Multiple plant-wax compounds record differential sources and ecosystem structure in large river catchments

© The Author(s), 2016. This is the author's version of the work and is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Geochimica et Cosmochimica Acta 184 (2016): 20-40, doi:10.1016/j.gca.2016.04.003.The concentrations, distributions, and stable carbon isotopes (δ13C) of plant waxes carried by fluvial suspended sediments contain valuable information about terrestrial ecosystem characteristics. To properly interpret past changes recorded in sedimentary archives it is crucial to understand the sources and variability of exported plant waxes in modern systems on seasonal to inter-annual timescales. To determine such variability, we present concentrations and δ13C compositions of three compound classes (n-alkanes, n-alcohols, n-alkanoic acids) in a 34-month time series of suspended sediments from the outflow of the Congo River. We show that exported plant-dominated n-alkanes (C25 – C35) represent a mixture of C3 and C4 end members, each with distinct molecular distributions, as evidenced by an 8.1 ± 0.7‰ (±1σ standard deviation) spread in δ13C values across chain-lengths, and weak correlations between individual homologue concentrations (r = 0.52 – 0.94). In contrast, plant-dominated n-alcohols (C26 – C36) and n-alkanoic acids (C26 – C36) exhibit stronger positive correlations (r = 0.70 – 0.99) between homologue concentrations and depleted δ13C values (individual homologues average ≤ -31.3‰ and -30.8‰, respectively), with lower δ13C variability across chain-lengths (2.6 ± 0.6‰ and 2.0 ± 1.1‰, respectively). All individual plant-wax lipids show little temporal δ13C variability throughout the time-series (1σ ≤ 0.9‰), indicating that their stable carbon isotopes are not a sensitive tracer for temporal changes in plant-wax source in the Congo basin on seasonal to inter-annual timescales. Carbon-normalized concentrations and relative abundances of n-alcohols (19 – 58% of total plant-wax lipids) and n-alkanoic acids (26 – 76%) respond rapidly to seasonal changes in runoff, indicating that they are mostly derived from a recently entrained local source. In contrast, a lack of correlation with discharge and low, stable relative abundances (5 – 16%) indicate that n-alkanes better represent a catchment-integrated signal with minimal response to discharge seasonality. Comparison to published data on other large watersheds indicates that this phenomenon is not limited to the Congo River, and that analysis of multiple plant-wax lipid classes and chain lengths can be used to better resolve local vs. distal ecosystem structure in river catchments.J.D.H. was supported by the National Science Foundation Graduate Research Fellowship under Grant No. 2012126152. V.V.G. was partly supported by the US National Science Foundation, grants OCE-0851015 and OCE-0928582. Parts of this work were supported by the DFG Research Center/Cluster of Excellence “The Ocean in the Earth System” at MARUM - Center for Marine Environmental Science, University of Bremen.2017-04-0

Particulate multi-element geochemical concentrations, dissolved barium concentrations and barium-isotopic data collected during the R/V Blue Heron cruise BH15-11 in Lake Superior during August 2015

Dataset: Particulate and dissolved Lake Superior geochemistryParticles are important vectors of nutrients, carbon, and several trace metals within large bodies of water. Broadly speaking, particle distributions can be classified into three major groups on the basis of their multi-element geochemistry: biogenic (organic matter-associated phases and tests); lithogenic (highly refractory rock-derived materials); and authigenic (formed in situ below the euphotic zone). We collected particulate samples spanning the full water column of Lake Superior at Stations FWM (46.998528, -91.246250) and WM (47.331611, -89.821389) during the height of 2015 summer thermal stratification (cruise BH15-11). We analyzed particle leachates for their multi-element geochemistry using ICP-MS (inductively-coupled plasma mass spectrometry) at the Woods Hole Oceanographic Institution Plasma Facility. We report elemental concentrations in Lake Superior particulate matter in (nano or pico) moles per liter, defined by a 0.44 um filter cutoff. Lithogenic cycles are resolved by Al, Fe, Ti, V, and Y; biogenic phases by Ca, Cd, P, and Sr; and authigenic processes by Ba, Cd, and Mn. Several elements exhibit hybrid-type distributions depending on the depth range under investigation. Also reported are stable barium-isotopic distributions for particulate and total dissolvable Ba, measured using multiple-collector ICP-MS and reported relative to NIST SRM 3104a in permill. For a complete list of measurements, refer to the supplemental document 'Field_names.pdf', and a full dataset description is included in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: http://www.bco-dmo.org/dataset/680091NSF Division of Ocean Sciences (NSF OCE) OCE-1430015, NSF Division of Ocean Sciences (NSF OCE) OCE-144357

Spicule morphology impacts stable silicon isotopic composition of sponge archives

