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  • 1
    Publication Date: 2021-02-08
    Description: 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 along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 22 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017.
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  • 2
    Publication Date: 2020-02-06
    Description: Highlights • High lithogenic input in surface waters in the Panama Basin results in radiogenic εNd of up to +4.3. • Radiogenic Nd derived from particles can reset the Nd IC of water masses within time scales years. • Lithogenic input of REEs and corresponding Nd IC in surface waters are seasonally influenced. The distribution of dissolved rare earth elements (REEs) and neodymium isotopes (εNd) in the open ocean traces water mass mixing and provides information on lithogenic inputs to the source regions of the water masses. However, the processes influencing the REE budget at the ocean margins, in particular source and sink mechanisms, are not yet well quantified. In this study the first dissolved REE concentrations and Nd isotope compositions of seawater from the Panama Basin (RV Meteor cruise M90) in the Eastern Equatorial Pacific (EEP) are presented. The EEP is characterized by one of the world's largest oxygen minimum zones (OMZs). It is dominated by high particle fluxes that are expected to enhance the removal of REEs from the water column by scavenging. The measured REE concentrations peak at the surface indicating high lithogenic input, which is supported by shale-normalized REE patterns in surface waters and highly radiogenic εNd signatures ranging between +1.4 and +4.3, the latter value constituting the most radiogenic value measured for seawater to date. In contrast, intermediate and deep water REE concentrations are low compared to other Pacific Basins and suggest enhanced removal via scavenging associated with high particle fluxes. The εNd signatures of intermediate and deep waters are less radiogenic than surface waters ranging between −1.4 and +1.3 but significantly more radiogenic than source water masses in the EEP. The εNd signatures consequently do not reflect mixing of intermediate and deep water masses entering the Panama Basin but can only be explained by lithogenic inputs originating from source rocks with highly radiogenic Nd isotope signatures such as the Central American Volcanic Arc (εNd=+3 to +10). Our data demonstrate significant surface input via continental particles, which are partially dissolved in the water column and thereby release REEs and particularly radiogenic Nd isotope signatures to the subsurface ocean. Data obtained from a re-occupied station in the southern Panama Basin for the first time shows that these processes can partially reset water mass Nd isotope and REE signatures of the entire water column proximal to continental sources on time scales of a few years.
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  • 3
    Publication Date: 2020-02-06
    Description: Highlights • First comprehensive seawater Nd isotope and REE data for the Laptev Sea. • Dissolved Nd isotopes, salinity and stable oxygen isotopes trace water masses. • No evidence for REE release from particles of the organic-rich Siberian Rivers. • Preferential estuarine LREE removal follows increasing salinity from 10 to 34. • Formation and melting of sea ice redistribute REEs within water column. Abstract Marine neodymium (Nd) isotope and rare earth element (REE) compositions are valuable tracers for present and past ocean circulation and continental inputs. Yet their supply via high latitude estuaries is largely unknown. Here we present a comprehensive dissolved Nd isotope (expressed as εNd values) and REE data set together with seawater stable oxygen isotope ( O) compositions of samples from the Laptev Sea recovered in two Arctic summers and one winter. The Laptev Sea is a shallow Siberian Shelf sea characterized by extensive river-runoff, sea-ice production and ice transport into the Arctic Ocean. The large variability in εNd (−6 to −17), REE concentrations (16 to 600 pmol/kg for Nd) and REE patterns is controlled by freshwater supply from distinct riverine sources and open ocean Arctic Atlantic Water. Strikingly and contrary to expectations, except for cerium no evidence for significant release of REEs from particulate phases is found, which is attributed to low amounts of suspended particulate matter and high dissolved organic carbon concentrations present in the contributing rivers. Essentially all shelf waters are depleted in light (L)REEs, while the distribution of the heavy REEs shows a deficiency at the surface and a pronounced excess in the bottom layer. This distribution is consistent with REE removal through coagulation of riverine nanoparticles and colloids starting at salinities near 10 and resulting in a drop of all REE concentrations by ∼30%. With increasing salinity preferential LREE removal is observable reaching ∼75% for Nd at a salinity of 34. Although the delayed onset of dissolved REE removal contrasts with most previous observations from other estuarine environments, it agrees remarkably well with results from recent experiments simulating estuarine mixing of seawater with organic-rich river waters. In addition, melting and formation of sea ice leads to further REE depletion at the surface and strong REE enrichment near the shelf bottom as a function of ice melting and brine transfer, respectively. The ice-related processes significantly affect the distribution of dissolved REEs in high-latitude estuaries and likely also similarly contribute to the redistribution of other dissolved seawater constituents.
