadmium uptake and translocation in the hyperaccumulator Sedum plumbizincicola as evidenced by isotope fractionation., Environmental Science and Technology (Washington), Vol: 57, Pages: 5891-5902, ISSN: 0013-936X
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.
Barati E, Moore R, Ullah I, et al., 2023, 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, Scientific Reports, Vol: 13, Pages: 1-13, ISSN: 2045-2322
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.
Martins R, Kuthning S, Coles B, et al., 2023, Nucleosynthetic isotope anomalies of zinc in meteorites constrain the origin of Earth’s volatiles, Science, Vol: 379, Pages: 369-372, ISSN: 0036-8075
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.
Pickard H, Palk E, Schönbächler M, et al., 2022, The cadmium and zinc isotope compositions of the silicate Earth – implications for terrestrial volatile accretion, Geochimica et Cosmochimica Acta, Vol: 338, Pages: 165-180, ISSN: 0016-7037
Zinc and Cd isotope compositions are presented for a comprehensive suite of terrestrial rocks to constrain the extent of Zn and Cd isotope fractionation during igneous processes and better define the δ66Zn and δ114Cd values of the silicate Earth (the δ values denote per mille deviations of 66Zn/64Zn from JMC Lyon Zn and of 114Cd/110Cd from NIST SRM 3108 Cd). Analyses of spinel lherzolites provide a bulk silicate Earth (BSE) δ114CdBSE value of –0.06 ± 0.03‰ (2SD). For Zn, the peridotite data of the current and previous studies define a mean δ66ZnBSE = 0.20 ± 0.05‰ (2SD). Komatiite analyses of this and published investigations yield similar mean values, which suggests that the Zn and Cd isotope compositions of the mantle remained fairly constant since the Archean. Data for loess provide upper continental crust compositions of δ114Cd = 0.03 ± 0.10‰ and δ66Zn = 0.23 ± 0.07‰. The Zn isotope and abundance data for peridotites and oceanic basalts are in accord with the previous observation of a mantle array, with basalts having higher Zn concentrations and δ66Zn values than the peridotites. To a first order, this reflects slightly incompatible behaviour of Zn during mantle melting and melt differentiation with associated enrichment of heavy Zn isotopes in the melt phase. Cadmium is marginally more incompatible than Zn during igneous processes and the oceanic basalts also display a minor enrichment of heavy Cd isotopes relative to peridotites. However, secondary processes produce significant Cd isotope variability in both mantle melts and peridotites, obscuring the primary igneous array. The δ66ZnBSE estimates of this and previous studies resemble the Zn isotope compositions of CV and CO carbonaceous and some enstatite chondrites. In contrast, the BSE has a lower δ114CdBSE value than enstatite and carbonaceous chondrites. This implies that the Cd isotope
Packman H, Little SH, Baker AR, et al., 2022, Tracing natural and anthropogenic sources of aerosols to the Atlantic Ocean using Zn and Cu isotopes, Chemical Geology, Vol: 610, Pages: 1-14, ISSN: 0009-2541
Anthropogenic activities have significantly enhanced atmospheric metal inputs to the ocean, which has potentially important consequences for marine ecosystems. This study assesses the potential of Zn and Cu isotope compositions to distinguish between natural and anthropogenic atmospheric inputs of these metals to the surface ocean. To this end, the isotopic compositions of Zn and Cu in aerosols collected from the eastern tropical Atlantic Ocean on the GEOTRACES GA06 cruise are examined. Enrichment factors and fractional solubility measurements indicate the presence of a significant anthropogenic component in the aerosols collected furthest from the North African dust plume for both Zn and Cu. The mean δ65CuNIST SRM 976 for the fully digested aerosols is +0.07 ± 0.39 ‰ (n = 9, 2 SD), which is indistinguishable from the lithogenic value, and implies that Cu isotopes are not an effective tracer of aerosol sources in this region. The mean δ66ZnJMC-Lyon value for the aerosols that underwent a total digestion is +0.17 ± 0.22 ‰ (n = 11, 2 SD). The aerosols leached with ammonium acetate have similar Zn isotope compositions, with a mean of +0.15 ± 0.16 ‰ (n = 7, 2 SD). The aerosols were collected in a region with prevalent mineral dust but, despite this, exhibit isotopically lighter Zn than lithogenic Zn with δ66Zn ≈ +0.3 ‰. When coupled with the previously published Pb isotope data, the aerosols exhibit coupled Zn-Pb isotope systematics that are indicative of mixing between mineral dust (δ66Zn = +0.28 ‰ and 206Pb/207Pb = 1.205) and anthropogenic emissions (δ66Zn = −0.22 ‰ and 206Pb/207Pb = 1.129). This demonstrates the potential of Zn isotopes to trace atmospheric Zn inputs from anthropogenic sources to the surface ocean.
