Bulk Sediment Research Articles

Distribution of Pb isotopes in different chemical fractions in bed sediments from lower reaches of the Xiangjiang River, Hunan province of China

This paper reports Pb isotopes in different fractions following the three step BCR and 1 M HCl extractions on river sediments from lower reaches of the Xiangjiang river in China, and highlights the importance of Pb isotopes in heavy metal contamination assessment. Lead concentrations and Pb isotopes in bulk sediments and sediment fractions (leachates and residues) from the river were analysed using ICP-MS techniques. Results showed that sediments were highly enriched with Pb with enrichment factors >5.5, while Pb in sediments was dominated by reducible and residual Pb fractions, residing mainly in Fe-oxide and silicate minerals. Pb isotopes in sediments was characterized by radiogenic Pb produced from the decay of uranium and thorium with 206Pb/207Pb ratios of 1.1744 for less radiogenic Pb and 1.1816 for more radiogenic Pb. The leachates and residues from BCR extraction generally had similar Pb isotope compositions, of which the 206Pb/207Pb ratios were 1.1798 ± 0.002 and 1.1844 ± 0.008 respectively. Differentiation of Pb isotopes between BCR leachates and residues was insignificant. However, differentiation between leachates and residues using 1 M HCl extraction was significant, as shown by average 206Pb/207Pb ratios of 1.1746 ± 0.005 and 1.1858 ± 0.008 for leachates and residues respectively. Pb isotopic tracing suggests that Pb in sediments from Zhuzhou section arose from the mixing of anthropogenic Pb from coal combustion (39%) and mining-smelting for Pb-Zn ores (58%); while Pb in sediments from Xiangtan, Changsha and Xiangyin sections arose from the mixing of anthropogenic Pb from mining-smelting for Pb-Zn ores (54%), and lithologically inherited Pb from granite weathering (35%) with a small amount of contribution from coal combustion (10%). The present study suggests that the BCR extraction scheme was not appropriate for ecological risk assessment of heavy metal contamination in mining-impacted (ore-Pb dominated) river sediments.

Sediment and ocean crust both melt at subduction zones

Hydrous arc magmas are produced when water-bearing materials from subducted oceanic plates are transported to the mantle beneath volcanic arcs, though the mechanism of mass transport remains debated. The geochemical characteristics of the slab component have important implications for the thermal structures of down-going plates and the fluxes of elements into the deep mantle. If slab temperatures are low, then elemental fluxes from the slab will be carried in a dilute fluid. If temperatures are high, the slab may melt instead. While a long-standing paradigm for arc volcanism has been that sediments melt and ocean crust dehydrates, a growing body of evidence from arc geochemistry and experimental petrology suggests both sediment and ocean crust melt. The low solubility of many elements in aqueous fluids prevents them from making a substantial contribution to arc mass-balance. Constraints from Sr concentrations and 87Sr/86Sr ratios require a large flux of Sr from the ocean crust, which is only possible if the crust melts. H2O/Sr ratios of arc volcanics are also inconsistent with slab fluids. These conclusions are supported by thermo-mechanical models indicating that slab temperatures exceed the hydrous solidus for both ocean crust and sediments. Examination of experimental data shows a likely strong effect of oxygen fugacity on residual phases during slab melting. Arc data are best explained if the ocean crust melts beneath all arcs under oxidizing conditions somewhere between FMQ and NNO+2. Experimental constraints on sediments also require melting and that sediment melt compositions depend on bulk composition as well as temperature. If these experiments serve as analogs to sediment melting beneath arcs, then sediment bulk compositions are a necessary input for any rare earth element-based slab thermometer. We present compositions for ocean crust partial melts and partition coefficients for sediment melting based on existing experiments, physical models, and arc data, that can be used in geochemical models of arc volcanism.

Quantifying the controlling mineral phases of rare-earth elements in deep-sea pelagic sediments

Recent studies suggest that pelagic sediments can enrich rare-earth elements (REE) acting as a significant reservoir for the global REE budget as well as a potential resource for future exploitation. Although Ca-phosphate (e.g., bioapatite fossils) and Fe-Mn (oxyhydr)oxides (e.g., micronodule) have been considered important REE carriers in deep-sea sediments, the proportion of REE held by each mineral phase remains enigmatic. Here, we have investigated the sediments from two promising REE-rich prospective areas: the Tiki Basin in the Southeast Pacific (TKB) and the Central Indian Ocean Basin (CIOB). The mineral grains including bioapatite fossils and Fe-Mn micronodules have been inspected individually by in-situ microscale analytical methods. Correspondently, the REE bound to Ca-phosphate and Fe-Mn (oxyhydr)oxides have been sequentially extracted and quantified. The crucial role of Ca-phosphate is substantiated by sequential leaching which reveals its dominance in hosting ~69.3–89.4% of total REE. The Fe-Mn (oxyhydr)oxides carry ~8.2% to 22.0% of REE in bulk sediments, but they account for ~70.0–80.5% of Ce owing to their preferential adsorption of Ce over the other REE. Surface sediment on modern seafloor can accumulate high REE contents resulting from the REE scavenging by the host phases within the range of sediment-seawater interface. Differences between TKB and CIOB samples indicate that the REE enrichment in the deep-sea environment may be controlled by multiple factors including the productivity of overlying seawater (e.g., phosphorus flux), water depth relative to carbonate compensation depth (CCD), sedimentation rate, redox condition, and hydrothermal vent input (e.g., Fe-Mn precipitations).

