Imperial College London

Professor Mark Rehkämper

Faculty of EngineeringDepartment of Earth Science & Engineering

Professor of Isotope Geochemistry
 
 
 
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Contact

 

+44 (0)20 7594 6391markrehk Website

 
 
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Location

 

450Royal School of MinesSouth Kensington Campus

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Summary

 

Publications

Publication Type
Year
to

178 results found

Capper MS, Rehkämper M, Packman H, 2020, Rhenium-based complexes and in vivo testing: A brief history, ChemBioChem, Vol: 21, Pages: 2111-2115, ISSN: 1439-4227

The success of metal‐based anticancer therapeutics in the treatment of cancer is best exemplified by cisplatin. Currently used in 32 / 78 cancer regimens, the use for metal‐based therapeutics has a clear role in cancer therapy. Despite this, metal‐based 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 therapeutics such as auranofin, a gold‐based drug candidate as well as ruthenium‐based candidates, NAMI‐A, NKP‐1339 and TLD‐1433. All are undergoing current clinical trials. Another class of complexes under study are rhenium‐based; such complexes have undergone extensive in vitro testing but only seven have displayed antitumor in vivo activity which is a necessary step before entering clinical trials. This present review will document, chronologically, the rhenium‐based drug candidates that have undergone in vivo testing and the outlook for such complexes.

Journal article

Griffiths A, Packman H, Leung YL, Coles BJ, Kreissig K, Little SH, van de Flierdt T, Rehkämper Met 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.

Journal article

Sullivan K, Moore RET, Rehkämper M, Leybourne MI, Layton-Matthews D, Puxty J, Kyser Ket al., 2020, Postprandial zinc stable isotope response in human blood serum, Metallomics, ISSN: 1756-5901

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 concentration decrease by about 20%, depending on the size of meal, approximately 3 hours postprandially (i.e. after eating), before returning to baseline values if no meals are consumed over the following 4 to 5 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 peak 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.

Journal article

Moore R, Ullah I, de Oliveira VH, Hammond SJ, Strekopytov S, Tibbett M, Dunwell JM, Rehkamper Met al., 2020, 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, Horticulture Research, Vol: 7, ISSN: 2052-7276

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.

Journal article

Barraza F, Moore R, Rehkamper M, Schreck E, Lefeuvre G, Kreissig K, Coles B, Maurice Let 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.

Journal article

Xie RC, Rehkamper M, Grasse P, van de Flierdt T, Frank M, Xue Zet al., 2019, Isotopic evidence for complex biogeochemical cycling of Cd in the eastern tropical South Pacific (vol 512, 134, 2019), EARTH AND PLANETARY SCIENCE LETTERS, Vol: 524, ISSN: 0012-821X

Journal article

Zhang P, Misra S, Guo Z, Rehkamper M, Valsami-Jones Eet al., 2019, Stable isotope labelling of metal/metal oxide nanomaterials for environmental and biological tracing, Nature Protocols, Vol: 14, Pages: 2878-2899, ISSN: 1750-2799

Engineered nanomaterials are often compositionally indistinguishable from their natural counterparts and thus their tracking in the environment or within biota requires the development of appropriate labelling tools. Stable isotope labelling has become a well-established such tool, developed to assign “ownership” or “source” to engineered nanomaterial enabling their tracing and quantification, especially in complex environments. A particular methodological challenge for the stable isotope labelling is to ensure the label is traceable in a range of environmental scenarios but without inducing modification of the properties of the nanoamaterial and without loss of signal from the label, thus retaining realism and relevance. This protocol describes the strategy for stable isotope labelling of several widely used metal and metal oxide nanomaterials, namely ZnO, CuO, Ag, and TiO2, using isotopically enriched precursors, namely 67Zn or 68Zn metal, 65CuCl2, 107Ag or 109Ag metal, and 47 TiO2 powder. A complete synthesis requires 1 to 8 days depending on the type of nanomaterial, 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 monitoring the environmental transformation of labelled silver nanomaterials are also described. We anticipate this labelling strategy can be adopted by industry to facilitate applications such as nanosafety assessments before nanomaterials enter the market and environment as well as product authentication and tracking.

Journal article

Rehkamper M, Moore R, Maret W, Larner Fet al., 2019, Assessment of coupled Zn concentration and natural stable isotope analyses of urine as a novel probe of Zn status, Metallomics, Vol: 11, Pages: 1506-1517, ISSN: 1756-5901

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.