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  • 4
    Publication Date: 2021-02-08
    Description: This study investigates chromium isotope variations (δ53Cr) and REE patterns in present-day biogenic carbonates and ocean waters from Lady Elliot Island (LEI) located in the southern Great Barrier Reef (GBR), Australia, which is one of the world's largest carbonate-producing shelf ecosystems. Our results from thoroughly cleaned biogenic carbonates collected at LEI, with no detectable evidence for lithogenic Cr and/or Mn–Fe oxide coating contamination, revealed a systematic and statistically significant correlation (r2=0.83, p〈0.05) between δ53Cr and cerium anomaly (Ce/Ce*) data in molluscan shells (i.e., gastropods). This in turn implies a redox-controlled incorporation of Cr from seawater into a shell during mineralization mediated by the organism. In particular, shells with higher δ53Cr values, which approach the Cr isotope composition of local seawater, tend to be associated with more negative Ce/Ce*. Importantly, the intercept of the above δ53Cr vs. Ce/Ce* correlation points to the Cr isotope composition of local ocean water, which has an average δ53Cr of +0.82±0.13‰ (2σ relative to SRM 979). These findings thus indicate that the above multi-proxy approach could be used to reconstruct the δ53Cr signature of local paleo-seawater based on Ce/Ce* and δ53Cr data in a set of well-preserved fossil skeletal carbonates (i.e., molluscan shells) collected at a specific site. Interestingly, the only calcifying organism from LEI that yielded identical δ53Cr vs. Ce/Ce* values as those in ambient ocean water was a microbial calcitic carbonate produced by red coralline algae (Lithothamnion sp.). This organism thus seems to incorporate Cr isotopes and REE from seawater without additional biological discrimination and/or isotope fractionation effects. Considering that calcite is a more stable CaCO3 polymorph during post-depositional alternation and diagenetic stabilization of marine carbonates (compared to aragonite), the fossil counterparts of these algal-microbial carbonates (microbialites) might thus represent ideal natural archives of the paleo-seawater δ53Cr and Ce/Ce* variations over geological time. Finally, our compilation of δ53Cr data from recent marine biogenic carbonates originating from the main oceanic provinces (South/North Pacific, South/North Atlantic, Caribbean, Mediterranean Sea) confirms that marine carbonates tend to be systematically enriched in light Cr isotopes relative to local ocean waters. Trace element constraints, however, indicate that some of these shifts to lower δ53Cr values (i.e., approaching −0.1 per mil) are related to a presence of lithogenic Cr in the shells, causing a diagenetic overprint of the primary marine δ53Cr signal.
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  • 5
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    Elsevier
    In:  Earth and Planetary Science Letters, 434 . pp. 1-9.
