Cadmium and neodymium geochemical cycles in the marine environment

The roles of trace elements and their isotopes in the marine environment are essential and diverse (e.g., nutrients, tracers of oceanic processes, anthropogenic pollutants), but are not well understood yet. In this thesis, two elements and their isotopes were investigated in two distinct marine environments: cadmium (Cd) in the Siberian shelf seas and neodymium (Nd) in the western North Atlantic Ocean. Whereas the role of Cd as nutrient in the open ocean is reflected by Cd isotope data, its behaviour in estuaries is poorly constrained. Chapter 2 of this thesis presents new Cd isotopes and concentrations of 19 water samples from the mixing zone of Siberian rivers with the Arctic Ocean. The results provide the first constraints on the isotope composition of natural riverine Cd fluxes to the ocean and the cycling of Cd in a shelf environment. Chapter 3 describes the method developed to isolate and analyse seawater Nd isotopes and concentrations in the MAGIC laboratories. The Nd isotopic composition of seawater is a promising tracer for ocean circulation and exchange between the continental margins and the oceans. By analysing 12 seawater depth profiles from the Dutch GEOTRACES transect GA02 (Chapters 4 and 5), we demonstrate that Nd features different behaviour in regions close to the formation area of deep water masses compared to export areas, where it behaves conservatively away from continental margins. Besides, we show that upper- North Atlantic Deep Water (NADW) and lower-NADW have distinct Nd isotopic compositions, and that the signature of lower-NADW is significantly more radiogenic than the commonly accepted value, which should be taken into account for future applications. Overall, the present thesis underlines the important role that isotope analyses can play in deciphering marine biogeochemical cycles of trace elements.Open Acces

Lycopene isomerisation takes place within enterocytes during absorption in human subjects

Lycopene in fruits and vegetables occurs mostly (80-97%) in the all-E configuration, whereas a considerable proportion of lycopene in the human body is present as Z-isomers. The Z-isomers offer potentially better health benefits and show improved antioxidant activity in vitro when compared with the all-E-isomer. The absorption of dietary lycopene is a complex process involving transfer of the carotenoid from the food matrix into micelles, uptake by enterocytes, packaging into chylomicrons and finally secretion into plasma. Isomerisation could take place at any of these individual steps. By exploiting in vitro and in vivo models, we traced lycopene isomerisation during absorption using various methods to mimic gastric and duodenal conditions, incorporation into mixed micelles, absorption and metabolism by various Caco-2 cell clones, and performed a postprandial study in human subjects to identify the profile of lycopene isomers in plasma chylomicrons. We demonstrate that all-E-lycopene remains unchanged during its passage in the gastrointestinal tract, including its incorporation into mixed micelles. The key site of lycopene isomerisation is inside the intestinal cells resulting in 29% of lycopene as Z-isomers. Lycopene isomerisation in the various Caco-2 cell clones is consistent with that observed in human chylomicrons formed in a postprandial state. There is no selection in the release of lycopene isomers from enterocytes. Although there is a huge inter-individual variability of total lycopene absorption reported both in in vitro intestinal cell lines as well as in human chylomicrons, the lycopene isomer profile is quite simila

The proportion of lycopene isomers in human plasma is modulated by lycopene isomer profile in the meal but not by lycopene preparation

Dietary lycopene consists mostly of the (all-E) isomer. Upon absorption, (all-E) lycopene undergoes isomerisation into various (Z)-isomers. Because these isomers offer potentially better health benefits than the (all-E) isomer, the aim of the present study was to investigate if the profile of lycopene isomers in intestinal lipoproteins is affected by the profile of lycopene isomers in the meal and by the tomato preparation. Six postprandial, crossover tests were performed in healthy men. Three meals provided about 70% of the lycopene as (Z)-isomers, either mainly as 5-(Z) or 13-(Z), or as a mixture of 9-(Z) and 13-(Z) lycopene, while three tomato preparations provided lycopene mainly as the (all-E) isomer. Consumption of the 5-(Z) lycopene-rich meal led to a high (60%) proportion of this isomer in TAG-rich lipoproteins (TRL), indicating a good absorption and/or a low intestinal conversion of this isomer. By contrast, consumption of meals rich in 9-(Z) and 13-(Z) lycopene isomers resulted in a low level of these isomers but high amounts of the 5-(Z) and (all-E) isomers in TRL. This indicates that the 9-(Z) and 13-(Z) isomers were less absorbed or were converted into 5-(Z) and (all-E) isomers. Dietary (Z)-lycopene isomers were, therefore, differently isomerised and released in TRL during their intestinal absorption in men. Consuming the three meals rich in (all-E) lycopene resulted in similar proportions of lycopene isomers in TRL: 60% (all-E), 20% 5-(Z), 9% 13-(Z), 2% 9-(Z) and 9% unidentified (Z)-isomers. These results show that the tomato preparation has no impact on the lycopene isomerisation occurring during absorption in human

Neodymium in the oceans: a global database, a regional comparison, and implications for palaeoceanographic research

