Description: Sulfate reduction is a globally important yet poorly quantified redox process in marine sediments. We developed an artificial neural network trained with 199 sulfate profiles, constrained with geomorphological and geochemical maps to estimate global sulfate reduction rate distributions. Globally, 11.3 Tmol sulfate are reduced yearly, ~15% of previous estimates, accounting for the oxidation of 12-29% of the organic carbon flux to the sea floor. Combined with global cell distributions in marine sediments, these results indicate a strong contrast in sub–sea-floor prokaryote habitats: in continental margins global cell numbers in sulfate-depleted sediment exceed those in the overlying sulfate-bearing sediment by an order of magnitude, whereas in the abyss most life occurs in oxic and/or sulfate-reducing sediments.

Description: Dissolved organic matter (DOM) in marine sediment pore waters derives largely from decomposition of particulate organic matter and its composition is influenced by various biogeochemical and oceanographic processes in yet undetermined ways. Here, we determine the molecular inventory of pore water DOM in marine sediments of contrasting depositional regimes with ultrahigh-resolution mass spectrometry and complementary bulk chemical analyses in order to elucidate the factors that shape DOM composition. Our sample sets from the Mediterranean, Marmara and Black Seas covered different sediment depths, ages and a range of marine environments with different (i) organic matter sources, (ii) balances of organic matter production and preservation, and (iii) geochemical conditions in sediment and water column including anoxic, sulfidic and hypersaline conditions. Pore water DOM had a higher molecular formula richness than overlying water with up to 11,295 vs. 2114 different molecular formulas in the mass range of 299–600 Da and covered a broader range of element ratios (H/C = 0.35–2.19, O/C = 0.03–1.19 vs. H/C = 0.56–2.13, O/C = 0.15–1.14). Formula richness was independent of concentrations of DOC and TOC. Near-surface pore water DOM was more similar to water column DOM than to deep pore water DOM from the same core with respect to formula richness and the molecular composition, suggesting exchange at the sediment–water interface. The DOM composition in the deeper sediments was controlled by organic matter source, selective decomposition of specific DOM fractions and early diagenetic molecule transformations. Compounds in pelagic sediment pore waters were predominantly highly unsaturated and N-bearing formulas, whereas oxygen-rich CHO-formulas and aromatic compounds were more abundant in pore water DOM from terrigenous sediments. The increase of S-bearing molecular formulas in the water column and pore waters of the Black Sea and the Mediterranean Discovery Basin was consistent with elevated HS- concentrations reflecting the incorporation of sulfur into biomolecules during early diagenesis. Sulfurization resulted in an increased average molecular mass of DOM and higher formula richness (up to 5899 formulas per sample). In sediments from the methanogenic zone in the Black Sea, the DOM pool was distinctly more reduced than overlying sediments from the sulfate-reducing zone. Bottom and pore water DOM from the Discovery Basin contained the highest abundances of aliphatic compounds in the entire dataset; a large fraction of abundant N-bearing formulas possibly represented peptide and nucleotide formulas suggesting preservation of these molecules in the life inhibiting environment of the Discovery Basin. Our unique data set provides the basis for a comprehensive understanding of the molecular signatures in pore water DOM and the turnover of sedimentary organic matter in marine sediments.

Description: In paleoenvironmental studies, the mineralogical composition of sediments is an important indicator. In combination with other indicators, they contribute to the understanding of changes in sediment sourcing as well as in weathering and depositional processes. Fourier transforminfrared spectroscopy (FTIRS) spectra contain information on mineralogical composition because eachmineral has a unique absorption pattern in the mid-IR range. Although easily obtained, FTIR spectra are often too complex to infermineral concentrations directly. In this study, we use a calibration set of ca. 200 sediment samples conventionally measured using X-ray diffraction (XRD) in order to developmultivariate, partial least squares (PLS) regressionmodels relatingmineral contents to sediment spectra. Good correlations were obtained for the most common minerals (e.g. quartz, K-feldspar, illite, plagioclase, smectite, calcite). Correlation coefficients ranged from 0.85 to 0.92, coefficients for the validation varied from 0.64 to 0.80, the number of latent variables (PLS regression components) in the models ranged between 3 and 7 and the range of variation of the RMSEcv gradient was from 15.28 to 5.7.