Concurrent effects of flooding regimes and floodwater quality on sediment properties in a Yangtze River-connected floodplain wetland: Insights from field investigations during 2011–2020

Changes in flood regimes, floodwater quality, and macrophyte types may affect sediment characteristics post-flooding. However, few studies have attempted to unravel their complex influences in floodplain wetlands. From 2011 to 2020, the physical and chemical properties of surface layer sediment pre- and post-flooding was investigated through field surveys in the Dongting Lake wetland. Results indicated that the pre-flooding soil total phosphorus (TP) and total nitrogen (TN) exhibited an increasing trend during 2011–2020. Soil TP increased post-flooding relative to that pre-flooding. The changes in TN, sediment organic matter (SOM), sediment moisture content (SMC), and sediment bulk density (SBD) fluctuated over the years. The best-fitting multi-regression model demonstrated that the changes in sediment variables post-flooding showed a parabolic trajectory along the inundation duration (ID), except for SMC. Changes in soil properties post-flooding were negatively correlated with ID for sediment with a low IDs (<148 days). Meanwhile, changes in soil properties post flooding were positively correlated with ID for sediment with a high IDs (>193 days). Changes in SBD and SOM post-flooding were positively influenced by the TP content in the floodwater. These findings indicate that changes in the flooding regime, and water quality generated by anthropogenic disturbances such as the Three Gorges Dam significantly affect sediment properties, and subsequently influence the ecological functions of the Dongting Lake wetland.

The core root microbiome of Spartina alterniflora is predominated by sulfur-oxidizing and sulfate-reducing bacteria in Georgia salt marshes, USA

BackgroundSalt marshes are dominated by the smooth cordgrass Spartina alterniflora on the US Atlantic and Gulf of Mexico coastlines. Although soil microorganisms are well known to mediate important biogeochemical cycles in salt marshes, little is known about the role of root microbiomes in supporting the health and productivity of marsh plant hosts. Leveraging in situ gradients in aboveground plant biomass as a natural laboratory, we investigated the relationships between S. alterniflora primary productivity, sediment redox potential, and the physiological ecology of bulk sediment, rhizosphere, and root microbial communities at two Georgia barrier islands over two growing seasons.ResultsA marked decrease in prokaryotic alpha diversity with high abundance and increased phylogenetic dispersion was found in the S. alterniflora root microbiome. Significantly higher rates of enzymatic organic matter decomposition, as well as the relative abundances of putative sulfur (S)-oxidizing, sulfate-reducing, and nitrifying prokaryotes correlated with plant productivity. Moreover, these functional guilds were overrepresented in the S. alterniflora rhizosphere and root core microbiomes. Core microbiome bacteria from the Candidatus Thiodiazotropha genus, with the metabolic potential to couple S oxidation with C and N fixation, were shown to be highly abundant in the root and rhizosphere of S. alterniflora.ConclusionsThe S. alterniflora root microbiome is dominated by highly active and competitive species taking advantage of available carbon substrates in the oxidized root zone. Two microbially mediated mechanisms are proposed to stimulate S. alterniflora primary productivity: (i) enhanced microbial activity replenishes nutrients and terminal electron acceptors in higher biomass stands, and (ii) coupling of chemolithotrophic S oxidation with carbon (C) and nitrogen (N) fixation by root- and rhizosphere-associated prokaryotes detoxifies sulfide in the root zone while potentially transferring fixed C and N to the host plant.5gNBGD5xoDXmzcUFa4HG9gVideo

Reliability of mangrove radiocarbon chronologies: A case study from Mahé, Seychelles