Journal article

Junk T, Rehkamper M, Laycock A, 2019, High-sensitivity tracing of stable isotope labeled Ag nanoparticles in environmental samples using MC-ICP-MS, Journal of Analytical Atomic Spectrometry, Vol: 34, Pages: 1173-1183, ISSN: 1364-5544

Silver nanoparticles (Ag NPs) are among the most widely used engineered nanomaterials and this warrants further investigation of their behaviour and fate in the environment. To support such work, we developed new techniques for efficient tracing of Ag NPs that are produced from, and hence labelled with, enriched 109 28 Ag (Ag-En). The methods encompass a one-step anion exchange separation of Ag from the sample matrix and precise determination of 109Ag/107Ag ratios and 109Ag abundances by multiple-collector ICP-MS. The sample preparation procedure has an Ag yield of 104 ± 13% (1 SD) and a procedural Ag blank of less than 7 pg, enabling analysis of samples with only trace Ag contents.Analyses of Ag solutions and realistic samples show that careful correction of memory effects is paramount for ensuring data quality. Using appropriate procedures, the 109Ag/107Ag ratios of samples containing Ag-En can be determined to a precision and trueness of better than about 0.5%, when more than 0.5 ng Ag are available for analysis. Even if Ag is only present at 50 pg or less, the Ag isotope ratios and Ag-En concentrations of samples can be measured to better than 5 to 10%. The methods are therefore able to resolve the presence of 1 pg of Ag-En in samples that contain as little as 10 pg and to up to 1 ng of natural Ag. As such, the techniques allow robust detection and quantification of Ag-En in environmental samples even when highly variable quantities of Ag-En and natural Ag are present. The new methodology thus enables the use of stable isotope tracing to investigate the fate of Ag NPs in complex environmental systems at dosing concentrations similar to the predicted environmental concentrations and for very small samples, whilst also providing high sample throughput.

Journal article

Xie RC, Rehkamper M, Grasse P, van de Flierdt T, Frank M, Xue Zet al., 2019, Isotopic evidence for complex biogeochemical cycling of Cd in the eastern tropical South Pacific, Earth and Planetary Science Letters, Vol: 512, Pages: 134-146, ISSN: 0012-821X

Over the past decades, observations have confirmed decreasing oxygen levels and shoaling of oxygen minimum zones (OMZs) in the tropical oceans. Such changes impact the biogeochemical cycling of micronutrients such as Cd, but the potential consequences are only poorly constrained. Here, we present seawater Cd concentrations and isotope compositions for 12 depth profiles at coastal, nearshore and offshore stations from 4ºS to 14ºS in the eastern tropical South Pacific, where one of the world’s strongest OMZs prevails.The depth profiles of Cd isotopes display high δ114/110 Cd at the surface and decreasing δ114/110 Cd with increasing water depth, consistent with preferential utilization of lighter Cd isotopes during biological uptake in the euphotic zone and subsequent remineralization of the sinking biomass. In the surface and subsurface ocean, seawater displays similar δ114/110 Cd signatures of 0.47 ±0.23‰ to 0.82±0.05‰ across the entire eastern tropical South Pacific despite highly variable Cd concentrations between 0.01 and 0.84 nmol/kg. This observation, best explained by an open system steady-state fractionation model, contrasts with previous studies of the South Atlantic and South Pacific Oceans, where only Cd-deficient waters have a relatively constant Cd isotope signature. For the subsurface to about 500 m depth, the variability of seawater Cd isotope compositions can be modeled by mixing of remineralized Cd with subsurface water from the base of the mixed layer. In the intermediate and deep eastern tropical South Pacific (>500 m), seawater [Cd] and δ114/110 Cd appear to follow the distribution and mixing of major water masses. We identified modified AAIW of the ETSP to be more enriched in [Cd] than AAIW from the source region, whilst both water masses have similar δ114/110 Cd. A mass balance estimate thus constrains a δ114/110 Cd of between 0.38‰ and 0.56‰ for the

Journal article

Wiggenhauser M, Bigalke M, Imseng M, Keller A, Rehkämper M, Wilcke W, Frossard Eet al., 2019, Using isotopes to trace freshly applied cadmium through mineral phosphorus fertilization in soil-fertilizer-plant systems, Science of the Total Environment, Vol: 648, Pages: 779-786, ISSN: 0048-9697

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.