Martins R, Kuthning S, Coles BJ, et al., 2022, Nucleosynthetic Zn anomalies reveal the origin of Earth’s volatiles, 85th Annual Meeting of the Meteoritical Society (2022), Publisher: Wiley, ISSN: 1086-9379
Evangelinos D, Escutia C, van de Flierdt T, et al., 2022, Absence of a strong, deep-reaching Antarctic Circumpolar Current zonal flow across the Tasmanian gateway during the Oligocene to early Miocene, Global and Planetary Change, Vol: 208, Pages: 1-12, ISSN: 0921-8181
The vigorous eastward flow of the Antarctic Circumpolar Current (ACC) connects all major ocean basins and plays a prominent role in the transport of heat, carbon and nutrients around the globe. However, the establishment of a deep circumpolar flow, similar to the present-day ACC, remains controversial thereby obscuring our understanding of its climatic impact. Deciphering the chemical composition of Circumpolar Deep Water (CDW) within the ACC can provide critical insights about its development and evolution. Here we present new fossil fish teeth/bone debris neodymium isotope (εNd) records from Deep Sea Drilling Project (DSDP) Sites 278 and 274 in the southwest Pacific Ocean, with the aim to trace changes in deep water masses across the Tasmanian Gateway between the early Oligocene and early Miocene (~ 33–22 Ma). Site 274 provides the first Nd isotope record proximal to the Ross Sea during the Oligocene (33.5–23.4 Ma). Its Nd isotope composition shows excursions to very radiogenic values, εNd(t) = −3.1 and εNd(t)= − 3.7, at 33.5 Ma and 23.8 Ma, respectively, in response to major steps in Antarctic ice sheet expansion. A shift to lower, more unradiogenic εNd(t) values between 29.7 and 29.1 Ma is linked to an increased influence of proto-CDW upwelling at the site. In contrast, the Nd isotope record from Site 278 in the southern Emerald Basin shows little variability (εNd(t) = −6.0 to −6.7) throughout the Oligocene and early Miocene (30.9–21.8 Ma). Comparison with published data north of the ACC path, demonstrates the presence of two deep water masses in the South Pacific prior to the inferred onset of the ACC (33–30 Ma), one occupying depths between ~2500 and 3000 m (εNd(t)= ~ −3 to −5) and a deep/bottom water mass (> 3000 m) with a more unradiogenic Nd isotope composition (εNd(t)= ~ −6). Site 278 located close to the proto-polar front (proto-PF)
Sullivan KV, Moore RET, Capper MS, et al., 2021, Zinc stable isotope analysis reveals Zn dyshomeostasis in benign tumours, breast cancer, and adjacent histologically normal tissue, Matallomics, Vol: 13, Pages: 1-12, ISSN: 1756-591X
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.
Chen L, Little SH, Kreissig K, et al., 2021, Isotopically light Cd in sediments underlying oxygen deficient zones, Frontiers in Earth Science, Vol: 9, Pages: 1-17, ISSN: 2296-6463
Cadmium is a trace metal of interest in the ocean partly because its concentration mimics that of phosphate. However, deviations from the global mean dissolved Cd/PO4 relationship are present in oxygen deficient zones, where Cd is depleted relative to phosphate. This decoupling has been suggested to result from cadmium sulphide (CdS) precipitation in reducing microenvironments within sinking organic matter. We present Cd concentrations and Cd isotope compositions in organic-rich sediments deposited at several upwelling sites along the northeast Pacific continental margin. These sediments all have enriched Cd concentrations relative to crustal material. We calculate a net accumulation rate of Cd in margin settings of between 2.6 to 12.0 × 107 mol/yr, higher than previous estimates, but at the low end of a recently published estimate for the magnitude of the marine sink due to water column CdS precipitation. Cadmium in organic-rich sediments is isotopically light (δ114/110CdNIST-3108 = +0.02 ± 0.14‰, n = 26; 2 SD) compared to deep seawater (+0.3 ± 0.1‰). However, isotope fractionation during diagenesis in continental margin settings appears to be small. Therefore, the light Cd isotope composition of organic-rich sediments is likely to reflect an isotopically light source of Cd. Non-quantitative biological uptake of light Cd by phytoplankton is one possible means of supplying light Cd to the sediment, which would imply that Cd isotopes could be used as a tracer of past ocean productivity. However, water column CdS precipitation is also predicted to preferentially sequester light Cd isotopes from the water column, which could obfuscate Cd as a tracer. We also observe notably light Cd isotope compositions associated with elevated solid phase Fe concentrations, suggesting that scavenging of Cd by Fe oxide phases may contribute to the light Cd isotope composition of sediments. These multiple possible sources of isotopically light Cd
Griffiths A, Packman H, Leung YL, et al., 2020, Evaluation of optimized procedures for high-precision Pb isotope analyses of seawater by MC-ICP-MS, Analytical Chemistry, Vol: 92, Pages: 11232-11241, ISSN: 0003-2700
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 MC-ICP-MS measurements of seawater Pb isotope compositions following Pb separation by either solid-phase extraction with Nobias Chelate PA-1 resin or co-precipitation 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 (2SD) of 100–1200 ppm for 206Pb/207Pb, 208Pb/207Pb and 300–1700 ppm for ratios involving the minor 204Pb isotope. All four procedures enable significantly improved sample throughout compared to an established TIMS double-spike method and produce unbiased seawater Pb isotope compositions with similar or improved precision. Nobias extraction is preferable to co-precipitation 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, co-precipitation 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.
