Temporal reconstruction of Hg deposition from sediment archives is relatively straightforward in organic-rich or high sedimentation rate environments, such as lakes and ocean margins. To retrieve long-term records at regional or global scales, deep-sea sediments are more appropriate, but such records are scarce and their reliability has been questioned because of possible post-depositional Hg diagenetic remobilization. Here, we investigated the accumulation of Hg in the Balearic Abyssal Plain (2850 m deep) of the Western Mediterranean through a comprehensive characterization of the chemical and isotopic composition (organic carbon, nitrogen, sulfur, major and redox-sensitive elements) of sediment trap material and sediment cores. The analysis of material collected in the sediment traps, deployed at 250, 1440, and 2820 m, indicates that Hg is (i) partially re-emitted to the atmosphere and mobilized in the twilight zone and that (ii) the Hg downward flux depends on the primary production in surface waters, suggesting that organic matter (OM) acts as the main Hg-carrier phase. As the Hg concentrations of material collected in the traps vary little with depth but the Hg: C-org ratio of the settling particulate matter decreases with depth, Hg must be re-adsorbed onto the more refractory fraction of the settling OM. Results of selective chemical extractions of the sediment indicate that Hg is very weakly coupled to the iron cycle but strongly associated with sulfur, supporting the assumption that its vertical distribution was only weakly altered by diagenetic remobilization. In addition, the distributions of S and delta S-34 in the sedimentary column exclude the possibility that local volcanism impacted on Hg enrichment of the sediments. Accordingly, a reconstruction of Hg accumulation rates (Hg-AR) during the Late Holocene is readily achieved. Biological mixing and smoothing of the sediment record, as revealed by the distribution of radionuclides in surface sediments, was considered in the interpretation of the Hg-AR record. The first anthropogenic Hg signal recorded in the studied cores corresponds to the Iron Age and the Roman Empire period, as Hg-ARs rose from the baseline (0.7 +/- 0.2 mu g m(-2) yr(-1)) to an average value of 2.2 +/- 0.5 mu g m(-2) yr(-1). The Hg-ARs return to baseline values at the decline of the Roman Empire, display a small increase during the Medieval Period (1.5 +/- 0.5 mu g m(-2) yr(-1)), increase abruptly at the onset of the Industrial Era, leading to a similar to 10-fold increase in Hg deposition in the last 120 years (8.9 +/- 1.4 mu g m(-2) yr(-1)), and retreat progressively over the past 50 years. (C) 2021 Elsevier Ltd. All rights reserved.

In Earth and planetary sciences, the chemical composition of chondritic meteorites provides an essential reference to constrain the composition and differentiation history of planetary reservoirs. Yet, for many trace elements, and in particular for volatile trace elements the composition of chondrites is not well constrained. Here we present new compositional data for carbonaceous chondrites with an emphasis on the origin of the volatile element depletion pattern. Our database includes 25 carbonaceous chondrites from 6 different groups (CI, CM, CR, CV, CO, CK), two ungrouped carbonaceous chondrites and Murchison powder samples heated up to 1000 degrees C in O-2 or Ar gas streams, respectively. A total of 51 major and trace elements were analyzed by sector field inductively coupled plasma mass spectrometry (SF-ICP-MS), using chondrite-matched calibration solutions. Our results confirm that parent body alteration and terrestrial weathering only have minor effects on the bulk chondrite compositions. Thermal metamorphism can lead to the loss of some volatile elements, as best observed in the heating experiments and two thermally overprinted chondrites Y-980115 (CI) and EET 96026 (CV4/5 or CK4/5). The effects of aqueous alteration and terrestrial weathering on the Antarctic samples are difficult to discriminate. Both processes may redistribute fluid mobile elements such as K, Na, Rb, U and the light rare earth elements (LREE) within the meteorite. In hot desert finds, the typical weathering effects are enrichments of Sr, Ba and U and a depletion of S. In general, moderately volatile elements with 50% condensation temperatures (T-c) ranging from 1250 K to 800 K show an increasing depletion, whereas 11 moderately volatile elements with 50% T-c between 800 K and 500 K are unfractionated from each other in most samples. Their extent of depletion is characteristic for the different chondrite groups. Because of this welldefined "hockey stick" pattern, we propose to divide the moderately volatile elements into two subgroups, the 'slope volatile elements' and the unfractionated 'plateau volatile elements' with lower T-c . Notably, the abundances of plateau volatile elements exhibit a co-variation with the matrix abundances of the respective host meteorites. Carbonaceous chondrite matrices are likely mixes of: (i) CI-like material and (ii) chondrule-related matrix. Chondrule-related matrix is expected to be depleted in volatile elements relative to CI and likely formed contemporaneously with chondrules, leading to chondrule-matrix complementarity. The addition of CI-like material only changed the absolute elemental concentrations of bulk matrix and bulk chondrite, while refractory and main component element ratios such as Mg/Si remain unaffected. Such a model can also account for the co-existence of low temperature CI-like material and high temperature chondrule and chondrule-related matrix. However, elevated volatile element abundances observed in chondrules still provide a challenge for the model as proposed here. (C) 2018 The Author(s). Published by Elsevier Ltd.

