Description: Previous studies have demonstrated the potential for the Li content of coral aragonite to record information about environmental conditions, but no detailed study of tropical corals exists. Here we present the Li and Mg to Ca ratios at a bimonthly to monthly resolution over 25 years in two modern Porites corals, the genus most often used for paleoclimate reconstructions in the tropical Indo-Pacific. A strong relationship exists between coral Li/Ca and locally measured SST, indicating that coral Li/Ca can be used to reconstruct tropical SST variations. However, Li/Ca ratios of the skeleton deposited during 1979-1980 do not track local SST well and are anomalously high in places. The Mg/Ca ratios of this interval are also anomalously high, and we suggest Li/Ca can be used to reconstruct tropical SST only when Mg/Ca data are used to carefully screen for relatively rare biological effects. Mg/Li or Li/Mg ratios provide little advantage over Li/Ca ratios, except that the slope of the Li/Mg temperature relationship is more similar between the two corals. The Mg/Li temperature relationship for the coral that experienced a large temperature range is similar to that found for cold water corals and aragonitic benthic foraminifera in previous studies. The comparison with data from other biogenic aragonites suggests the relationship between Li/Mg and water temperature can be described by a single exponential relationship. Despite this hint at an overarching control, it is clear that biological processes strongly influence coral Li/Ca, and more calibration work is required before widely applying the proxy

Description: The Late Quaternary variability of the South Asian (or Indian) monsoon has been linked with glacial-interglacial and millennial scale climatic changes but past rainfall intensity in the river catchments draining into the Andaman Sea remains poorly constrained. Here we use radiogenic Sr, Nd, and Pb isotope compositions of the detrital clay-size fraction and clay mineral assemblages obtained from sediment core NGHP Site 17 in the Andaman Sea to reconstruct the variability of the South Asian monsoon during the past 60 kyr. Over this time interval eNd values changed little, generally oscillating between 27.3 and 25.3 and the Pb isotope signatures are essentially invariable, which is in contrast to a record located further northeast in the Andaman Sea. This indicates that the source of the detrital clays did not change significantly during the last glacial and deglaciation suggesting the monsoon was spatially stable. The most likely source region is the Irrawaddy river catchment including the Indo-Burman Ranges with a possible minor contribution from the Andaman Islands. High smectite/(illite1chlorite) ratios (up to 14), as well as low 87Sr/86Sr ratios (0.711) for the Holocene period indicate enhanced chemical weathering and a stronger South Asian monsoon compared to marine oxygen isotope stages 2 and 3. Short, smectite-poor intervals exhibit markedly radiogenic Sr isotope compositions and document weakening of the South Asian monsoon, which may have been linked to short-term northern Atlantic climate variability on millennial time scales.

Description: Stable carbon and oxygen isotopes (δ13C and δ18O) of foraminiferal tests are amongst the most important tools in paleoceanography, but the extent to which recrystallization can alter the isotopic composition of the tests is not well known. Here we compare three middle Miocene (16–13 Ma) benthic foraminiferal stable isotope records from eastern equatorial Pacific sites with different diagenetic histories to investigate the effect of recrystallization. To test an extreme case, we analyzed stable isotope compositions of benthic foraminifera from Integrated Ocean Drilling Program Site U1336, for which the geochemistry of bulk carbonates and associated pore waters indicates continued diagenetic alteration in sediments 〉 14.7 Ma. Despite this diagenetic overprinting, the amplitudes and absolute values of the analyzed U1336 stable isotopes agree well with high-resolution records from better preserved Sites U1337 and U1338 nearby. Our results suggest that although benthic foraminiferal tests of all three sites show some degree of textural changes due to recrystallization, they have retained their original stable isotope signatures. The good agreement of the benthic foraminiferal stable isotope records demonstrates that recrystallization occurred extremely rapidly (〈 100 kyr) after deposition. This is confirmed by the preservation of orbital cyclicities in U1336 stable isotope data and δ18O values being different to inorganic calcite that would precipitate from U1336 pore waters during late recrystallization. The close similarity of the benthic foraminiferal stable isotope records between the sites allows the well-resolved paleomagnetic results of Site U1336 to be transferred to Sites U1337 and U1338 improving the global geological timescale.