Barraza F, Moore R, Rehkamper M, et al., 2019, Cadmium isotope fractionation in soil-cacao systems of Ecuador: a pilot field study, RSC Advances: an international journal to further the chemical sciences, Vol: 9, Pages: 34011-34022, ISSN: 2046-2069
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.
Imseng M, Wiggenhauser M, Keller A, et al., 2019, Towards an understanding of the Cd isotope fractionation during transfer from the soil to the cereal grain, Environmental Pollution, Vol: 244, Pages: 834-844, ISSN: 0269-7491
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.
Moore R, Rehkamper M, Kreissig K, et al., 2018, Determination of major and trace element variability in healthy human urine by ICP-QMS and specific gravity normalisation, RSC Advances, Vol: 8, Pages: 38022-38035, ISSN: 2046-2069
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.
Khondoker R, Weiss DJ, van de Flierdt T, et al., 2018, New constraints on elemental and Pb and Nd isotope compositions of South American and Southern African aerosol sources to the South Atlantic Ocean, Chemie der Erde / Geochemistry, Vol: 78, Pages: 372-384, ISSN: 0009-2819
Improving the geochemical database available for characterising potential natural and anthropogenic aerosol sources from South America and Southern Africa is a critical precondition for studies aimed at understanding trace metal controls on the marine biogeochemical cycles of the South Atlantic Ocean. We here present new elemental and isotopic data for a wide range of sample types from South America and Southern Africa that are potentially important aerosol sources. This includes road dust from Buenos Aires and lichen samples from Johannesburg, soil dust from Patagonia, volcanic ash from the Andean volcanic belt, and aerosol samples from São Paulo. All samples were investigated for major (Al, Ca, Fe, Mg, Na, K, Mn) and trace element (Cd, Co, Cr, Cu, Ni, Pb, REE, Sc, Th, Y, V, Zn) concentrations and Nd and Pb isotopic compositions. We show that diagrams of 208Pb/207Pb vs. εNd, 208Pb/207Pb vs. Pb/Al, 1/[Pb], Zn/Al, Cd/Al, Cu/Al, and εNd vs. Pb/Al, and 1/[Nd] are best suited to separate South American and South African source regions as well as natural and anthropogenic sources. A subset of samples from Patagonia and the Andes was additionally subjected to separation of a fine (<5 μm) fraction and compared to the composition of the bulk sample. We show that differences in the geochemical signature of bulk samples between individual regions and source types are significantly larger than between grain sizes. Jointly, these findings present an important step forward towards a quantitative assessment of aeolian trace metal inputs to the South Atlantic Ocean.
Imseng M, Wiggenhauser M, Keller A, et al., 2018, Fate of Cd in agricultural soils: a stable isotope approach to anthropogenic impact, soil formation and soil-plant cycling, Environmental Science and Technology, Vol: 52, Pages: 1919-1928, ISSN: 0013-936X
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.