The neodymium (Nd) isotopic composition of seawater has been used extensively to reconstruct ocean circulation on a variety of time scales. However, dissolved neodymium concentrations and isotopes do not always behave conservatively, and quantitative deconvolution of this non-conservative component can be used to detect trace metal inputs and isotopic exchange at ocean–sediment interfaces. In order to facilitate such comparisons for historical datasets, we here provide an extended global database for Nd isotopes and concentrations in the context of hydrography and nutrients. Since 2010, combined datasets for a large range of trace elements and isotopes are collected on international GEOTRACES section cruises, alongside classical nutrient and hydrography measurements. Here, we take a first step towards exploiting these datasets by comparing high-resolution Nd sections for the western and eastern North Atlantic in the context of hydrography, nutrients and aluminium (Al) concentrations. Evaluating those data in tracer–tracer space reveals that North Atlantic seawater Nd isotopes and concentrations generally follow the patterns of advection, as do Al concentrations. Deviations from water mass mixing are observed locally, associated with the addition or removal of trace metals in benthic nepheloid layers, exchange with ocean margins (i.e. boundary exchange) and/or exchange with particulate phases (i.e. reversible scavenging). We emphasize that the complexity of some of the new datasets cautions against a quantitative interpretation of individual palaeo Nd isotope records, and indicates the importance of spatial reconstructions for a more balanced approach to deciphering past ocean changes

Particle-seawater interaction of neodymium in the North Atlantic

Dissolved neodymium (Nd) isotopes (expressed as εNd) have been widely used as a water mass tracer in paleoceanography. However, one aspect of the modern biogeochemical cycle of Nd that has been sparsely investigated is the interplay between dissolved and particulate phases in seawater. We here present the first regional data set on particulate Nd isotope compositions (εNdp) and concentrations ([Nd]p) from five stations in the western North Atlantic Ocean along the GEOTRACES GA02 transect, in conjunction with previously published dissolved Nd isotope compositions (εNdd) and concentrations ([Nd]d)1. Key observations and interpretations from our new particulate data set include the following: (1) A low fractional contributions of [Nd]p to the total Nd inventory per volume unit of seawater (~5%), with significant increases of up to 45% in benthic boundary layers. (2) Increasing Nd concentrations in suspended particulate matter ([Nd]SPM) and fractions of lithogenic material with water depth, suggesting the removal of Nd poor phases. (3) Different provenances of particulates in the subpolar and subtropical gyres as evidenced by their Nd isotope fingerprints reaching from εNdp ≈ -20 near the Labrador Basin (old continental crust), over εNdp ≈ -4 between Iceland and Greenland (young mafic provenance), to values of εNdp ≈-13 in the subtropics (similar to African dust signal). (4) Vertical heterogeneity of εNdp, as well as large deviations from ambient seawater values in the subpolar gyre, indicate advection of lithogenic particles in this area. (5) Vertically homogenous εNdp values in the subtropical gyre, indistinguishable from εNdd values, are indicative of predominance of vertical particulate supply. The process of reversible scavenging only seems to influence particulate signatures below 3 km. Overall, we do not find evidence on enhanced particle dissolution, often invoked to explain the observed increase in dissolved Nd in the North Atlantic

Neodymium isotope analyses after combined extraction of actinide and lanthanide elements from seawater and deep-sea coral aragonite

Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 17 (2016): 232–240, doi:10.1002/2015GC006130.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.Funding that supported this work was received from the National Science Foundation (NSF 0752402), the Leverhulme Trust (RPG-398), the Natural Environmental Research Council (NE/J021636/1 and NE/N003861/1), the European Research Council (278705), and the Grantham Institute for Climate Change.2016-07-0

Neodymium isotopic composition and concentration in the western North Atlantic Ocean:results from the GEOTRACES GA02 section

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 subtropical gyres and throughout the vertical water column. While our data set provides additional insights into the contribution of boundary exchange in areas of sediment resuspension, the results for open ocean seawater demonstrate, at an unprecedented level, the suitability of Nd isotopes to trace modern water masses in the strongly advecting western Atlantic Ocean

Neodymium in the oceans: a global database, a regional comparison and implications for palaeoceanographic research

The neodymium (Nd) isotopic composition of seawater has been used extensively to reconstruct ocean circulation on a variety of timescales. However, dissolved neodymium concentrations and isotopes do not always behave conservatively, and quantitative deconvolution of this non-conservative component can be used to detect trace metal inputs and isotopic exchange at ocean–sediment interfaces. In order to facilitate such comparisons for historical datasets, we here provide an extended global database for Nd isotopes and concentrations in the context of hydrography and nutrients. Since 2010, combined datasets for a large range of trace elements and isotopes are collected on international GEOTRACES section cruises, alongside classical nutrient and hydrography measurements. Here, we take a first step towards exploiting these datasets by comparing high-resolution Nd sections for the western and eastern North Atlantic in the context of hydrography, nutrients and aluminium (Al) concentrations. Evaluating those data in tracer–tracer space reveals that North Atlantic seawater Nd isotopes and concentrations generally follow the patterns of advection, as do Al concentrations. Deviations from water mass mixing are observed locally, associated with the addition or removal of trace metals in benthic nepheloid layers, exchange with ocean margins (i.e. boundary exchange) and/or exchange with particulate phases (i.e. reversible scavenging). We emphasize that the complexity of some of the new datasets cautions against a quantitative interpretation of individual palaeo Nd isotope records, and indicates the importance of spatial reconstructions for a more balanced approach to deciphering past ocean changes

Particulate Neodymium Isotopes and Concentrations in the Western North Atlantic

Particulate neodymium (Nd) isotopes and concentration were measured on samples collected along a transect during cruises PE-319 and PE-321 (R/V Pelagia, NED) in 2010. Samples were collected using in-situ pumps (ISP) at 5 stations at 6 depths each. Samples were analysed for Nd isotopes and concentrations at Imperial College London (UK). Detailed methodology and data interpretation can be accessed via the peer-reviewed publication: doi:acsearthspacechem.0c0003