Journal article

Kocher S, Wilkinson JJ, Armstrong RN, McDonald L, Rehkaemper M, Creaser RA, Lode JNet al., 2019, Trace element chemistry, polytypes, isotopic composition and Re-Os dates of molybdenite from the Bingham Canyon Cu-Au-Mo porphyry deposit, Utah, 15th SGA Biennial Meeting on Life with Ore Deposits on Earth, Publisher: SOC GEOLOGY APPLIED MINERAL DEPOSITS-SGA, Pages: 1120-1123

Conference paper

Imseng M, Wiggenhauser M, Keller A, Müller M, Rehkamper M, Murphy K, Kreissig K, Frossard E, Wilcke W, Bigalke Met 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.

Journal article

Moore R, Rehkamper M, Kreissig K, Strekopytov S, Larner Fet 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.

Journal article

Brett A, Prytulak J, Hammond SJ, Rehkamper Met al., 2018, Thallium mass fraction and stable isotope ratios of sixteen geological reference materials, Geostandards and Geoanalytical Research, Vol: 42, Pages: 339-360, ISSN: 1639-4488

Thallium stable isotope ratio and mass fraction measurements were performed on sixteen geological reference materials spanning three orders of magnitude in thallium mass fraction, including both whole-rock and partially-separated mineral powders. For stable isotope ratio measurements, a minimum of three independent digestions of each reference material were obtained. High-precision trace element measurements (including Tl) were also performed for the majority of these RMs. The range of Tl mass fractions represented is 10 ng g-1 to 16 μg g-1, and Tl stable isotope ratios (reported for historical reasons as ε205Tl relative to NIST SRM 997) span the range -4 to +2. With the exception – attributed to between-bottle heterogeneity – of G-2, the majority of data are in good agreement with published or certified values, where available. The precision of mean of independent measurement results between independent dissolutions suggests that, for the majority of materials analysed, a minimum digested mass of 100 mg is recommended tomitigate the impact of small-scale powder heterogeneity. Of the sixteen materials analysed, we therefore recommend for use as Tl reference materials the USGS materials BCR-2, COQ-1, GSP-2, and STM-1; CRPG materials AL-I, AN-G, FK-N, ISH-G, MDO-G, Mica-Fe, Mica-Mg, and UB-N; NIST SRM 607; and OREAS14P.

Journal article

Khondoker R, Weiss DJ, van de Flierdt T, Rehkamper M, Kreissig K, Coles BJ, Strekopytov S, Humphreys-Williams E, Dong S, Bory A, Bout-Roumazeilles V, Smichowski P, Cid-Agüero P, Babinski M, Losno R, Monna Fet 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.

Journal article

Schlitzer R, Anderson RF, Dodas EM, Lohan M, Geibert W, Tagliabue A, Bowie A, Jeandel C, Maldonado MT, Landing WM, Cockwell D, Abadie C, Abouchami W, Achterberg EP, Agather A, Aguliar-Islas A, van Aken HM, Andersen M, Archer C, Auro M, de Baar HJ, Baars O, Baker AR, Bakker K, Basak C, Baskaran M, Bates NR, Bauch D, van Beek P, Behrens MK, Black E, Bluhm K, Bopp L, Bouman H, Bowman K, Bown J, Boyd P, Boye M, Boyle EA, Branellec P, Bridgestock L, Brissebrat G, Browning T, Bruland KW, Brumsack HJ, Brzezinski M, Buck CS, Buck KN, Buesseler K, Bull A, Butler E, Cai P, Mor PC, Cardinal D, Carlson C, Carrasco G, Casacuberta N, Casciotti KL, Castrillejo M, Chamizo E, Chance R, Charette MA, Chaves JE, Cheng H, Chever F, Christl M, Church TM, Closset I, Colman A, Conway TM, Cossa D, Croot P, Cullen JT, Cutter GA, Daniels C, Dehairs F, Deng F, Dieu HT, Duggan B, Dulaquais G, Dumousseaud C, Echegoyen-Sanz Y, Edwards RL, Ellwood M, Fahrbach E, Fitzsimmons JNet al., 2018, The GEOTRACES Intermediate Data Product 2017, Chemical Geology, Vol: 493, Pages: 210-223, ISSN: 0009-2541