Palk C, Andreasen R, Rehkamper M, et al., 2017, Variable Tl, Pb and Cd concentrations and isotope compositions of enstatite and ordinary chondrites – evidence for volatile element mobilization and decay of extinct 205Pb, Meteoritics and Planetary Science, Vol: 53, Pages: 167-186, ISSN: 1086-9379
New Tl, Pb, and Cd concentration and Tl, Pb isotope data are presented for enstatite as well as L- and LL-type ordinary chondrites, with additional Cd stable isotope results for the former. All three chondrite suites have Tl and Cd contents that vary by more than 1–2 orders of magnitude but Pb concentrations are more uniform, as a result of terrestrial Pb contamination. Model calculations based on Pb isotope compositions indicate that for more than half of the samples, more than 50% of the measured Pb contents are due to addition of modern terrestrial Pb. In part, this is responsible for the relatively young and imprecise Pb-Pb ages determined for EH, L, and LL chondrites, which are hence only of limited chronological utility. In contrast, four particularly pristine EL chondrites define a precise Pb-Pb cooling age of 4559 ± 6 Ma. The enstatite chondrites (ECs) have highly variable ε114/110Cd of between about +3 and +70 due to stable isotope fractionation from thermal and shock metamorphism. Furthermore, nearly all enstatite meteorites display ε205Tl values from −3.3 to +0.8, while a single anomalous sample is highly fractionated in both Tl and Cd isotopes. The majority of the ECs thereby define a correlation of ε205Tl with ε114/110Cd, which suggests that at least some of the Tl isotope variability reflects stable isotope fractionation rather than radiogenic ingrowth of 205Tl from 205Pb decay. Considering L chondrites, most ε205Tl values range between −4 and +1, while two outliers with ε205Tl ≤ −10 are indicative of stable isotope fractionation. Considering only those L chondrites which are least likely to feature Pb contamination or stable Tl isotope effects, the results are in accord with the former presence of live 205Pb on the parent body, with an initial 205Pb/204Pb = (1.5 ± 1.4) × 10−4, which suggests late equilibration of the Pb-Tl system 26–113 Ma after
Hunt AC, Benedix GK, Hammond SJ, et al., 2016, A geochemical study of the winonaites: Evidence for limited partial melting and constraints on the precursor composition, Geochimica et Cosmochimica Acta, Vol: 199, Pages: 13-30, ISSN: 0016-7037
The winonaites are primitive achondrites which are associated with the IAB iron meteorites. Textural evidence implies heating to at least the Fe, Ni-FeS cotectic, but previous geochemical studies are ambiguous about the extent of silicate melting in these samples. Oxygen isotope evidence indicates that the precursor material may be related to the carbonaceous chondrites. Here we analysed a suite of winonaites for modal mineralogy and bulk major- and trace-element chemistry in order to assess the extent of thermal processing as well as constrain the precursor composition of the winonaite-IAB parent asteroid. Modal mineralogy and geochemical data are presented for eight winonaites. Textural analysis reveals that, for our sub-set of samples, all except the most primitive winonaite (Northwest Africa 1463) reached the Fe, Ni-FeS cotectic. However, only one (Tierra Blanca) shows geochemical evidence for silicate melting processes. Tierra Blanca is interpreted as a residue of small-degree silicate melting. Our sample of Winona shows geochemical evidence for extensive terrestrial weathering. All other winonaites studied here (Fortuna, Queen Alexander Range 94535, Hammadah al Hamra 193, Pontlyfni and NWA 1463) have chondritic major-element ratios and flat CI-normalised bulk rare-earth element patterns, suggesting that most of the winonaites did not reach the silicate melting temperature. The majority of winonaites were therefore heated to a narrow temperature range of between ~1220 (the Fe, Ni-FeS cotectic temperature) and ~1370 K (the basaltic partial melting temperature). Silicate inclusions in the IAB irons demonstrate partial melting did occur in some parts of the parent body (Ruzicka and Hutson, 2010), thereby implying heterogeneous heat distribution within this asteroid. Together, this indicates that melting was the result of internal heating by short-lived radionuclides. The brecciated nature of the winonaites suggests that the parent body was later disrupted by a cat
Wiggenhauser M, Bigalke M, Imseng M, et al., 2016, Cadmium isotope fractionation in soil-wheat systems, Environmental Science and Technology, Vol: 50, Pages: 9223-9231, ISSN: 0013-936X
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.