Mangrove sediments are valuable archives of paleoenvironmental and relative sea-level changes. The most widely applied method to obtaining chronologies of past changes in mangrove sediments is radiocarbon dating, because mangroves produce large amounts of organic matter in situ. However, there are many challenges to obtaining reliable radiocarbon chronologies because bioturbation processes from roots and crabs can rework mangrove sediments, resulting in ages that are not in stratigraphic order. Previous studies have suggested that methods that isolate specific sediment size fractions may yield ages closer to the age of the paleo depositional surface by removing younger carbon contamination from fine roots. This study examines which sample types are more likely to yield reliable radiocarbon ages using shallow cores from a mangrove environment on Mahé, Seychelles, in the Indian Ocean. We compare radiocarbon ages from bulk sediment, sieved organic concentrates and above-ground macrofossils collected from the same stratigraphic depths. Bulk sediment and organic concentrate ages are comparable, which suggests that methods that separate out different size fractions do not sample different carbon sources in Seychelles mangrove cores. Identifiable above-ground macrofossils are rare in Seychelles mangrove cores, but yield older radiocarbon ages than comparable bulk sediment or organic concentrate ages. We suggest that in Seychelles, limited accommodation space over the late-Holocene, determined by relatively stable relative sea levels, has resulted in poor preservation of above-ground macrofossils for radiocarbon dating due to low rates of burial and sediment accretion. Low accretion rates have likely resulted in a mangrove sediment sequence that is highly bioturbated and degraded, meaning both bulk sediment and organic concentrate samples are impacted by contamination from younger roots. We argue that the availability of accommodation space and sediment composition controls the reliability of mangrove radiocarbon chronologies, which has implications for sample choice and site selection.

Assessing the chemical anthropocene – Development of the legacy pollution fingerprint in the North Sea during the last century

The North Sea and its coastal zones are heavily impacted by anthropogenic activities, which has resulted in significant chemical pollution ever since the beginning of the industrialization in Europe during the 19th century. In order to assess the chemical Anthropocene, natural archives, such as sediment cores, can serve as a valuable data source to reconstruct historical emission trends and to verify the effectiveness of changing environmental legislation. In this study, we investigated 90 contaminants covering inorganic and organic pollutant groups analyzed in a set of sediment cores taken in the North Seas' main sedimentation area (Skagerrak). We thereby develop a chemical pollution fingerprint that records the constant input of pollutants over time and illustrates their continued great relevance for the present. Additionally, samples were radiometrically dated and PAH and PCB levels in porewater were determined using equilibrium passive sampling. Furthermore, we elucidated the origin of lead (Pb) contamination utilizing non-traditional stable isotopic analysis. Our results reveal three main findings: 1. for all organic contaminant groups covered (PAHs, OCPs, PCBs, PBDEs and PFASs) as well as the elements lead (Pb) and titanium (Ti), determined concentrations decreased towards more recent deposited sediment. These decreasing trends could be linked to the time of introductions of restrictions and bans and therefor our results confirm, amongst possible other factors, the effectiveness of environmental legislation by revealing a successive change in contamination levels over the decades. 2. concentration trends for ΣPAH and ΣPCB measured in porewater correspond well with the ones found in sediment which suggests that this method can be a useful expansion to traditional bulk sediment analysis to determine the biologically available pollutant fraction. 3. Arsenic (As) concentrations were higher in younger sediment layers, potentially caused by emissions of corroded warfare material disposed in the study area after WW II.

Benthic foraminifera as indicators of recent mixed turbidite-contourite sediment transport system in the Eastern Mediterranean upper continental slope, offshore Israel

Nile derived siliciclastic sediments are the main source of sedimentation along the Levant continental margins of the Mediterranean Sea. These sediments are transported along the southeastern Mediterranean coast via well-documented longshore currents, mainly operating along the shelf. However, the cross shelf component of sediment transport, responsible for conveying sediments toward the upper slope, is less known. To better understand the cross-shelf vs. the longshore component of sediment transport we studied a ~6 m long piston core (DOR280) sampled on the upper continental slope (280 m water depth) and analyzed benthic foraminiferal assemblages and their shell taphonomy alongside the particle size distribution and mineralogy of bulk sediments, to document both the source and the transport mechanism of those upper continental-slope sediments. The radiocarbon dating at the core-base is ~650 Cal. Yrs BP, indicating an exceptionally high average sedimentation rate of ~800 cm/kyr.DOR280 consists of two alternating distinct sedimentary facies: (1) laminated (L) intervals up to ~40 cm thick each and showing a high ratio of allochthonous vs. autochthonous (allo/auto) benthic foraminiferal species and a high percentage of broken shells, indicating contribution of transported sediments originating from mid-shelf habitats; (2) non-laminated (NL) intervals up to ~200 cm thick each and showing a low allo/auto ratio and low percentages of broken shells, indicating mostly in-situ hemipelagic deposition. The L intervals are interpreted here as turbidites. The sedimentation rates calculated only for the NL intervals are still exceptionally high, thus excluding hemipelagic sedimentation as the sole mechanism for the NL deposition. Therefore, a contour bottom current transported component is suggested here as a source of the NL sedimentation.We conclude that a mixed contourite-turbidite system actively prevails along the upper continental slope of the Levant coast, offshore Israel. The mid-shelf to upper slope sediment transport is nearly continuous and presents occasional turbidite events of average decadal reoccurrence time.