The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or alo

Journal article

Bridgestock L, Rehkamper M, van de Flierdt T, Paul M, Milne A, Lohan MC, Achterberg EPet al., 2018, The distribution of lead concentrations and isotope compositions in the eastern Tropical Atlantic Ocean, Geochimica et Cosmochimica Acta, Vol: 225, Pages: 36-51, ISSN: 0016-7037

Anthropogenic emissions have dominated marine Pb sources during the past century. Here we present Pb concentrations and isotope compositions for ocean depth profiles collected in the eastern Tropical Atlantic Ocean (GEOTRACES section GA06), to trace the transfer of anthropogenic Pb into the ocean interior. Variations in Pb concentration and isotope composition were associated with changes in hydrography. Water masses ventilated in the southern hemisphere generally featured lower 206Pb/207Pb and 208Pb/207Pb ratios than those ventilated in the northern hemisphere, in accordance with Pb isotope data of historic anthropogenic Pb emissions. The distributions of Pb concentrations and isotope compositions in northern sourced waters were consistent with differences in their ventilation timescales. For example, a Pb concentration maximum at intermediate depth (600–900 m, 35 pmol kg−1) in waters sourced from the Irminger/Labrador Seas, is associated with Pb isotope compositions (206Pb/207Pb = 1.1818–1.1824, 208Pb/207Pb = 2.4472–2.4483) indicative of northern hemispheric emissions during the 1950s and 1960s close to peak leaded petrol usage, and a transit time of ∼50–60 years. In contrast, North Atlantic Deep Water (2000–4000 m water depth) featured lower Pb concentrations and isotope compositions (206Pb/207Pb = 1.1762–1.184, 208Pb/207Pb = 2.4482–2.4545) indicative of northern hemispheric emissions during the 1910s and 1930s and a transit time of ∼80–100 years. This supports the notion that transient anthropogenic Pb inputs are predominantly transferred into the ocean interior by water mass transport. However, the interpretation of Pb concentration and isotope composition distributions in terms of ventilation timescales and pathways is complicated by (1) the chemical reactivity of Pb in the ocean, and (2) mixing of waters ventilated during different time periods. The complex effects of water mass mixing on Pb distri

Journal article

Imseng M, Wiggenhauser M, Keller A, Müller M, Rehkamper M, Murphy K, Kreissig K, Frossard E, Wilcke W, Bigalke Met 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.

Journal article

Palk C, Andreasen R, Rehkamper M, Stunt A, Kreissig K, Coles B, Schönbächler M, Smith Cet 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

Journal article

Laycock A, Romero-Freire A, Najorka J, Svendsen C, van Gestel CAM, Rehkamper Met al., 2017, A novel multi-isotope tracer approach to test ZnO nanoparticle and soluble Zn bioavailability in joint soil exposures, Environmental Science and Technology, Vol: 51, Pages: 12756-12763, ISSN: 0013-936X

Here we use two enriched stable isotopes, 68Znen and 64Znen (>99%), to prepare 68ZnO nanoparticles (NPs) and soluble 64ZnCl2. The standard LUFA 2.2 test soil was dosed with 68ZnO NPs and soluble 64ZnCl2 to 5 mg kg-1 each, plus between 0 and 95 mg kg-1 of soluble ZnCl2 with a natural isotope composition. After 0, 1, 3, 6 and 12 months of soil incubation, earthworms (Eisenia andrei) were introduced for 72-hour exposures. Analyses of soils, pore waters and earthworm tissues using multiple collector ICP-MS allowed the simultaneous measurement of the diagnostic 68Zn/66Zn, 64Zn/66Zn and 68Zn/64Zn ratios, from which the three different isotopic forms of Zn were quantified. Eisenia andrei was able to regulate Zn body concentrations with no difference observed between the different total dosing concentrations. The accumulation of labelled Zn by the earthworms showed a direct relationship with the proportion of labelled to total Zn in the pore water, which increased with longer soil incubation times and decreasing soil pH. The 68Znen/64Znen ratios determined for earthworms (1.09 ± 0.04), soils (1.09 ± 0.02) and pore waters (1.08 ± 0.02) indicate indistinguishable environmental distribution and uptake of the Zn forms, most likely due to rapid dissolution of the ZnO NPs.

