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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 Δ 114/110 Cd tot-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 Δ 114/110 Cd seq-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.

Silicate weathering is the primary control of atmospheric CO2 concentrations on multiple timescales. However, tracing this process has proven difficult. Lithium isotopes are a promising tracer of silicate weathering. This study has reacted basalt sand with natural river water for ~9 months in closed experiments, in order to examine the behaviour of Li isotopes during weathering. Aqueous Li concentrations decrease by a factor of ~10 with time, and d 7 Li increases by ~19‰, implying that Li is being taken up into secondary phases that prefer 6 Li. Mass balance using various selective leaches of the exchangeable and secondary mineral fractions suggest that ~12-16% of Li is adsorbed, and the remainder is removed into neoformed secondary minerals. The exchangeable fractionation factors have a D 7 Liexch-soln =-11.6 to-11.9‰, while the secondary minerals impose D 7 Lisecmin-soln =-22.5 to-23.9‰. Overall the experiment can be modelled with a Rayleigh fractionation factor of a = 0.991, similar to that found for natural basaltic rivers. The mobility of Li relative to the carbon-cycle-critical cations of Ca and Mg changes with time, but rapidly evolves within one month to remarkably similar mobilities amongst these three elements. Th evolution shows a linear relationship with d 7 Li (largely due to a co-variation between aqueous [Li] and d 7 Li), suggesting that Li isotopes have the potential to be used as a tracer of Ca and Mg mobility during basaltic weathering, and ultimately CO2 drawdown.

. (2012) 'Inter-element fractionation of highly siderophile elements in the Tonga Arc due to ux melting of a depleted source. ', Geochimica et Cosmochimica Acta., Further information on publisher's website:http://dx.doi.org/10.1016/j.gca.2012.03.025Publisher's copyright statement: NOTICE: this is the author's version of a work that was accepted for publication in Geochimica et Cosmochimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reected in this document. Changes may have been made to this work since it was submitted for publication. A denitive version was subsequently published in Geochimica et Cosmochimica Acta, 89, 2012Acta, 89, , 10.1016Acta, 89, /j.gca.2012 Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. with a high fluid flux is thought to have produced boninitic magmas at several arc and FSC locations.As such, this arc system provides an opportunity to assess the fluid mobility of HSEs and to investigate the effects of fluid-induced melting and prior melt depletion on HSE behaviour during both mantle melting and magma evolution.

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2018). Geochemical ngerprints of glacially eroded bedrock from West Antarctica: Detrital thermochronology, radiogenic isotope systematics and trace element geochemistry in Late Holocene glacial-marine sediments. Earth-Science Reviews, 182 pp. 204-232.For guidance on citations see FAQs. fingerprints of glacially eroded bedrock from West Antarctica: Detrital thermochronology, radiogenic isotope systematics and trace element geochemistry in Late Holocene glacial-marine sediments. AbstractGeochemical provenance studies of glacial-marine sediments provide a powerful approach to describe subglacial geology, sediment transport pathways, and past ice sheet dynamics. The marinebased West Antarctic Ice Sheet (WAIS) is considered highly vulnerable to ocean warming and sea level rise that is likely to cause its rapid and irreversible retreat. Studies of its past response to climate change are hence essential for projecting its future behaviour. The application of radiogenic and trace element provenance studies for past ice sheet reconstructions requires surveying the geographic variability of geochemical compositions of glaciomarine sediments. In this study, we characterize the provenance of the detrital fraction of 67 Late Holocene marine sediment samples collected off the Pacific margin of West Antarctica (60°W to 160°W), including 40 Ar/ 39 Ar ages of individual hornblende and biotite grains (>150μm), as well as Sr and Nd isotope and trace element composition of the fine-grained (<63μm) sediment fraction. Overall, this approach allows differentiating West Antarctica into five source regions: the Antarctic Peninsula, Bellingshausen Sea, Amundsen Sea, Wrigley Gulf-Hobbs Coast and Sulzberger Bay. Minor geochemical variability is found within each individual sector due to local variability in onland geology. 40 Ar/ 39 Ar ages of icebergrafted hornblende and biotite grains record primarily Carboniferous to Lates Quaternary ages (~0 to 380 Ma), with a notable age peak of ~100 Ma, associated with plutonic intrusions or deformation events during the mid-Cretaceous. Permian-Jurassic 40 Ar/ 39 Ar ages are widespread in the Amundsen Sea sector, marking episodes of large-volume magmatism along the long-lived continental margin.Metasedimentary rocks and Late Cenozoic alkali basalts in West Antarctica cannot be detected using detrital hornblende and biotite 40 Ar/ 39 Ar ages due to the absence or small grain-size (i.e. <150μm) of these minerals in such rocks. These sources can however be readily recognized by their fine-grained geochemical composition. In addition, geographic trends in the provenance from proximal to distal sites provide insights into major sediment transport pathways. While the transport of fine-grained detritus follows bathymetric cross-shelf troughs, the distribution of iceberg-rafted grains shows

We assess early‐to‐middle Eocene seawater neodymium (Nd) isotope records from seven Southern Ocean deep‐sea drill sites to evaluate the role of Southern Ocean circulation in long‐term Cenozoic climate change. Our study sites are strategically located on either side of the Tasman Gateway and are positioned at a range of shallow (<500 m) to intermediate/deep (~1000–2500 m) paleowater depths. Unradiogenic seawater Nd isotopic compositions, reconstructed from fish teeth at intermediate/deep Indian Ocean pelagic sites (Ocean Drilling Program (ODP) Sites 738 and 757 and Deep Sea Drilling Project (DSDP) Site 264), indicate a dominant Southern Ocean‐sourced contribution to regional deep waters (εNd(t) = −9.3 ± 1.5). IODP Site U1356 off the coast of Adélie Land, a locus of modern‐day Antarctic Bottom Water production, is identified as a site of persistent deep water formation from the early Eocene to the Oligocene. East of the Tasman Gateway an additional local source of intermediate/deep water formation is inferred at ODP Site 277 in the SW Pacific Ocean (εNd(t) = −8.7 ± 1.5). Antarctic‐proximal shelf sites (ODP Site 1171 and Site U1356) reveal a pronounced erosional event between 49 and 48 Ma, manifested by ~2 εNd unit negative excursions in seawater chemistry toward the composition of bulk sediments at these sites. This erosional event coincides with the termination of peak global warmth following the Early Eocene Climatic Optimum and is associated with documented cooling across the study region and increased export of Antarctic deep waters, highlighting the complexity and importance of Southern Ocean circulation in the greenhouse climate of the Eocene.

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 catastrophic impact, which allowed the preservation of the largely unmelted winonaites. Despite major-element similarities to both ordinary and enstatite chondrites, trace-element analysis suggests the winonaite parent body had a arbonaceous chondrite-like precursor composition. The parent body of the winonaites was volatile -depleted relative to CI, but enriched compared to the other carbonaceous classes. The closest match are the CM chondrites, however, the specific precursor is not sampled in current meteorite collections