Description: The relative abundance of the C32 1,15 long-chain alkyl diol (LCD) is an emerging proxy for the input of riverine aquatic particulate organic carbon (POC) into coastal oceans. This compound has the potential to complement other established proxies reflecting riverine terrestrial POC input and allows for a more nuanced assessment of riverine POC export to coastal seas. The current understanding of this proxy is, however, limited. In this study, we compare different indices for riverine sediment input to coastal marine waters (i.e. C32 1,15-LCD, BIT index and Fe/Ca ratio) in a source-to-sink assessment in the Amazon River drainage system and the northeast South American continental margin, and we test their down-core applicability in a marine gravity core containing late Pleistocene fluvial Amazonian sediments. We show that the relative abundance of the C32 1,15-LCD is highest in water bodies with low flow velocity and low turbidity such as the downstream portion of lowland tributaries and floodplain lakes. Relative C32 1,15-LCD abundance is lowest in Andean white water tributaries where autotrophic productivity is hindered by high turbidity and high flow velocity. We also find that suspended particulate matter from all major tributaries during the extreme 2015 dry season has a similar LCD distribution to that of floodplain lakes. This indicates that the chemical composition of the tributaries is less relevant for the LCD distribution than their physical properties such as flow velocity and turbidity. Results from marine surface sediments offshore the Amazon River estuary show significant positive correlations between all three studied proxies. In contrast, we find that the relative C32 1,15-LCD abundance in the down-core record is anti-correlated to the BIT index and Fe/Ca ratio. While BIT index and Fe/Ca ratio show high (low) values during Heinrich stadials (Dansgaard-Oeschger interstadials), the C32 1,15-LCD proxy shows the opposite signal. BIT values are also higher during Marine Isotope Stage (MIS) 2 than during MIS 3, in contrast to trends in the C32 1,15-LCD proxy. We posit that this pattern arises from a reduction in relative C32 1,15-LCD abundance and total LCD productivity in the Amazon River during MIS 2 when less-humid conditions and lower sea level led to reduced area of floodplains. During Heinrich stadials, Andean sediment input increased and led to higher turbidity that resulted in lower C32 1,15-LCD production. Our study shows that major changes in water discharge, sediment transport and river morphology can lead to discrepancies between the BIT index and the relative abundance of the C32 1,15-LCD. Thus, we suggest that Amazonian aquatic and terrestrial POC pools had contrasting responses to changes related to both climate (e.g. increased Andean precipitation) and river morphology (e.g. steeper along-channel slope due to falling and low stand sea level).

Description: Abundant hydroclimatic evidence from western Amazonia and the adjacent Andes documents wet conditions during Heinrich Stadial 1 (HS1, 18–15 ka), a cold period in the high latitudes of the North Atlantic. This precipitation anomaly was attributed to a strengthening of the South American summer monsoon due to a change in the Atlantic interhemispheric sea surface temperature (SST) gradient. However, the physical viability of this mechanism has never been rigorously tested. We address this issue by combining a thorough compilation of tropical South American paleorecords and a set of atmosphere model sensitivity experiments. Our results show that the Atlantic SST variations alone, although leading to dry conditions in northern South America and wet conditions in northeastern Brazil, cannot produce increased precipitation over western Amazonia and the adjacent Andes during HS1. Instead, an eastern equatorial Pacific SST increase (i.e., 0.5–1.5 °C), in response to the slowdown of the Atlantic Meridional Overturning Circulation during HS1, is crucial to generate the wet conditions in these regions. The mechanism works via anomalous low sea level pressure over the eastern equatorial Pacific, which promotes a regional easterly low-level wind anomaly and moisture recycling from central Amazonia towards the Andes.