Lambelet M, van de Flierdt T, Crocket K, et al., 2016, Neodymium isotopic composition and concentration in the western North Atlantic Ocean: results from the GEOTRACES GA02 section, Geochimica et Cosmochimica Acta, Vol: 177, Pages: 1-29, ISSN: 0016-7037
The neodymium (Nd) isotopic composition of seawater is commonly used as a proxy to study past changes in the thermohaline circulation. The modern database for such reconstructions is however poor and the understanding of the underlying processes is incomplete. Here we present new observational data for Nd isotopes and concentrations from twelve seawater depth profiles, which follow the flow path of North Atlantic Deep Water (NADW) from its formation region in the North Atlantic to the northern equatorial Atlantic. Samples were collected during two cruises constituting the northern part of the Dutch GEOTRACES transect GA02 in 2010. The results show that the different water masses in the subpolar North Atlantic Ocean, which ultimately constitute NADW, have the following Nd isotope characteristics: Upper Labrador Sea Water (ULSW), εNd = -14.2 ± 0.3; Labrador Sea Water (LSW), εNd = -13.7 ± 0.9; Northeast Atlantic Deep Water (NEADW), εNd = -12.5 ± 0.6; Northwest Atlantic Bottom Water (NWABW), εNd = -11.8 ± 1.4. In the subtropics, where these source water masses have mixed to form NADW, which is exported to the global ocean, upper-NADW is characterised by εNd values of -13.2 ± 1.0 (2sd) and lower-NADW exhibits values of εNd = -12.4 ± 0.4 (2sd). While both signatures overlap within error, the signature for lower-NADW is significantly more radiogenic than the traditionally used value for NADW (εNd = -13.5) due to the dominance of source waters from the Nordic Seas (NWABW and NEADW). Comparison between the concentration profiles and the corresponding Nd isotope profiles with other water mass properties such as salinity, silicate concentrations, neutral densities and chlorofluorocarbon (CFC) concentration provides novel insights into the geochemical cycle of Nd and reveals that different processes are necessary to account for the observed Nd characteristics in the subpolar and su
Struve T, van de Flierdt T, Robinson LF, et al., 2016, Neodymium isotope analyses after combined extraction of actinide and lanthanide elements from seawater and deep-sea coral aragonite, Geochemistry Geophysics Geosystems, Vol: 17, Pages: 232-240, ISSN: 1525-2027
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 (εNd = -9.20 ± 0.21 and -13.11 ± 0.21 for 15 and 2000 m water depths, respectively; intercalibration results from 14 laboratories: εNd = -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.
Jimenez-Espejo FJ, Pardos-Gene M, Martinez-Ruiz F, et al., 2015, Geochemical evidence for intermediate water circulation in the westernmost Mediterranean over the last 20 kyr BP and its impact on the Mediterranean Outflow, Global and Planetary Change, Vol: 135, Pages: 38-46, ISSN: 1872-6364
The Mediterranean Outflow (MOW) is generated by deep and intermediate waters from different basins in the Mediterranean Sea. Despite the number of studies on Mediterranean water masses, little work has been done on the source and properties of intermediate waters in the westernmost Mediterranean Sea and their links with MOW. Here we examine three marine sediment records spanning the last 20 kyr, located at key depths to trace intermediate waters along the Alboran Sea. We use a combination of redox-sensitive elements, which can serve as proxies to reconstruct variations in the water column oxygenation and the Nd isotopic composition of foraminiferal ferromanganese coatings, in order to reconstruct water mass provenance of Eastern/Western Mediterranean waters.As measured, εNd < − 9.2 and a low U/Th ratio during glacial periods can be attributed to the presence of Western Mediterranean Deep Water (WMDW) at the study sites. During deglaciation, higher Nd isotopic compositions and U/Th ratios point to an enhanced contribution of the modified Levantine Intermediate Water (LIW). The comparison between our data and other LIW and MOW records suggests that i) the lower branch of MOW is linked to WMDW during the glacial period, ii) the middle MOW branch follows LIW activity during deglaciation, while iii) the upper branch is more active during late Holocene, coinciding with LIW formation increase after sapropel deposits. This reconstruction has significant implications for an understanding of the MOW evolution.
Murphy K, Rehkämper M, Kreissig K, et al., 2015, Improvements in Cd stable isotope analysis achieved through use of liquid–liquid extraction to remove organic residues from Cd separates obtained by extraction chromatography, Journal of Analytical Atomic Spectrometry, Vol: 31, Pages: 319-327, ISSN: 1364-5544
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–liqui
Laycock A, Coles B, Kreissig K, et al., 2015, High precision Ce-142/Ce-140 stable isotope measurements of purified materials with a focus on CeO2 nanoparticles, Journal of Analytical Atomic Spectrometry, Vol: 31, Pages: 297-302, ISSN: 1364-5544
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.
Kersten M, Xiao T, Kreissig K, et al., 2014, Tracing Anthropogenic Thallium in Soil Using Stable Isotope Compositions, ENVIRONMENTAL SCIENCE & TECHNOLOGY, Vol: 48, Pages: 9030-9036, ISSN: 0013-936X
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