Description: The rare earth elements (REEs) with their systematically varying properties are powerful tracers of continental inputs, particle scavenging intensity and the oxidation state of seawater. However, their generally low (∼pmol/kg) concentrations in seawater and fractionation potential during chemical treatment makes them difficult to measure. Here we report a technique using an automated preconcentration system, which efficiently separates seawater matrix elements and elutes the preconcentrated sample directly into the spray chamber of an ICP-MS instrument. The commercially available “seaFAST” system (Elemental Scientific Inc.) makes use of a resin with ethylenediaminetriacetic acid and iminodiacetic acid functional groups to preconcentrate REEs and other metals while anions and alkali and alkaline earth cations are washed out. Repeated measurements of seawater from 2000 m water depth in the Southern Ocean allows the external precision (2σ) of the technique to be estimated at 〈23% for all REEs and 〈15% for most. Comparison of Nd concentrations with isotope dilution measurements for 69 samples demonstrates that the two techniques generally agree within 15%. Accuracy was found to be good for all REEs by using a five point standard addition analysis of one sample and comparing measurements of mine water reference materials diluted with a NaCl matrix with recommended values in the literature. This makes the online preconcentration ICP-MS technique advantageous for the minimal sample preparation required and the relatively small sample volume consumed (7 mL) thus enabling large data sets for the REEs in seawater to be rapidly acquired.

Description: Mg/Ca ratios of surface and subsurface dwelling foraminifera provide valuable information about the past temperature of the water column. Planktonic foraminifera calcify over a period of weeks to months. Therefore, the range of Mg/Ca temperatures obtained from single specimens potentially records seasonal temperature changes. We present solution-derived Mg/Ca ratios for single specimens of the planktonic foraminifera species Globigerinoides ruber (pink), Globigerinoides ruber (white), and Globorotalia inflata from a sediment trap off northwest Africa (20°45.6′N, 18°41.9′W). Cleaning of single specimens was achieved using a flow-through system in order to prevent sample loss. Mg/Ca ratios of surface dwelling G. ruber (pink) show strong seasonality linked to sea surface temperature. Mg/Ca ratios of G. ruber (white) do not show such seasonality. Subsurface dwelling G. inflata flux is largest during the main upwelling season, but Mg/Ca ratios reflect annual temperatures at intermediate water depths. The sediment trap time series suggests that changes in the range of Mg/Ca ratios exhibited by single specimens of G. ruber (pink) and G. inflata from the sedimentary record should provide information on the past temperature range under which these species calcified. Statistical analysis suggests detectable changes in the Mg/Ca range are ≥0.80 mmol/mol (G. ruber (pink)) and ≥0.34 mmol/mol (G. inflata). For G. ruber (pink), such changes would indicate changes in the seasonal sea surface temperature range 〉4°C or a shift in the main calcification and reproductive period. For G. inflata, such changes would indicate 〉1.7°C changes in the thermocline temperature or a change in the depth habitat.

Description: The ocean plays a major role in the global carbon cycle, and attempts to reconstruct past changes in the marine carbonate system are increasing. The speciation of dissolved uranium is sensitive to variations in carbonate system parameters, and previous studies have shown that this is recorded in the uranium-to-calcium ratio (U/Ca) of the calcite shells of planktonic foraminifera. Here we test whether U/Ca ratios of deep-sea benthic foraminifera are equally suited as an indicator of the carbonate system. We compare U/Ca in two common benthic foraminifer species (Planulina wuellerstorfi and Cibicidoides mundulus) from South Atlantic core top samples with the calcite saturation state (Δ[CO32−] = [CO32−]in situ − [CO32−]sat) of the ambient seawater and find significant negative correlations for both species. Compared with planktonic foraminifera, the sensitivity of U/Ca in benthic foraminifera to changes in Δ[CO32−] is about 1 order of magnitude higher. Although Δ[CO32−] exerts the dominant control on the average foraminiferal U/Ca, the intertest and intratest variability indicates the presence of additional factors forcing U/Ca.

Description: Dissolved rare earth element (REE) concentration data from intermediate and deep seawater form an array characterized by higher middle REE enrichments (MREE/MREE*) in the North Atlantic and a progressive increase in heavy-to-light REE ratios (HREE/LREE) as water masses age. The REEs in foraminifera are fractionated towards higher MREE/MREE* and lower HREE/LREE relative to seawater. Calculations based on a scavenging model show that the REE patterns in uncleaned core-top foraminifera resemble those adsorbed onto calcite, particulate organic material, and hydrous ferric oxides but the full extent of the REE fractionation measured in foraminifera was not reproduced by the model. However, differences in the HREE/LREE, MREE/MREE* ratios and the cerium anomaly between ocean basins are preserved and are in agreement with the seawater REE distribution. Under oxic conditions, the HREE/LREE and MREE/MREE* compositions of uncleaned foraminifera at the sediment/seawater boundary are preserved during burial but the cerium anomaly is sensitive to burial depth. In suboxic sedimentary environments, all uncleaned foraminiferal REE concentrations are elevated relative to core-top values indicating addition of REEs from pore waters. The HREE/LREE ratio is highest when sedimentation rates were greatest [Lippold et al., 2009] and when high Fe/Ca ratios in the uncleaned foraminifera indicate that Fe was mobile. In sediments that have not experienced suboxic conditions during burial, uncleaned foraminifera preserve the seawater signal taken up at the sediment/seawater interface and are therefore suggested to be a suitable archive of changes in the REE signal of past bottom waters. This article is protected by copyright. All rights reserved.

