Sedimentary Organic Matter Research Articles

System efficiency of methylmercury production, an important indicator for evaluating the long-term risk of mercury: From a case study in the Jiaozhou Bay to global coastal seas

With the implementation of the Minamata Convention, total Hg (THg) in coastal seas are expected to be reduced. However, methylmercury (MeHg) levels in aquatic environments depend not only on THg, but also the system efficiency of MeHg production (represented by MeHg/THg ratio in seawater) whose variations with time remain unclear. By choosing the Jiaozhou Bay (JZB) as a typical coastal system, combined with the published data from the global coastal systems, system efficiency of MeHg production in coastal seas were investigated. The mass budget of MeHg showed that the in situ production and degradation are the major source and sink of MeHg in the JZB. The relationships of MeHg in the seawater and fish with MeHg/THg in seawater indicate that system efficiency of MeHg production may control the risk of MeHg in coastal systems. The sulfate and nitrate in seawater, organic matter in sediment, biotic methylation, and transport of inorganic Hg from the seawater to sediment were identified to be critical parameters and processes for the MeHg/THg in global coastal seas. The findings of this study highlight the importance of monitoring the system efficiency of MeHg production and its controlling processes and parameters for evaluating the long-term risk of Hg.

Spatiotemporal distribution of sedimentary chloropigments and organic carbon in a shelf sea ecosystem, with a focus on the cold water mass

The Yellow Sea is one of the most thoroughly studied shelf seas in the northwestern Pacific. However, many aspects of the northern Yellow Sea sediments remain poorly understood. Sedimentary chloropigments and total organic carbon (TOC) are crucial components that indicate benthic primary productivity and ecosystem functioning in the marginal sea system. The present study investigated the temporal and spatial variations of sediment chloroplastic pigments (Chl-a and Pha-a) and TOC contents in relation to seasons and the northern Yellow Sea Cold Water Mass (NYSCWM). Decadal trends were also examined using linear regression on time-series data from 12 cruises conducted over a nine-year period (2006–2014). The correlations between sedimentary Chorophy-a (Chl-a), Pheophorbide-a (Pha-a), TOC, and their ratios with other abiotic and biotic factors were analyzed to detect any effects of the NYSCWM on the spatiotemporal distribution of sediment Chl-a, Pha-a, TOC contents, as well as the ecological relevance of their ratios as indicators of food quality (freshness) in the benthic system. The NYSCWM substantially influences the spatial and seasonal distribution of sedimentary Chl-a, Pha-a, and TOC contents. High values of Pha-a, TOC, and the ratios of Pha-a/(Chl-a + Pha-a) and TOC/Chl-a were often observed in the central region of the NYSCWM, where Chl-a showed clear seasonal fluctuations while Pha-a and TOC remained relatively constant. While sedimentary TOC appears to negatively mirror the spatial pattern of primary productivity in the water column, the spatial pattern of sedimentary Chl-a in relation to NYSCWM is less evident. However, the contents of Pha-a and TOC in the central NYSCWM sediments were higher than those at surrounding NYSCWM stations. Surface sediment Pha-a/(Chl-a + Pha-a) ratio was negatively correlated with meiofauna abundance and biomass and positively correlated with nematode/copepod ratio. This finding indicates that the quality of sediment organic matter is important to meiofauna. Conversely, the lower organic degradation rate at the lower bottom temperature of the NYSCWM may explain the observed higher Pha-a and TOC contents in its central area. Time-series data collected over nine years at the NYSCWM stations showed a decreasing trend for Chl-a, while TOC and the ratio of Pha-a/(Chl-a + Pha-a) exhibited increasing tendencies. This trend may imply a reduced quality of food supply to the benthic food web in the shelf sea system, along with degraded ecosystem functioning and service under the impacts of global change and anthropogenic disturbances.

Sargassum beaching on mangrove sediments shifts microbial and crab metabolisms and enhances blue carbon storage

AbstractBenthic metabolism and net carbon accumulation in mangroves sediments strongly depend on the quantity and quality of organic matter (OM) supplied, including material brought by coastal waters such as the macroalgae Sargassum spp. Mesocosms were used to assess the effect of eutrophication by Sargassum on mangrove sediments. The concentration of fatty acids (FAs), organic carbon and its carbon isotopic signature, and the sediments–air CO2 fluxes were used to follow the evolution of sedimentary OM in surface and subsurface sediments for 60 d. Sargassum beaching shifted microbial and crab metabolism, leading to a preferential degradation of the labile fraction of OM from both Sargassum (δ13C = −17.7‰ and high concentration of essential FAs) and mangrove leaves (δ13C: −28.9‰ and high concentrations of 18:2ω6 and 18:3ω3). Fatty acids composition of crabs hepatopancreas revealed they preferentially fed on Sargassum and these invertebrates also increased the particulate OM tidal export. In addition, microbial activity at the sediment surface was enhanced, as revealed by strong production of branched FAs and higher CO2 fluxes in mesocosms containing Sargassum. However, Sargassum beaching also increased the transfer and preservation of more refractory OM from mangrove leaves found in higher quantity in subsurface sediments (6–8 cm) after 60 d. Inputs of macroalgae induced a negative priming effect and enhanced the preservation of blue carbon in the sediments. This negative priming effect was enhanced by crab activities. These biotic interactions that include microbial communities apparently make mangrove efficient in storing carbon in a context of growing eutrophication of the tropical ocean.