    Publication Date: 2020-01-07
    Description: Highlights • We present a Ba isotope data set of seawater, river waters and biogenic particles. • Ba isotope signatures of upper ocean waters are heavier than river and deep waters. • Adsorption of lighter Ba isotopes on biogenic particles induces the fractionation. • Ba isotopes trace land–sea interactions and ocean mixing processes. • Decoupling of Ba from major nutrients confirms Ba to be a biointermediate element. Abstract The distribution of barium (Ba) concentrations in seawater resembles that of nutrients and Ba has been widely used as a proxy of paleoproductivity. However, the exact mechanisms controlling the nutrient-like behavior, and thus the fundamentals of Ba chemistry in the ocean, have not been fully resolved. Here we present a set of full water column dissolved Ba (DBa) isotope (δ137BaDBa) profiles from the South China Sea and the East China Sea that receives large freshwater inputs from the Changjiang (Yangtze River). We find pronounced and systematic horizontal and depth dependent δ137BaDBa gradients. Beyond the river influence characterized by generally light signatures (0.0 to +0.3‰+0.3‰), the δ137BaDBa values in the upper water column are significantly higher (+0.9‰+0.9‰) than those in the deep waters (+0.5‰+0.5‰). Moreover, δ137BaDBa signatures are essentially constant in the entire upper 100 m, in which dissolved silicon isotopes are fractionated during diatom growth resulting in the heaviest isotopic compositions in the very surface waters. Combined with the decoupling of DBa concentrations and δ137BaDBa from the concentrations of nitrate and phosphate this implies that the apparent nutrient-like fractionation of Ba isotopes in seawater is primarily induced by preferential adsorption of the lighter isotopes onto biogenic particles rather than by biological utilization. The subsurface δ137BaDBa distribution is dominated by water mass mixing. The application of stable Ba isotopes as a proxy for nutrient cycling should therefore be considered with caution and both biological and physical processes need to be considered. Clearly, however, Ba isotopes show great potential as a new tracer for land–sea interactions and ocean mixing processes.
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  • 6
    Publication Date: 2020-02-06
    Description: The Labrador Sea is one of the key areas for deep water formation driving the Atlantic thermohaline circulation and thus plays an important role in Northern Hemisphere climatic fluctuations. In order to better constrain the overturning processes and the origins of the distinct water masses, combined dissolved Hf–Nd isotopic compositions and rare earth element (REE) distribution patterns were obtained from four water depth profiles along a section across the Labrador Sea. These were complemented by one surface sample off the southern tip of Greenland, three shallow water samples off the coast of Newfoundland, and two deep water samples off Nova Scotia. Although light REEs are markedly enriched in the surface waters off the coast of Newfoundland compared to north Atlantic waters, the REE concentration profiles are essentially invariant throughout the water column across the Labrador Sea. The hafnium concentrations of surface waters exhibit a narrow range between 0.6 and 1 pmol/kg but are not significantly higher than at depth. Neodymium isotope signatures (ɛNd) vary from unradiogenic values between −16.8 and −14.9 at the surface to more radiogenic values near −11.0 at the bottom of the Labrador Sea mainly reflecting the advection of the Denmark Strait Overflow Water and North East Atlantic Deep Water, the signatures of which are influenced by weathering contributions from Icelandic basalts. Unlike Nd, water column radiogenic Hf isotope signatures (ɛHf) are more variable representing diverse weathering inputs from the surrounding landmasses. The least radiogenic seawater ɛHf signatures (up to −11.7) are found in surface waters close to Greenland and near the Canadian margin. This reflects the influence of recirculating Irminger Current Waters, which are affected by highly unradiogenic inputs from Greenland. A three to four ɛHf unit difference is observed between Denmark Strait Overflow Water (ɛHf ∼ −4) and North East Atlantic Deep Water (ɛHf ∼ −0.1), although their source waters have essentially the same ɛNd signature. This most likely reflects different weathering signals of hafnium delivered to Denmark Strait Overflow Water and North East Atlantic Deep Water (incongruent weathering of old rocks from Greenland versus basaltic rocks from Iceland). In addition, the ɛHf data resolve two layers within the main body of Labrador Sea Water not visible in the ɛNd distribution, which are shallow Labrador Sea Water (ɛHf ∼ −2) and deep Labrador Sea Water (ɛHf ∼ −4.5). The latter layer was formed between the late 1980’s and mid 1990’s during the last cold state of the Labrador Sea and underwent substantial modification since its formation through the admixture of Irminger Water, Iceland Slope Water and North East Atlantic Deep Water, which is reflected in its less radiogenic ɛHf signature. The overall behavior of Hf in the water column suggests its higher sensitivity to local changes in weathering inputs on annual to decadal timescales. Although application of Hf isotopes as a tracer for global water mass mixing is complicated by their susceptibility to incongruent weathering inputs they are a promising tracer of local processes in restricted basins such as the Labrador Sea.