Diagenetic dissolution, maghemitization and sulphidization of magnetic minerals in rapidly deposited gas hydrate bearing sediments from the Bay of Bengal

We conducted a comprehensive rock magnetic investigation complemented by a scanning electron microscopy analyses on a 148.8 m sediment core (NGHP-01-20A) from the methane-hydrate bearing site in the Bay of Bengal to systematically evaluate how magnetic minerals selectively respond to a range of diagenetic processes in the sulfidic and methanic sediments. For diagenetic analysis, we defined five distinct sediment magnetic zones (I–V) based on the sediment magnetic signatures. Rock magnetic property is mainly carried by complex magnetic mineral assemblages of detrital (titanomagnetite, silicate hosted magnetic inclusions), altered (titanomaghemite, titanohematite) and fine-grained diagenetic (pyrite) and authigenic (greigite) iron sulfide minerals. Three distinct bands of enhanced magnetic susceptibility in Z-II, Z-III and Z-V mainly comprised of detrital magnetite-rich minerals delivered by the peninsular river systems as a result of higher sedimentation events in the Krishna-Godavari (K-G) basin. Progressive diagenetic dissolution of primary iron oxide and consequent formation of iron sulfide in the uppermost sulfidic zone (Z-I) is clearly mirrored in the magnetic susceptibility (χlf) profile. Presence of moderately altered coarse-grained detrital Fe–Ti particles in the deeper methanic and magnetically enhanced zones (Z-II, Z-III, Z-V) suggest that sediment diagenesis at this site was significantly constrained by the multiple events of rapid sedimentation which might have restricted the complete dissolution of the primary minerals. Decline in magnetic grain size diagnostic proxy (ARM/IRM2.5T) in the uppermost sulfidic zones (Z-I, Z-II) can be attributed to the preferential dissolution of fine-grained magnetite. Further, downcore increases could be linked with the authigenic formation of fine-grained magnetite in methanic zones (Z-III to Z-V). Ferrimagnetic iron sulfide (greigite) indicative (SIRM/χlf) parameter showed sudden rise in Z-II and remain fairly constant throughout, suggesting the presence of authigenic greigite. Scanning electron microscopy in-line with energy dispersive X-ray spectroscopy analyses of magnetic particles from different sediment magnetic zones revealed a range of ferrimagnetic (titanomagnetite, titanomaghemite), antiferromagnetic (titanohematite) iron oxides and iron sulfide (pyrite). Detrital titanomagnetite with angular, irregular, spherical and well-defined octahedral with micron and submicron sized particles mainly derived from Deccan Volcanic Province (DVP) dominates the rock magnetic signal of bulk sediments in the studied core. We noticed several evidence of diagenetic dissolution, sulphidization and maghemitization of magnetic particles in the studied sediment core. Few nanometre-sized detrital magnetic particles occur as inclusions within the silicate minerals and remains protected against the sulfidic dissolution fronts through geologic times. Optical microscopy revealed the dominance of diagenetic pyrite occurring as overgrowth on the ferrimagnetic particles. We demonstrate that the rockmagnetic methods in combination with focussed electron microscope analyses provide valuable insights into the mineralogy, genesis and state of preservation of magnetic particles in sulfidic and methanic environments and thereby enhances the interpretative value of rock magnetic proxies.

Glaciomarine sediment deposition on the continental slope and rise of the central Ross Sea since the Last Glacial Maximum

The continental margin of the Ross Sea has been consistently sensitive to the advance and retreat of the Ross Ice Sheet (RIS) between the interglacial and glacial periods. This study examines changes of the glaciomarine sedimentation on the continental slope and rise to the eastern side of Hillary Canyon in the central Ross Sea, using three gravity cores collected at increasing water depths. Besides older AMS 14C ages of bulk sediments, based on the analytical results, sediment lithology was divided into units A, B1, and B2, representing Holocene, deglacial, and glacial periods, respectively. The sedimentation rate decreased as the water depth increased, with a higher sedimentation rate in the deglacial period (unit B1) than the Holocene (unit A). Biological productivity proxies were significantly higher in glacial unit B2 than in interglacial unit A, with transitional values observed in deglacial unit B1. Biological productivity generally decreased in the Antarctic continental margin during the glacial period because of extensive sea ice coverage. The higher biogenic contents in unit B2 are primarily attributed to the increased transport of eroded and reworked shelf sediments that contained abundant biogenic components to the continental slope and rise beneath the advancing RIS. Thus, glacial sedimentation on the continental slope and rise of the central Ross Sea was generally governed by the activity of the RIS, which generated melt-water plumes and debris flows at the front of the grounding line, although the continental rise might have experienced seasonally open conditions and lateral effects due to the bottom current.