Germanium (Ge) and Silicon (Si) exhibit similar geochemical behavior in marine environments but are variably enriched in seafloor hydrothermal fluids relative to seawater. In this study, Ge isotope and Ge/Si ratio systematics were investigated in low temperature hydrothermal vents from Loihi Seamount (Pacific Ocean, 18°54′N, 155°15′W) and results were compared to high-temperature vents from the East Pacific Rise (EPR) at 9°50′N. Loihi offers the opportunity to understand contrasting Ge and Si behavior in low temperature seafloor hydrothermal systems characterized by abundant Fe oxyhydroxide deposition at the seafloor. The results show that both Ge/Si and δ74/70Ge in hydrothermal fluids are fractionated relative to the basaltic host rocks. The enrichment in Ge vs. Si relative to fresh basalts, together with Ge isotope fractionation (Δ74/70Gefluid-basalt up to 1.15‰ at EPR 9°50′N and 1.64‰ at Loihi) are best explained by the precipitation of minerals (e.g. quartz and Fe-sulfides) during higher temperature seawater–rock reactions in the subsurface. The study of Fe-rich hydrothermal deposits at Loihi, largely composed of Fe-oxyhydroxides, shows that Ge isotopes are also fractionated upon mineral precipitation at the seafloor. We obtained an average Ge isotope fractionation factor between Fe-oxyhydroxide (ferrihydrite) and dissolved Ge in the fluid of −2.0 ± 0.6‰ (2sd), and a maximum value of −3.6 ± 0.6‰ (2sd), which is consistent with recent theoretical and experimental studies. The study of a hydrothermal chimney at Bio 9 vent at EPR 9°50′N also demonstrates that Ge isotopes are fractionated by approximately −5.6 ± 0.6‰ (2sd) during precipitation of metal sulfides under hydrothermal conditions. Using combined Ge/Si and estimated Ge isotope signatures of Ge sinks and sources in seawater, we propose a preliminary oceanic budget of Ge which reveals that an important sink, referred as the “missing Ge sink”, may correspond to Ge sequestration into authigenic Fe-oxyhydroxides in marine sediments. This study shows that combining Ge/Si and δ74/70Ge systematics provides a useful tool to trace hydrothermal Ge and Si sources in marine environments and to understand formation processes of seafloor hydrothermal deposits.