The stable silicon isotopic composition of siliceous sponge skeletal elements, spicules, forms a potential proxy for past dissolved silicon (DSi) concentrations of bottom waters. Field-based studies have shown that there is a non-linear relationship between the concentration of ambient DSi and both the isotopic composition (denoted by δ30Si) of spicules and apparent isotopic fractionation by sponges during growth. There is considerable scatter in the calibration, with some studies highlighting variation within an individual sponge, and between individuals, in both monospecific and more diverse communities. Furthermore, some derived sponge forms, including hypersilicified and carnivorous sponges, appear to have anomalous isotopic fractionation, deviating significantly from other sponges. When reconstructing past DSi, it is only possible to differentiate spicules by their morphology, which in many cases will not be taxonomically diagnostic. However, there has yet to be a systematic study of core top and downcore δ30Si measurements from different spicule types. Here we address that gap using spicules extracted from two sediment cores taken at the summit of the Schulz Bank, a seamount located on the Arctic Mid-Ocean Ridge between the Norwegian and Greenland Seas. Mean isotopic compositions of downcore spicules of a given morphology were similar between nearby cores and mainly did not show any significant differences. Our results did reveal a systematic difference between spicule types extracted from a given sediment horizon, and a significant difference in the downcore mean compositions, between needle-like Oxea and other morphologies. These new findings imply that picking a single spicule type is best practice for palaeoceanographic applications of sponge archives, but the choice of Oxea spicules could bias these reconstructions towards high DSi concentrations

Barium isotopes reveal role of ocean circulation on barium cycling in the Atlantic

© The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 204 (2017): 286-299, doi: 10.1016/j.gca.2017.01.043.We diagnose the relative influences of local-scale biogeochemical cycling and regional-scale ocean circulation on Atlantic barium cycling by analyzing four new depth profiles of dissolved Ba concentrations and isotope compositions from the South and tropical North Atlantic. These new profiles exhibit systematic vertical, zonal, and meridional variations that reflect the influence of both local-scale barite cycling and large-scale ocean circulation. Previously reported epipelagic decoupling of Ba and Si in the tropics is also found to be associated with significant Ba isotope heterogeneity. We contend that this decoupling originates from the depth segregation of opal & barite formation but is exacerbated by weak vertical mixing, as in the tropics. Zonal influence from isotopically-‘heavy’ water masses in the western North Atlantic evidence the advective inflow of Ba-depleted Upper Labrador Sea Water, which is not seen in the eastern basin or the South Atlantic. Meridional variations in Atlantic Ba isotope systematics below 2,000 m appear entirely controlled by conservative mixing. Using an inverse isotopic mixing model, we calculate the Ba isotope composition of the Ba-poor northern end member as +0.45 ‰ and the Ba-rich southern end member +0.26 ‰, relative to NIST SRM 3104a. The near-conservative behaviour of Ba in the deep ocean indicates that Ba isotopes may serve as an independent tracer of the provenance of advected water masses in the Atlantic Ocean. The clearly resolved Ba-isotope signatures of northern- and southern-sourced waters may also prove useful in paleoceanographic studies, should appropriate sedimentary archives be identified. Overall, our results offer new insights into the controls on Ba cycling in seawater and thus the mechanisms that underpin the utility of Ba-based proxies in paleoceanography.D357/GA10E was funded by the UK-GEOTRACES National Environment Research Council Consortium Grant (NE/H006095/1) and JC094 by the European Research Council. KH thanks The Royal Society (University Research Fellowship UF120084) and FP7-PEOPLE-2012-CIG Proposal No 320070 for funding; TJH thanks The Andrew W. Mellon Foundation Endowed Fund for Innovative Research, NSF (OCE-1443577), and the Agouron Institute Geobiology Postdoctoral Fellowship Program for supporting isotope research at NIRVANA

The influence of glacial cover on riverine silicon and iron exports in Chilean Patagonia

Glaciated environments have been highlighted as important sources of bioavailable nutrients, with inputs of glacial meltwater potentially influencing productivity in downstream ecosystems. However, it is currently unclear how riverine nutrient concentrations vary across a spectrum of glacial cover, making it challenging to accurately predict how terrestrial fluxes will change with continued glacial retreat. Using 40 rivers in Chilean Patagonia as a unique natural laboratory, we investigate how glacial cover affects riverine Si and Fe concentrations, and infer how exports of these bioessential nutrients may change in the future. Dissolved Si (as silicic acid) and soluble Fe (0.45 mu m) phases of both Si and Fe, which are not typically accounted for in terrestrial nutrient budgets but can dominate riverine exports. Dissolved Si and soluble Fe yield estimates showed no trend with glacial cover, suggesting no significant change in total exports with continued glacial retreat. However, yields of colloidal-nanoparticulate and reactive sediment-bound Si and Fe were an order of magnitude greater in highly glaciated catchments and showed significant positive correlations with glacial cover. As such, regional-scale exports of these phases are likely to decrease as glacial cover disappears across Chilean Patagonia, with potential implications for downstream ecosystems