Journal article

de Baar HJW, van Heuven SMAC, Abouchami W, Xue ZICHEN, Galer SJG, Rehkamper M, Middag R, van Ooijen Jet al., 2017, Interactions of dissolved CO2 with Cadmium Isotopes in the Southern Ocean, Marine Chemistry, Vol: 195, Pages: 105-121, ISSN: 1872-7581

Here we report the first ever observations of a strong correlation in ocean surface waters of the dissolved δ114Cd with dissolved CO2. This is observed in the Southern Ocean along the 0°W meridian in both the Antarctic Circumpolar Current and the Weddell Gyre, as well as in the Weddell Sea proper, near the Antarctic Peninsula and in Drake Passage. This uniform trend in several surface water masses hints at a uniform biochemical mechanism within the Southern Ocean. One hypothesis for the underlying mechanism would be a role of Cd in the carbonic anhydrase function for conversion of bicarbonate ion [HCO3−] into CO2, the latter being required by RuBisCO (ribulose-1,5-bisphosphate carboxylase/oxygenase) that only accepts CO2. At low ambient [CO2] the algae maintain growth by also operating a Carbon Concentrating Mechanism (CCM) for utilization of [HCO3−] and its conversion to CO2. For this the algae need more enzyme carbonic anhydrase that normally has Zn as its co-factor, but Cd may substitute for Zn and there also are Cd-specific carbonic anhydrases known for some phytoplankton species. Indeed in incubations of the local plankton communities it is shown that the phytoplankton have a very strong preferential uptake of CO2, such that the uptake ratio {[CO2]/[HCO3−]} is much higher than the dissolved ratio {[CO2]/[HCO3−]} in ambient seawater. Therefore the here reported observations in the Southern Ocean are also expressed for δ114Cd as function of the ratio {[CO2]/[HCO3−]} in ambient seawater. Future research of local phytoplankton in unperturbed natural waters of the Southern Ocean is recommended to be able to verify the hypothesis of a function of Cd in carbonic anhydrase in Antarctic phytoplankton.

Journal article

Poole GM, Rehkamper M, Coles BJ, Goldberg T, Smith CLet al., 2017, Nucleosynthetic molybdenum isotope anomalies in ironmeteorites – new evidence for thermal processing of solarnebula material, Earth and Planetary Science Letters, Vol: 473, Pages: 215-226, ISSN: 1385-013X

We have investigated nucleosynthetic Mo isotope anomalies in 38 different bulk iron meteorites from 11 groups, to produce by far the largest and most precise dataset available to date for such samples. All magmatic iron groups were found to display deficits in s-process Mo isotopes, with essentially constant anomalies within but significant variations between groups. Only meteorites of the non-magmatic IAB/IIICD complex revealed terrestrial Mo isotopic compositions.The improved analytical precision achieved in this study enables two isotopically distinct suites of iron meteorites to be identified. Of these, the r=p suite encompasses the IC, IIAB, IIE, IIIAB, IIIE and IVA groups and exhibits relatively modest but ‘pure’ s-process deficits, relative to Earth. The second r>p suite includes groups IIC, IIIF and IVB. These iron meteorites show larger s-process deficits than the r=p suite, coupled with an excess of r-process relative to p-process components.Comparison of the results with data for other elements (e.g., Cr, Ni, Ru, Ti, Zr) suggests that the Mo isotope variability is most likely produced by thermal processing and selective destruction of unstable presolar phases. An updated model is proposed, which relates the iron meteorite suites to different extents of thermal processing in the solar nebula, as governed by heliocentric distance. In detail, the r=p suite of iron meteorite parent bodies is inferred to have formed closer to the Sun, where the extent of thermal processing was similar to that experienced by terrestrial material, so that the meteorites exhibit only small s-process deficits relative to Earth. In contrast, the r>p suite formed at greater heliocentric distance, where more subtle thermal processing removed a smaller proportion of r- and p-process host phases, thereby generating larger s-process deficits relative to the terrestrial composition. In addition, the thermal conditions enabled selective destruction of p- versus r-isotope

Journal article

Bridgestock L, Rehkamper M, van de Flierdt T, Murphy K, Khondoker R, Baker AR, Chance R, Strekopytov S, Humphreys-Williams E, Achterberg EPet al., 2017, The Cd isotope composition of atmospheric aerosols from the tropical Atlantic Ocean, Geophysical Research Letters, Vol: 44, Pages: 2932-2940, ISSN: 1944-8007