The influence of lateral transport on sedimentary alkenone paleoproxy signals

Abstract. Alkenone signatures preserved in marine sedimentary records are considered one of the most robust paleothermometers available and are often used as a proxy for paleoproductivity. However, important gaps remain regarding the provenance and fate of alkenones, as well as their impact on derived environmental signals in marine sediments. Here, we analyze the abundance, distribution and radiocarbon (14C) age of alkenones in bulk sediments and corresponding grain-size fractions in surficial sediments from seven continental margin settings in the Pacific and Atlantic oceans to evaluate the impact of organo-mineral associations and hydrodynamic sorting on sedimentary alkenone signals. We find that alkenones preferentially reside within fine-grained mineral fractions of continental margin sediments, with the preponderance of alkenones residing within the fine-silt fraction (2–10 µm) and most strongly influencing alkenone-14C age and sea surface temperature (SST) signals from bulk sediments as a consequence of their proportional abundance and higher degree of organic matter protection relative to other fractions. Our results provide further evidence for the key role of selective association of alkenones with mineral surfaces and associated hydrodynamic mineral sorting processes on the reliability of alkenone signals encoded in marine sediments (14C age, content and distribution) and the fidelity of corresponding proxy records (productivity and sea SST) in the spatial and temporal domain.

SOIL ORGANIC CARBON DATING OF PALEOSOILS OF ALLUVIAL FANS IN A BLOWN SAND AREA (NYÍRSÉG, HUNGARY)

ABSTRACTThe most widely used dating techniques in quaternary research are the radiocarbon (14C) and optically stimulated luminescence (OSL) dating methods. In some environments, the investigated sediments do not contain enough material for14C dating. In these cases,14C dating of bulk sediment may be used as a last resort. The major aim of the present study was to determine the reliability and limitations of the different fractions of the soil organic carbon (SOC)14C ages in the Nyírség blown-sand study area, in Hungary. Therefore, the low- and high-temperature combustions of SOC (LT-SOC and HT-SOC)14C age of fossil soils were compared with the charcoal ages from the same fossil soil layer, and their (LT-SOC, HT-SOC, and charcoal) age reliability was verified independently by applying OSL to the quartz fraction of the sediment samples. The14C data show variable agreement with OSL ages. Charcoal fragments were collected from some of the best material for14C dating and their ages are in agreement with the LT and HT-SOC14C ages and OSL data. The14C age LT-SOC gives a reliable, credible ages, which were confirmed by independent OSL measurements. If buried soils do not contain any other macroscopic remnants for14C dating, the LT-SOC14C ages can be used, in the case of the Nyírség study area. The LT-SOC, which is the younger fraction of the soil organic carbon, may be considered to represent the burial time of the fossil soil layer. The HT-SOC14C ages are sometimes unrealistically older than expected and cannot be considered to be reliable.

Examining the effects of chemical cleaning, leaching, and partial dissolution on zinc and cadmium isotope fractionation in marine carbonates

The application of zinc (Zn) and cadmium (Cd) isotopes as palaeo-proxies in carbonate sediment is rapidly expanding due to their potential for tracing changes in biological productivity in the modern and past oceans. However, there are limited investigations into the chemical cleaning methods required to produce the most consistent and accurate data for these novel isotope systems. This could impact their use as palaeo-proxies to reconstruct ocean-atmosphere-climate interactions throughout Earth's history.To address this concern and expand the utility of the Zn and Cd stable isotope systems as palaeo-productivity tracers, the performance of two standard chemical cleaning protocols for acquiring robust and reliable Zn and Cd isotope datasets were assessed. These include (i) the Cd-cleaning method that uses a reductive step to selectively leach contaminating secondary iron (Fe)‑manganese (Mn) (oxyhydr)oxide coatings from the carbonate surface, and an oxidative step that is used to remove post-depositional organic matter and sulphide precipitates; and (ii) the magnesium/calcium cleaning protocol that includes an oxidative step only, leaving secondary FeMn (oxyhydr)oxide coatings largely intact. Well-preserved Holocene-, and Mesozoic-aged carbonate sediments were used to test the reliability of these two chemical cleaning methods. The Holocene samples comprised not only aliquots of bulk sediment, but also individual species of planktic and benthic foraminifera.Our results show that the best practice chemical cleaning method for retrieving consistent and accurate Zn and Cd isotope, and Zn/Ca and Cd/Ca datasets for carbonate sediments, requires both reductive and oxidative cleaning following the Cd-cleaning method. This differs from most methodological approaches applied to date that remove the reductive step from the chemical cleaning protocol and apply an oxidative step only, or no chemical cleaning at all. Inclusion of the reductive step in the chemical cleaning method typically shifts δ66Zn by ~0.1‰ lower and δ114Cd by 0.3‰ higher in the solid phase, while Zn/Ca and Cd/Ca typically decrease 2-fold. The benthic foraminifera, C. wuellerstorfi, that live in ocean bottom waters where the seawater Zn and Cd isotope composition is homogeneous display evidence of Zn and Cd isotope fractionation between seawater and carbonate on the order of 0.08 ± 0.08‰ (2SE, n = 4) and − 0.25 ± 0.13‰ (2SE, n = 4), respectively, in agreement with experimental constraints. Furthermore, evidence of Zn isotope fractionation effects are recorded in a naturally-dissolved carbonate sediment, together with laboratory-controlled carbonate dissolution experiments. Based on these results, we recommend the Cd-cleaning method and the application of Zn and Cd isotope fractionation factors to accurately reconstruct past seawater Zn and Cd isotope compositions from carbonate sediments.