The input of iron to the Arctic Ocean plays a critical role in the productivity of aquatic ecosystems and is potentially impacted by climate change. We examine Fe isotope systematics of dissolved and colloidal Fe from several Arctic and sub-Arctic rivers in northern Eurasia and Alaska. We demonstrate that the Fe isotopic (δ56Fe) composition of large rivers, such as the Ob’ and Lena, has a restricted range of δ56Fe values ca.–0.11 ± 0.13‰, with minimal seasonal variability, in stark contrast to smaller organic-rich rivers with an overall δ56Fe range from–1.7 to + 1.6‰. The preferential enrichment with heavy Fe isotopes observed in low molecular weight colloidal fraction and during the high-flow period is consistent with the role of organic complexation of Fe. The light Fe isotope signatures of smaller rivers and meltwater reflect active redox cycling. Data synthesis reveals that small organic-rich rivers and meltwater in Arctic environments may contribute disproportionately to the input of labile Fe in the Arctic Ocean, while bearing contrasting Fe isotope compositions compared to larger rivers.

Recent analytical developments in germanium stable isotope determination by multicollector ICP‐MS have provided new perspectives for the use of Ge isotopes as geochemical tracers. Here, we report the germanium isotope composition of the NIST SRM 3120a elemental reference solution that has been calibrated relative to internal isotopic standard solutions used in the previous studies. We also intercalibrate several geological reference materials as well as geological and meteoritic samples using different techniques, including online hydride generation and a spray chamber for sample introduction to MC‐ICP‐MS, and different approaches for mass bias corrections such as sample–calibrator bracketing, external mass bias correction using Ga isotopes and double‐spike normalisation. All methods yielded relatively similar precisions at around 0.1‰ (2s) for δ74/70Ge values. Using igneous and mantle‐derived rocks, the bulk silicate Earth (BSE) δ74/70Ge value was re‐evaluated to be 0.59 ± 0.18‰ (2s) relative to NIST SRM 3120a. Several sulfide samples were also analysed and yielded very negative values, down to −4.3‰, consistent with recent theoretical study of Ge isotope fractionation. The strong heavy isotope depletion in ore deposits also contrasts with the generally positive Ge isotope values found in many modern and ancient marine sediments.

Recent studies have suggested that rivers may present an isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22μm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high-resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive δ56Fe values (with an average of 0.43±0.04‰) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative δ56Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate δ56Fe values vary from −0.09‰ at no flocculation to ∼0.1‰ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that δ56Fe composition of rivers can also be characterized by more positive δ56Fe values (up to 0.3‰) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe-isotopes during continental run-off.

We examined the impact of a cyclonic eddy and mode-water eddy on particle flux in the Sargasso Sea. The primary method used to quantify flux was based on measurements of the natural radionuclide, 234Th, and these flux estimates were compared to results from sediment traps in both eddies, and a 210Po/210Pb flux method in the mode-water eddy. Particulate organic carbon (POC) fluxes at 150 m ranged 1–4 mmol C m−2 d−1 and were comparable between methods, especially considering differences in integration times scales of each approach. Our main conclusion is that relative to summer mean conditions at the Bermuda Atlantic Time-series Study (BATS) site, eddy-driven changes in biogeochemistry did not enhance local POC fluxes during this later, more mature stage of the eddy life cycle (>6 months old). The absence of an enhancement in POC flux puts a constraint on the timing of higher POC flux events, which are thought to have caused the local O2 minima below each eddy, and must have taken place >2 months prior to our arrival. The mode-water eddy did enhance preferentially diatom biomass in its center, where we estimated a factor of three times higher biogenic Si flux than the BATS summer average. An unexpected finding in the highly depth-resolved 234Th data sets is narrow layers of particle export and remineralization within the eddy. In particular, a strong excess 234Th signal is seen below the deep chlorophyll maxima, which we attribute to remineralization of 234Th-bearing particles. At this depth below the euphotic zone, de novo particle production in the euphotic zone has stopped, yet particle remineralization continues via consumption of labile sinking material by bacteria and/or zooplankton. These data suggest that further study of processes in ocean layers is warranted not only within, but below the euphotic zone.