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  • 7
    Publication Date: 2017-06-19
    Description: The radiogenic neodymium (Nd) isotope composition of foraminiferal shells provides a powerful archive to investigate past changes in sources and mixing of water masses. However, seawater Nd isotope ratios extracted from foraminiferal shells can be biased by contaminant phases such as organic matter, silicates, or ferromanganese coatings, the removal of which requires rigorous multiple step cleaning of the samples. Here we investigate the efficiency of Flow Through and batch cleaning methods to extract seawater Nd isotope compositions from planktonic foraminifera in a shelf setting in the Gulf of Guinea that is strongly influenced by riverine sediment inputs. Nd isotope analyses of reductively and oxidatively cleaned mono-specific planktonic foraminiferal samples and reductively cleaned mixed benthic foraminifera were complemented by analyses of non-reductively cleaned mono-specific planktonic foraminiferal samples, Fe–Mn coatings of de-carbonated bulk sediment leachates, and the residual detrital fraction of the same sediment. Al/Ca and Mn/Ca ratios of fully cleaned foraminiferal samples reveal indistinguishable levels of cleaning efficiency between the batch and the Flow Through methods and the Nd isotope compositions obtained from application of both methods are identical within error. Furthermore, non-reductively cleaned foraminiferal samples have the same Nd isotope composition as reductively cleaned foraminifera at our study sites. Close to the Niger River mouth the Nd isotope composition of the foraminifera agree with the seawater Nd isotope composition of nearby stations. Based on the combined extracted Nd isotope signatures and element to calcium ratios, as well as rare earth element distribution patterns, we infer that the planktonic foraminiferal Nd isotope signatures reflect bottom water/pore water signatures. The isotopic composition of the bulk de-carbonated sediment leachates (Fe–Mn coatings) differs significantly from the foraminiferal data at this site and probably reflects particles that acquired their ferromanganese/pre-formed pre-formed/ferromanganese coatings in nearby rivers. Therefore, in such river influenced shelf settings foraminiferal shells should be used to obtain unbiased bottom seawater signatures.
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  • 8
    Publication Date: 2019-09-23
    Description: The recrystallisation (dissolution–precipitation) of carbonate sediments has been successfully modelled to explain profiles of pore water Sr concentration and radiogenic Sr isotope composition at different locations of the global ocean. However, there have been few systematic studies trying to better understand the relative importance of factors influencing the variability of carbonate recrystallisation. Here we present results from a multi-component study of recrystallisation in sediments from the Integrated Ocean Drilling Program (IODP) Expedition 320/321 Pacific Equatorial Age Transect (PEAT), where sediments of similar initial composition have been subjected to different diagenetic histories. The PEAT sites investigated exhibit variable pore water Sr concentrations gradients with the largest gradients in the youngest sites. Radiogenic Sr isotopes suggest recrystallisation was relative rapid, consistent with modelling of other sediment columns, as the 87Sr/86Sr ratios are indistinguishable (within 2σ uncertainties) from contemporaneous seawater 87Sr/86Sr ratios. Bulk carbonate leachates and associated pore waters of Site U1336 have lower 87Sr/86Sr ratios than contemporaneous seawater in sediments older than 20.2 Ma most likely resulting from the upward diffusion of Sr from older recrystallised carbonates. It seems that recrystallisation at Site U1336 may still be on-going at depths below 102.5 rmcd (revised metres composite depth) suggesting a late phase of recrystallisation. Furthermore, the lower Sr/Ca ratios of bulk carbonates of Site U1336 compared to the other PEAT sites suggest more extensive diagenetic alteration as less Sr is incorporated into secondary calcite. Compared to the other PEAT sites, U1336 has an inferred greater thermal gradient and a higher carbonate content. The enhanced thermal gradient seems to have made these sediments more reactive and enhanced recrystallisation. In this study we investigate stable Sr isotopes from carbonate-rich deep sea sediments for the first time. Pore water δ88/86Sr increases with depth (from 0.428‰ to values reaching up to 0.700‰) at Site U1336 documenting an isotope fractionation process during recrystallisation. Secondary calcite preferentially incorporates the lighter Sr isotope (86Sr) leaving pore waters isotopically heavy. The δ88/86Sr values of the carbonates themselves show more uniform values with no detectable change with depth. Carbonates have a much higher Sr content and total Sr inventory than the pore waters meaning pore waters are much more sensitive to fractionation processes than the carbonates. The δ88/86Sr results indicate that pore water stable Sr isotopes have the potential to indicate the recrystallisation of carbonate sediments.