Stable isotope compositions can potentially be used to trace atmospheric Cd inputs to the surface ocean and anthropogenic Cd emissions to the atmosphere. Both of these applications may provide valuable insights into the effects of anthropogenic activities on the cycling of Cd in the environment. However, a lack of constraints for the Cd isotope compositions of atmospheric aerosols is currently hindering such studies. Here we present stable Cd isotope data for aerosols collected over the Tropical Atlantic Ocean. The samples feature variable proportions of mineral dust-derived and anthropogenic Cd, yet exhibit similar isotope compositions, thus negating the distinction of these Cd sources by using isotopic signatures in this region. Isotopic variability between these two atmospheric Cd sources may be identified in other areas, and thus warrants further investigation. Regardless, these data provide important initial constraints on the isotope composition of atmospheric Cd inputs to the ocean.

Journal article

Moore RET, Larner F, Coles BJ, Rehkämper Met al., 2017, High precision zinc stable isotope measurement of certified biological reference materials using the double spike technique and multiple collector-ICP-MS, Analytical and Bioanalytical Chemistry, Vol: 409, Pages: 2941-2950, ISSN: 1618-2650

Biological reference materials with well-characterized stable isotope compositions are lacking in the field of ‘isotope biochemistry’, which seeks to understand bodily processes that rely on essential metals by determiningmetal stable isotope ratios. Here, we present Zn stable isotope data for six biological reference materials with certified trace metal concentrations, fish muscle, bovine muscle, pig kidney, human hair,human blood serum and human urine. Replicate analyses of multiple aliquots of each material achieved reproducibilities (2sd) of 0.04-0.13 ‰ for δ66/64Zn 22 (which denotes the deviation of the 66 Zn/64Zn ratio of a sample from a pure Zn reference material in parts per 1000). This implies only very minor isotopic heterogeneities within the samples, rendering them suitable as quality control materials for Zn isotopeanalyses. This endorsement is reinforced by (i) the close agreement of our Zn isotope data for two of the samples (bovine 2 muscle and human blood serum) to previously published results for different batches of the same material and (ii) the similarity of the isotopic data for the samples (δ66/64Zn≈ –0.8 to 0.0 ‰) to previously published Zn isotope results for similar biological materials. Further tests revealed that the applied Zn separation procedure is sufficiently effective to enable accurate data acquisition even at low mass resolving power (M/ΔM ≈ 400), as measurements and analyses conducted at much higher mass resolution (M/ΔM ≈ 8500) delivered essentially identicalresults.

Journal article

Nielsen SG, Rehkämper M, Prytulak, 2017, Investigation and application of thallium isotope fractionation, Reviews in Mineralogy and Geochemistry, Vol: 82, Pages: 759-798, ISSN: 1529-6466

This contribution summarizes the current state of understanding and recent advances made in the field of stable thallium (Tl) isotope geochemistry. High precision measurements of Tl isotope compositions were developed in the late 1990s with the advent ofmultiple collector inductively coupled plasma mass spectrometry(MC-ICP MS) and subsequent studies revealed that Tl, despite the small relative mass difference of the two isotopes, exhibits substantial stable isotope fractionation, especially in the marine environment. The most fractionated reservoirs identified are ferromanganese sediments with ε205 Tl≈ +15 and low temperature altered oceanic crust with ε205 Tl≈–20. The total isotopic variability of more than 35 ε 205 Tl-units hence exceeds the current analytical reproducibility ofthe measurement technique by more than a factor of 70. This isotopic variation can be explained by invoking a combination of conventional mass dependent equilibrium isotope effects and nuclear field shift isotope fractionation, but the specific mechanismsare still largely unaccounted for. Thallium isotopes have been applied to investigate paleoceanographic processes in the Cenozoic and there is evidence to suggest that Tl isotopes may be utilized as a monitor of the marine manganese oxide burial flux over million year time scales. In addition, Tl isotopes can be used to calculate the magnitude of hydrothermal fluid circulation through ocean crust. It has also been shown that the subduction of marine ferromanganese sediments can be detected with Tl isotopes in lavas erupted in subduction zone settings as well as in ocean island basalts. Meteorite samples display Tl isotope variations that exceed the terrestrial range with a total variability of about 50 ε205 Tl. The large isotopic diversity, however, is generated by both stable Tl isotope fraction