Equatorial Pacific bulk sediment δ15N supports a secular increase in Southern Ocean nitrate utilization after the mid-Pleistocene Transition

In much of the equatorial Pacific, surface nitrate is consistently available due to upwelling of sub-Antarctic Mode Water-derived nitrate from the thermocline. However, in the low-latitude western boundary current (WBC) region, surface nitrate is limited due to reduced upwelling and less nitrate-replete thermocline water masses. In order to explore South Pacific WBC paleoceanography via upper ocean nitrate dynamics, we present a new bulk sediment δ15N record from within this WBC region at International Ocean Discovery Program Site U1486 (2°22′S, 144°36′E) in the Bismarck Sea north of New Guinea. This record spans from 1420 ka to recent – surpassing nearby sediment δ15N reconstructions by over a million years and allowing for direct comparison to low-latitude Pacific sediment core δ15N records of similar length. Core-top and down-core bulk sediment δ15N, TOC/TN and δ13Corg values indicate minimal or no terrestrial influence on the organic fraction at Site U1486, which is consistent with previous studies of modern processes in the region. After comparison, differences in orbital variability and secular trends throughout the Middle and Late Pleistocene suggest that nitrate dynamics along the equator and in the WBCs were relatively disparate. We observe that δ15N at Site U1486 is consistent with patterns of eastern Pacific denitrification, while we suggest increasing δ15N after the mid-Pleistocene Transition (MPT; ∼1250–700 ka) at Sites 806 (0°19′N, 110°30′W) and 849 (0°19′N, 160°E) is linked to increasing Southern Ocean nitrate utilization. Enhanced nitrate utilization is a key indicator of the strengthened biological pump that contributed to a reduction in atmospheric pCO2 during the last glacial. Therefore, a post-MPT increase in nitrate utilization may bolster the role of the Southern Ocean biological pump in driving the deeper and longer glacial periods of the 100-kyr world.

Pre–treatment method to avoid contamination for radiocarbon dating of organic–rich coastal deposits

Establishing an accurate chronology for coastal sediment profiles using radiocarbon dating has been a challenging task for scientists around the world. In this study, we present a step-by-step procedure of an optimized pre-treatment method to remove roots, shell hashes, and other contaminants from organic-rich bulk sediments for radiocarbon dating. This procedure first applies loss-on-ignition analysis throughout the sediment profile to locate the ideal sampling intervals that have high organic and low carbonate contents, and then uses a two-step sieving procedure to remove contaminants from the bulk sediments. During the past five years, we have prepared a total of 64 samples for radiocarbon dating using this pre-treatment method, and 59 of them were deemed valid, a success rate of 92.2%. Thus, we believe this procedure can successfully remove contamination and optimize the sample pre-treatment for radiocarbon dating of organic-rich deposits from coastal and other environments.•Use loss-on-ignition analysis to locate the ideal sampling intervals.•Sieve each sample with 200 µm and then 100 µm sieve to remove roots and organic debris.•Acid-leach each of the sieved sediment samples (100-200 µm) with HCL to remove carbonates.

Zircon U‐Pb Age Constraints on NW Himalayan Exhumation From the Laxmi Basin, Arabian Sea