Description: Key Points Calibration of XRF core scanning data highlights the need for careful examination of sediment properties such as porosity/water Grain size and water content in the sediment trigger systematic artifacts in the signal intensity of light elements (e.g. Si and Al) Known terrigenous flux proxies (e.g Ti/Ca, Fe/Ca) are influenced by sea level variations X‐ray fluorescence (XRF) core scanning of marine and lake sediments has been extensively used to study changes in past environmental and climatic processes over a range of timescales. The interpretation of XRF‐derived element ratios in paleoclimatic and paleoceanographic studies primarily considers differences in the relative abundances of particular elements. Here we present new XRF core scanning data from two long sediment cores in the Andaman Sea in the northern Indian Ocean and show that sea level related processes influence terrigenous inputs based proxies such as Ti/Ca, Fe/Ca, and elemental concentrations of the transition metals (e.g. Mn). Zr/Rb ratios are mainly a function of changes in median grain size of lithogenic particles and often covary with changes in Ca concentrations that reflect changes in biogenic calcium carbonate production. This suggests that a common process (i.e. sea level) influences both records. The interpretation of lighter element data (e.g. Si and Al) based on low XRF counts is complicated as variations in mean grain size and water content result in systematic artifacts and signal intensities not related to the Al or Si content of the sediments. This highlights the need for calibration of XRF core scanning data based on discrete sample analyses and careful examination of sediment properties such as porosity/water content for reliably disentangling environmental signals from other physical properties. In the case of the Andaman Sea, reliable extraction of a monsoon signal will require accounting for the sea level influence on the XRF data.

Description: The isotopic composition of neodymium dissolved in seawater consists of a distal, advected component that reflects water mass mixing and circulation, but near land can also contain a large local component originating from terrestrial sources such as aeolian or fluvial material. In order to use Nd isotopes to reconstruct paleocirculation, it is important to detect any local influences on the seawater signal recorded in deep sea sediments. Here we present rare earth element (REE) and Nd isotope (εNd) records from the deep Caribbean for two well‐studied time intervals in the Late Pliocene and Early Pleistocene. We measured trace element and REE compositions of weakly cleaned foraminifera to investigate if the Nd isotope signal from the same samples contained a local component. We find distinct changes in REE compositions across glaciations that are consistent with increases in the supply of local terrestrial material to the basin likely the results of glacially driven changes in sea level. Despite these larger terrestrial inputs, the Ce anomaly (Ce/Ce*) became more pronounced during glaciations indicating a better deep Caribbean ventilation. Short negative Nd isotope excursions occurred during three of the four studied glaciations, independently of any other proxy indicators for changes in ocean circulation suggesting that inputs from local terrigenous sources of Nd controlled the signal. We recommend that studies that aim to use εNd as a paleocirculation tracer routinely measure REE compositions of the authigenic phase to identify any possible terrestrial influence on the signal.

Description: The correlation between concentrations of dissolved barium (dBa) and silicon (dSi) in the modern ocean supports the use of Ba as a paleoceanographic proxy. However, the mechanisms behind their linkage and the exact processes controlling oceanic Ba cycling remain enigmatic. To discern the extent to which this association arises from biogeochemical processes versus physical mixing, we examine the behavior of Ba and Si at the Congo River-dominated Southeast Atlantic margin where active biological processes and large boundary inputs override the large-scale ocean circulation. Here we present the first combined measurements of dissolved stable Ba (δ138Ba) and Si (δ30Si) isotopes as well as Ba and Si fluxes estimated based on 228Ra from the Congo River mouth to the northern Angola Basin. In the surface waters, river-borne particle desorption or dissolution and shelf inputs lead to non-conservative additions of both dBa and dSi to the Congo-shelf-zone, with the Ba flux increasing more strongly than that of Si across the shelf. In the epipelagic and mesopelagic layers, Ba and Si are decoupled likely due to different depths of in situ barite precipitation and biogenic silica production. In the deep waters of the northern Angola Basin, we observe large enrichment of dBa, likely originating from high benthic inputs from the Congo deep-sea fan sediments. Our results reveal different mechanisms controlling the biogeochemical cycling of Ba and Si and highlight a strong margin influence on marine Ba cycling. Their close association across the global ocean must therefore mainly be a consequence of the large-scale ocean circulation. Key Points Stronger enrichment of dissolved barium (dBa) than silicon (dSi) observed in the shelf-zone of the Congo plume Diatom silica production has negligible effect on dissolved Ba isotopic compositions in large river plumes Strong dBa enrichment (up to 24 nM) in the deep water of the northern Angola Basin likely originates from high benthic inputs