Journal article

Archer C, Andersen MB, Cloquet C, Conway TM, Dong S, Ellwood M, Moore R, Nelson J, Rehkamper M, Rouxel O, Samanta M, Shin KC, Sohrin Y, Takano S, Wasylenki Let al., 2016, Inter-calibration of a proposed new primary reference standard AA-ETH Zn for zinc isotopic analysis, Journal of Analytical Atomic Spectrometry, Vol: 32, Pages: 415-419, ISSN: 0267-9477

We have prepared a large volume of pure, concentrated and homogenous zinc standard solution. This new standard solution is intended to be used as a primary reference standard for the zinc isotope community, and to serve as a replacement for the nearly exhausted current reference standard, the so-called JMC-Lyon Zn. The isotopic composition of this new zinc standard (AA-ETH Zn) has been determined through an inter-laboratory calibration exercise, calibrated against the existing JMC-Lyon standard, as well as the certified Zn reference standard IRMM-3702. The data show that the new standard is isotopically indistinguishable from the IRMM-3702 zinc standard, with a weighted δ66/64Zn value of 0.28 ± 0.02‰ relative to JMC-Lyon. We suggest that this new standard be assigned a δ66/64Zn value of +0.28‰ for reporting of future Zn isotope data, with the rationale that all existing published Zn isotope data are presented relative to the JMC-Lyon standard. Therefore our proposed presentation allows for a direct comparison with all previously published data, and that are directly traceable to a certified reference standard, IRMM-3702 Zn. This standard will be made freely available to all interested labs through contact with the corresponding author.

Journal article

Prytulak J, Brett A, Webb M, Plank T, Rehkamper M, Savage PS, Woodhead Jet al., 2016, Thallium elemental behavior and stable isotope fractionation during magmatic processes, Chemical Geology, Vol: 448, Pages: 71-83, ISSN: 1872-6836

Stable thallium (Tl) isotopes are an extremely sensitive tracer for the addition of small amounts of sediments or materials altered at low temperatures to the source(s) of mantle-derived melts. The ability of Tl to trace such materials is due to the largeconcentration contrast between the mantle (Tl < 2ng/g) and possible exotic inputs (Tl$+" ~100ng/g to >g/g), which also often display fractionated Tl isotope compositions.However, the magnitude of Tl isotope fractionation induced by igneous processesalone has not been systematically assessed. Here, two suites of co-genetic magmas, spanning a large range of differentiation, from Hekla, Iceland, and Anatahan, in the Mariana arc, are used to assess the behavior of thallium and its stable isotope variations during magmatic processes. Thallium behaves as a near-perfectly incompatible lithophile element throughout magmatic evolution, mirroring elements such as Rb, Cs, and K. Lavas from Hekla have restricted Cs/Tl ratios and stable Tl isotope compositions, which overlap with mantle estimates. Lavas from subduction-related Anatahan volcano also have a restricted range in Tl isotope composition, which overlaps with Hekla and MORB, demonstrating that fractional crystallisation and partial melting does not fractionate stable Tl isotopes. Subduction environments display variable Cs/Tl, indicating that the subduction process commonly fractionates these two elements. The immunity of thallium stable isotopes to fractionation by magmatic processes coupled with its extreme sensitivity for tracing pelagic sediments, FeMn crusts and low temperature altered oceanic crust highlight its value in elucidating the nature of mantle sources of both oceanic basalts and arc lavas. Critically, meaningful interpretation of thallium isotope compositions need not be restricted to primitive lavas.

Journal article

Hunt AC, Benedix GK, Hammond SJ, Bland PA, Rehkamper M, Kreissig K, Strekopytov Set 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

Journal article

Bridgestock L, van de Flierdt T, Rehkamper M, Paul M, Middag R, Milne A, Lohan MC, Baker AR, Chance R, Khondoker R, Strekopytov S, Humphreys-Williams E, Achterberg EP, Rijkenberg MJA, Gerringa LJA, de Baar HJWet al., 2016, Return of naturally sourced Pb to Atlantic surface waters, NATURE COMMUNICATIONS, Vol: 7, ISSN: 2041-1723

Journal article

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