AbstractThe Indus Fan, located in the Arabian Sea, contains the bulk of the sediment eroded from the Western Himalaya and Karakoram. Scientific drilling in the Laxmi Basin by the International Ocean Discovery Program recovered a discontinuous erosional record for the Indus River drainage dating back to at least 9.8 Ma, and with a single sample from 15.6 Ma. We dated detrital zircon grains by U‐Pb geochronology to reconstruct how erosion patterns changed through time. Long‐term increases in detrital zircon U‐Pb components of 750–1,200 and 1,500–2,300 Ma record increasing preferential erosion of the Himalaya relative to the Karakoram between 8.3–7.0 and 5.9–5.7 Ma. The average contribution of Karakoram‐derived sediment to the Indus Fan fell from 70% of the total at 8.3–7.0 Ma to 35% between 5.9 and 5.7 Ma. An increase in the contribution of 1,500–2,300 Ma zircons starting between 2.5 and 1.6 Ma indicates significant unroofing of the Inner Lesser Himalaya (ILH) by that time. The trend in zircon age spectra is consistent with bulk sediment Nd isotope data. The initial change in spatial erosion patterns at 7.0–5.9 Ma occurred during a time of drying climate in the foreland. The increase in ILH erosion postdated the onset of dry‐wet glacial‐interglacial cycles suggesting some role for climate control. However, erosion driven by rising topography in response to formation of the ILH thrust duplex, especially during the Pliocene, also played an important role, while the influence of the Nanga Parbat Massif to the total sediment flux was modest.

Secular Variations in Provenance of Sedimentary Components in the Western North Pacific Ocean Constrained by Sr Isotopic Features of Deep‐Sea Sediments

AbstractDeep‐sea sediments around Minamitorishima Island in the western North Pacific Ocean record the depositional environment in the central to western North Pacific since the late Cretaceous. Previous studies on the bulk chemical composition of deep‐sea sediments in this area have revealed that the sediment column can be divided into five chemostratigraphic units with at least three intercalated layers enriched in rare‐earth elements. However, the end‐member components and their changes in abundance, which indicate compositional variation, as well as the environmental factors affecting them, remain unclear. Here, we report the bulk chemistry, including newly analyzed 87Sr/86Sr ratios of the sediments, seafloor Mn nodules, and fish teeth collected from the deep‐sea basin around Minamitorishima Island, to identify the end‐member components of the sediments. Our results suggest that the pelagic sediments in the study area are mainly composed of terrigenous components, hydrogenous Mn oxides, biogenic calcium phosphate, and volcanic materials. The combination of Sr isotope modeling and bulk chemistry revealed that the input of volcanic materials has increased twice, which might be Izu‐Bonin‐Mariana tephras of the latest Eocene to Oligocene explosive volcanism at the later event but is unclear at the earlier event. The provenance of terrigenous materials has changed from North America to East Asia. The bulk sediment chemostratigraphy around Minamitorishima Island could have resulted not only from the local environmental changes in the pelagic realm, but also from volcanism around the Pacific Ocean and the northwestward movement of the area due to the Pacific plate motion.

Primary deposition and early diagenetic effects on the high saturation accumulation of gas hydrate in a silt dominated reservoir in the Gulf of Mexico

On continental margins, high saturation gas hydrate systems (>60% pore volume) are common in canyon and channel environments within the gas hydrate stability zone, where reservoirs are dominated by coarse-grained, high porosity sand deposits. Recent studies, including the results presented here, suggest that rapidly deposited, silt-dominated channel-levee environments can also host high saturation gas hydrate accumulations. Here we present several sedimentological data sets, including sediment composition, biostratigraphic age from calcareous nannofossils, grain size, total organic carbon (TOC), C/N elemental ratio, δ13C-TOC, CaCO3, total sulfur (TS), and δ34S-TS from sediments collected with pressure cores from a gas hydrate rich, turbidite channel-levee system in the Gulf of Mexico during the 2017 UT-GOM2-1 Hydrate Pressure Coring Expedition. Our results indicate the reservoir is composed of three main lithofacies, which have distinct sediment grain size distributions (type A-silty clay to clayey silt, type B-clayey silt, and type C-sandy silt to silty sand) that are characteristic of variable turbidity current energy regimes within a Pleistocene (< 0.91 Ma) channel-levee environment. We document that the TOC in the sediments of the reservoir is terrestrial in origin and contained within the fine fraction of each lithofacies, while the CaCO3 fraction is composed of primarily reworked grains, including Cretaceous calcareous nannofossils, and part of the detrital load. The lack of biogenic grains within the finest grained sediment intervals throughout the reservoir suggests interevent hemipelagic sediments are not preserved, resulting in a reservoir sequence of silt dominated, stacked turbidites. We observe two zones of enhanced TS at the top and bottom of the reservoir that correspond with enriched bulk sediment δ34S, indicating stalled or slowly advancing paleo-sulfate-methane transition zone (SMTZ) positions likely driven by relative decreases in sedimentation rate. Despite these two diagenetic zones, the low abundance of diagenetic precipitates throughout the reservoir allowed the primary porosity to remain largely intact, thus better preserving primary porosity for subsequent pore-filling gas hydrate. In canyon, channel, and levee environments, early diagenesis may be regulated via sedimentation rates, where high rates result in rapid progression through the SMTZ and minimal diagenetic mineralization and low rates result in the stalling of the SMTZ, enhancing diagenetic mineralization. Here, we observed some enhanced pyritization to implicate potential sedimentation rate changes, but not enough to consume primary porosity, resulting in a high saturation gas hydrate reservoir. These results emphasize the important implications of sedimentary processes, sedimentation rates, and early diagenesis on the distribution of gas hydrate in marine sediments along continental margins.