Pelagic barite precipitation at micromolar ambient sulfate

The question of how significant barite deposits were able to form from early Earth’s low-sulfate seas remains controversial. Here, the authors show pelagic barite precipitation within a strongly barite-undersaturated ecosystem, highlighting the importance of particle-associated microenvironments

Publisher Correction : Pelagic barite precipitation at micromolar ambient sulfate

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Nature Communications 9 (2018): 305, doi:10.1038/s41467-017-02701-y.Correction to: Nature Communications https://doi.org/10.1038/s41467-017-01229-5, Article published online 07 November 201

Refining trace metal temperature proxies in cold-water scleractinian and stylasterid corals

The Li/Mg, Sr/Ca and oxygen isotopic (O) compositions of many marine biogenic carbonates are sensitive to seawater temperature. Corals, as cosmopolitan marine taxa with carbonate skeletons that can be precisely dated, represent ideal hosts for these geochemical proxies. However, efforts to calibrate and refine temperature proxies in cold-water corals (<20 °C) remain limited. Here we present skeletal Li/Mg, Sr/Ca, O and carbon isotope (C) data from live-collected specimens of aragonitic scleractinian corals (Balanophyllia, Caryophyllia, Desmophyllum, Enallopsammia, Flabellum, Lophelia, and Vaughanella), both aragonitic and high-Mg calcitic stylasterid genera (Stylaster and Errina), and shallow-water high-Mg calcite crustose coralline algae (Lithophyllum, Hydrolithon, and Neogoniolithon). We interpret these data in conjunction with results from previously explored taxa including aragonitic zooxanthellate scleractinia and foraminifera, and high-Mg calcite octocorals. We show that Li/Mg ratios covary most strongly with seawater temperature, both for aragonitic and high-Mg calcitic taxa, making for reliable and universal seawater temperature proxies. Combining all of our biogenic aragonitic Li/Mg data with previous calibration efforts we report a refined relationship to temperature: Li/MgAll Aragonite = (). This calibration now permits paleo-temperature reconstruction to better than ±3.4 °C (95% prediction intervals) across biogenic aragonites, regardless of taxon, from 0 to 30 °C. For taxa in this study, aragonitic stylasterid Li/Mg offers the most robust temperature proxy (Li/MgStylasterid (Arag) = ()) with a reproducibility of ±2.3 °C. For the first time, we show that high-Mg calcites have a similar exponential relationship with temperature, but with a lower intercept value (Li/Mg = ()). This calibration opens the possibility of temperature reconstruction using high-Mg calcite corals and coralline algae. The commonality in the relationship between Li/Mg and temperature transcends phylogeny and suggests abiogenic trace metal incorporation mechanism

Seasonal changes in dissolved organic matter composition in a Patagonian fjord affected by glacier melt inputs

Biogeochemical processes in fjords are likely affected by changes in surrounding glacier cover but very little is known about how meltwater directly influences dissolved organic matter (DOM) in fjords. Moreover, the data available are restricted to a handful of northern hemisphere sites. Here we analyze seasonal and spatial variation in dissolved organic carbon (DOC) concentration and DOM composition (spectrofluorescence, ultrahigh resolution mass spectrometry) in Baker-Martinez Fjord, Chilean Patagonia (48°S), to infer the impacts of rapid regional deglaciation on fjord DOM. We show that surface layer DOC concentrations do not vary significantly between seasons, but DOM composition is sensitive to differences in riverine inputs. In summer, higher protein-like fluorescence reflects increased glacial meltwater inputs, whilst molecular level data show weaker influence from marine DOM due to more intense stratification. We postulate that the shifting seasonal balance of riverine and marine waters affects the supply of biolabile peptides and organic nitrogen cycling in the surface layer. Trends in DOM composition with increasing salinity are consistent with patterns in estuaries (i.e. preferential removal of aromatic compounds and increasing relative contribution of unsaturated and heteroatom-rich DOM from marine sources). Preliminary estimates also suggest that at least 10 of the annual organic carbon stock in this fjord is supplied by the four largest, glacially fed rivers and that these inputs are dominated by dissolved (84) over particulate organic carbon. Riverine DOC may therefore be an important carbon subsidy to bacterial communities in the inner fjord. The overall findings highlight the biogeochemical sensitivity of a Patagonian fjord to changes in glacier melt input, which likely has relevance for other glaciated fjords in a warming climate