Description: Paleoenvironmental studies based on terrigenous biomarker proxies from sediment cores collected close to the mouth of large river systems rely on a proper understanding of the processes controlling origin, transport and deposition of biomarkers.Here, we contribute to the understanding of these processes by analyzing long-chain n-alkanes from the Amazon River system. We use the dD composition of long-chain n-alkanes from river bed sediments from the Amazon River and its major tributaries, as well as marine core-top samples collected off northeastern South America as tracers for different source areas. The d13C composition of the same compounds is used to differentiate between long-chain n-alkanes from modern forest vegetation and petrogenic organic matter. Our d13C results show depleted d13C values (-33 to -36‰) in most samples, indicating a modern forest source for most of the samples. Enriched values (-31 to -33‰) are only found in a few samples poor in organic carbon indicating minor contributions from a fossil petrogenic source. Long-chain n-alkane dD analyses show more depleted values for the western tributaries, the Madeira and Solimões Rivers (-152 to -168‰), while n-alkanes from the lowland tributaries, the Negro, Xingu and Tocantins Rivers (-142 to -154‰), yield more enriched values. The n-alkane dD values thus reflect the mean annual isotopic composition of precipitation, which is most deuterium-depleted in the western Amazon Basin and more enriched in the eastern sector of the basin. Samples from the Amazon estuary show a mixed long-chain n-alkane dD signal from both eastern lowland and western tributaries. Marine core-top samples underlying the Amazon freshwater plume yield dD values similar to those from the Amazon estuary, while core-top samples from outside the plume showed more enriched values. Although the variability in the river bed data precludes quantitative assessment of relative contributions, our results indicate that long-chain n-alkanes from the Amazon estuary and plume represent an integrated signal of different regions of the onshore basin. Our results also imply that n-alkanes are not extensively remineralized during transport and that the signal at the Amazon estuary and plume includes refractory compounds derived from the western sector of the Basin. These findings will aid in the interpretation of plant wax-based records of marine sediment cores collected from the adjacent ocean.

Description: The Amazon River transports large amounts of terrestrial organic carbon (OCterr/ from the Andean and Amazon neotropical forests to the Atlantic Ocean. In order to compare the biogeochemical characteristics of OCterr in the fluvial sediments from the Amazon drainage basin and in the adjacent marine sediments, we analysed riverbed sediments from the Amazon mainstream and its main tributaries as well as marine surface sediments from the Amazon shelf and fan for total organic carbon (TOC) content, organic carbon isotopic composition (δ13CTOC/, and lignin phenol compositions. TOC and lignin content exhibit positive correlations with Al = Si ratios (indicative of the sediment grain size) implying that the grain size of sediment discharged by the Amazon River plays an important role in the preservation of TOC and leads to preferential preservation of lignin phenols in fine particles. Depleted δ13CTOC values (-26.1 to -29.9 ‰) in the main tributaries consistently correspond with the dominance of C3 vegetation. Ratios of syringyl to vanillyl (S = V) and cinnamyl to vanillyl (C = V) lignin phenols suggest that non-woody angiosperm tissues are the dominant source of lignin in the Amazon basin. Although the Amazon basin hosts a rich diversity of vascular plant types, distinct regional lignin compositions are not observed. In the marine sediments, the distribution of δ13CTOC and 38 (sum of eight lignin phenols in organic carbon (OC), expressed as mg/100 mg OC) values implies that OCterr discharged by the Amazon River is transported north-westward by the North Brazil Current and mostly deposited on the inner shelf. The lignin compositions in offshore sediments under the influence of the Amazon plume are consistent with the riverbed samples suggesting that processing of OCterr during offshore transport does not change the encoded source information. Therefore, the lignin compositions preserved in these offshore sediments can reliably reflect the vegetation in the Amazon River catchment. In sediments from the Amazon fan, low lignin content, relatively depleted δ13CTOC values and high (Ad = Al)V ratios indicating highly degraded lignin imply that a significant fraction of the deposited OCterr is derived from petrogenic (sourced from ancient rocks) sources.