Tracing carbonate dissolution in subducting sediments by zinc and magnesium isotopes

Carbonate dissolution in subduction zones transfers surface carbon to the mantle and plays an important role in regulating global carbon cycles through geologic time. Petrological observations and thermodynamic models predict substantial dissolution of subducting carbonates induced by slab-derived fluids at arc mantle depths, but this dissolution process has rarely been verified by existing geochemical tracers. In this paper we show that zinc and magnesium isotopes can serve as such tracers through a comparative study on carbonate-bearing and carbonate-free sediments from the South China Sea and the Philippine Sea that are going to be subducted. Leaching experiments are further performed to characterize the isotopic difference between dissolved carbonates and silicate components in sediments. Bulk carbonate-bearing sediments and carbonate-free sediments surprisingly have indistinguishable δ66Zn (0.26 ± 0.04‰ versus 0.25 ± 0.04‰), but the former display systematically lower δ26Mg (−0.85‰ to −0.17‰, n = 10) than the latter (−0.26‰ to +0.13‰, n = 13). Leaching experiments show that dissolved carbonates have much higher δ66Zn (0.82 ± 0.26‰) and lower δ26Mg (−2.70 ± 0.35‰) compared with the silicate residues (δ66Zn = 0.21 ± 0.06‰; δ26Mg = −0.06 ± 0.14‰). These results indicate that the presence of carbonate components has insignificant influence on Zn isotopic compositions of bulk sediments but prominent influence on their Mg isotopic compositions. In this respect, the final fate of carbonates in subducting sediments can be tracked by a combined Mg and Zn isotope analysis on mantle-derived magmas. For instance, bulk carbonate-bearing sediment addition (i.e., no carbonate dissolution) during subduction would produce low δ26Mg but normal δ66Zn values (i.e., Mg-Zn isotopic “decoupling”) in mantle-derived magmas. By contrast, if carbonate dissolution occurs during subduction, the high δ66Zn and low δ26Mg (i.e., Mg-Zn isotopic “coupling”) signals of dissolved carbonates will be transferred to the sources of mantle-derived magmas. We test this application for a Cenozoic subduction-related, arc-like volcanic exposure from Tengchong, Southwestern China and find significant Mg-Zn isotopic coupling, which demonstrates carbonate dissolution during Indian Oceanic slab subduction. Our results also shed constraints on the amount of dissolved carbonates in the sub-arc mantle. Available data reveal the absence of high δ66Zn and low δ26Mg in global arc lavas, for which we suggest to be the result of a relatively low proportion (<20%) of dissolved calcium carbonates in the sub-arc mantle.

Carbon cycle dynamics and ecology revealed by the carbon isotopic composition of single organic microfossils during the Late Devonian Biotic Crisis.

We apply a new approach for the δ13 C analysis of single organic-walled microfossils (OWM) to three sites in the Appalachian Basin of New York (AB) that span the Late Devonian Biotic Crisis (LDBC). Our data provide new insights into the nature of the Frasnian-Famennian carbon cycle in the AB and also provide possible constraints on the paleoecology of enigmatic OWM ubiquitous in Paleozoic shale successions. The carbon isotope compositions of OWM are consistent with normal marine organic matter of autochthonous origins and range from -32 to -17‰, but average -25‰ across all samples and are consistently 13 C-enriched compared to bulk sediments (δ13 Cbulk ) by ~0-10‰. We observe no difference between the δ13 COWM of leiospheres (smooth-walled) and acanthomorphic (spinose) acritarch OWM, indicating that our data are driven by ecological rather than taxonomic signals. We hypothesize that the offset between δ13 COWM and δ13 Cbulk is in part due to a large δ13 C gradient in the AB water column where OWM utilized relatively 13 C-enriched dissolved inorganic carbon near the surface. Thus, the organisms producing the balance of the total organic carbon were assimilating 13 C-depleted C sources, including but not limited to respired organic carbon or byproducts of fermentation. We also observe a systematic decrease in both δ13 COWM and δ13 Cbulk of 3‰ from shoreward to open-ocean facies that may reflect the effect of 13 C-enriched dissolved inorganic carbon (DIC) derived from riverine sources in the relatively enclosed AB. The hypothesized steep carbon isotope gradient in the AB could be due to a strong biological pump; this in turn may have contributed to low oxygen bottom water conditions during the LDBC. This is the first time single-microfossil δ13 Corg analyses of eukaryotes have been directly compared to bulk δ13 Corg in the deep-time fossil record.