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  • 9
    Publication Date: 2020-10-21
    Description: Highlights: • High-precision glacial–interglacial 87Sr/86Sr record from planktic foraminifera. • Major oceans yield indistinguishable 87Sr/86Sr values at ±5 ppm level of precision. • Foraminifera show no resolvable 87Sr/86Sr variation since last glacial interval. • These data accommodate a ±12% variation for the steady-state weathering flux. • A short-term weathering pulse during de-glaciation is not accommodated by the data. Abstract Existing strontium radiogenic isotope (87Sr/86Sr) measurements for foraminifera over Quaternary glacial–interglacial climate cycles provide no evidence for variations in the isotope composition of seawater at the ±9–13 ppm level of precision. However, modelling suggests that even within this level of uncertainty significant (up to 30%) variations in chemical weathering of the continents are permitted, accounting for the longer-term rise in 87Sr/86Sr over the Quaternary, and the apparent imbalance of Sr in the oceans at the present-day. This study presents very high-precision 87Sr/86Sr isotope data for modern seawater from each of the major oceans, and a glacial–interglacial seawater record preserved by planktic foraminifera from Ocean Drilling Program (ODP) Site 758 in the north-east Indian ocean. Strontium isotope 87Sr/86Sr measurements for modern seawater from the Atlantic, Pacific and Indian Oceans are indistinguishable from one another (87Sr/86Sr = 0.7091792 ± 0.0000021, n=17n=17) at the level of precision obtained in this study (±4.9 ppm 2σ). This observation is consistent with the very long residence time of Sr in seawater, and underpins the utility of this element for high precision isotope stratigraphy. The 87Sr/86Sr seawater record preserved by planktic foraminifera shows no resolvable glacial–interglacial variation (87Sr/86Sr = 0.7091784 ± 0.0000035, n=10n=10), and limits the response of seawater to variations in the chemical weathering flux and/or composition to ±4.9 ppm or less. Calculations suggest that a variation of ±12% around the steady-state weathering flux can be accommodated by the uncertainties obtained here. The new data cannot accommodate a short-term weathering pulse during de-glaciation, although a more a diffuse weathering pulse accompanying protracted ice retreat is permissible. However, these results still indicate that modern weathering fluxes are potentially higher than average over the Quaternary, and such variations through glacial cycles can also account for the longer-term rise in 87Sr/86Sr over this time interval. The very high-precision measurements made for the marine 87Sr/86Sr record in this study place clear limits on the magnitude and timing of changes in the chemical weathering flux during glacial–interglacial cycles. Further, constraints must be sought from even higher precision measurement or elements with shorter residence times in the ocean, such as osmium (Os), that have the capacity to respond to short-term variations in input.
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  • 10
    Publication Date: 2017-09-26
    Description: Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANTXXIV/3 and ANTXXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (〈0.12 pmol/kg and 10 pmol/kg, respectively), most probably due to the low terrigenous flux in this area and efficient scavenging of Hf and Nd by biogenic opal. In the vicinity of landmasses the dissolved Hf and Nd isotope compositions are clearly labeled by terrigenous inputs. Near South Africa Nd isotope values as low as εNd = −18.9 indicate unradiogenic inputs supplied via the Agulhas Current. Further south the isotopic data show significant increases to εHf = 6.1 and εNd = −4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (εNd ∼ −8 to −8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Passage. The Hf isotope compositions in the entire study area only show a small range between εHf = + 6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from εNd = −18.9 to −4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.
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