Utilizing fluorescence indicators to apportion organic sources in estuarine/coastal sediments: A comparison with a stable isotopic model

Coastal sediments accumulate organic matter (OM) from diverse sources, including local anthropogenic pollution. Effective source tracking of sediment OM is crucial for pollution source management. This study compares fluorescence proxies and stable isotopic ratios as tracers for sediment OM in Gangu Port, Korea. An optimized extraction method using distilled water for 0.5 h yielded distinct fluorescence signatures. The humification index (HIX) and protein-like component (C3%) showed ideal mixing behavior with two end-members (fishery market sediment and algae). A Bayesian end-member mixing analysis model revealed that agricultural soil is the prevalent contributor to sediments, aligning with land use patterns. The fluorescence-based model showed higher sensitivity to anthropogenic influences compared to traditional stable isotope ratios. The results strongly agreed with isotope ratio-based predictions, exhibiting a positive correlation (p < 0.05) at 8 out of 14 sites. This study highlights the potential of fluorescence-based tracking to complement or replace conventional stable isotope methods.

Impacts of anthropogenic resuspension on sediment organic matter: An experimental approach

Globally coastal sediments are frequently disturbed by a wide range of physical anthropogenic processes (e.g. bottom trawling) which causes resuspension of sediment organic matter (OM) into the overlaying water column. In this study we present experimental results showing that anthropogenic sediment resuspension decreases the organic carbon (14x) and nitrogen (3x) content in the sediment material resuspended to the water column, while no measurable response was found for organic phosphorus. Our findings furthermore show that the OM bioavailability decreased and the Carbon:Nitrogen:Phosphorus stoichiometry was changed suggesting that anthropogenic resuspension changes the chemical composition, and/or production and degradation pathways of the OM pool. The detected changes in OM biogeochemistry could affect nutrient release, fuel oxygen consumption and at the same time increase CO2 production in coastal waters.

Microplastics impair extracellular enzymatic activities and organic matter cycling in oligotrophic sandy marine sediments

Microplastics (MPs) are ubiquitous and constantly accumulating in the marine environment, especially sediments. Yet, it is not well clarified if and how their carbon backbone could interact with surrounding sediments, eventually impairing key benthic processes. We assessed the effects of a ‘pulse’ contamination event of MPs on sedimentary organic matter (OM) quantity, quality and extracellular enzymatic activities (EEAs), which are well established descriptors of benthic ecosystem functioning. Marine sediments were exposed for 30 days to environmentally relevant concentrations (∼0.2 % in weight) of naturally weathered particles (size range 70–210 μm) of polyurethane, polyethylene, and a mixture of the most common polymers that are documented to accumulate in marine sediments. Despite the low concentration, contaminated sediments showed significantly different composition of OM, showing a decrease in lipid content and increase in protein. Moreover, we document a significant decrease (over 25 %) in quantity of biopolymeric C already after 15 days of exposure, compared to controls. Contaminated sediments showed lower C degradation rates (up to −40 %) and altered EEAs, with alkaline phosphatase being ∼50 % enhanced and aminopeptidase being reduced over 35 % compared to control treatments. Overall, the effects generated by the mixture of polymers were smaller than those exerted by the same amount of a single polymer. Our results provide insights on how that MPs can significantly alter marine sedimentary biogeochemistry through altered benthic processes, that could cumulatively impair whole benthic trophic webs by enhancing the accumulation and possible longer-term storage of recalcitrant organic C in the seabed.

Spatial and historical patterns of sedimentary organic matter sources and environmental changes in the Ross Sea, Antarctic: implication from bulk and n-alkane proxies

Organic carbon (OC) burial in the Antarctic marginal seas is essential for regulating global climate, particularly due to its association with ice shelf retreat. Here, we analyzed total OC (TOC), total nitrogen (TN), radiocarbon isotope, n-alkanes and relative indicators in surface and core sediments from the Ross Sea, West Antarctica. Our aim was to investigate spatial and historical changes in OC sources, and to explore the influencing factors and implications for ice shelf retreat since the last glacial maximum (LGM). Our results revealed distinct spatial patterns of OC sources as indicated by n-alkane indicators in surface sediments. In the Western Ross Sea, n-alkanes predominantly originated from phytoplankton and bacteria, as evidenced by their unimodal distribution, low carbon preference index (CPI) of short-chain n-alkanes (CPIL = 1.41 ± 0.30), and low terrestrial/aquatic ratio (TAR = 0.22 ± 0.14). In the Southwest Ross Sea, n-alkanes were derived from marine algae and terrestrial bryophytes, indicated by bimodal distribution, low ratio of low/high molecular-weight n-alkanes (L/H = 0.62 ± 0.21), low CPI of long-chain n-alkanes (CPIH = 1.18 ± 0.16), and high TAR (1.26 ± 0.66). In contrast, the Eastern Ross Sea exhibited n-alkanes that were a combination of phytoplankton and dust from Antarctic soils and/or leaf waxes from mid-latitude higher plant, as suggested by both unimodal and bimodal distributions, high L/H (1.60 ± 0.58) and CPIH (2.04 ± 0.28), and medium TAR (0.61 ± 0.30). Geologically, during the LGM (27.3 – 21.0 ka before present (BP)), there was an increased supply of terrestrial OC (TOC/TN = 13.63 ± 1.29, bimodal distribution of n-alkanes with main carbon peaks at nC17/nC19 and nC27). From 21.0 to 8.2 ka BP, as glaciers retreated and temperatures rose, the proportion of marine n-alkanes significantly increased (TOC/TN = 9.09 ± 1.82, bimodal distribution of n-alkanes with main carbon peaks at nC18/nC19 and nC25). From 8.2 ka BP to the present, as the ice shelf continued to retreat to its current position, the marine contribution became dominant (TOC/TN = 8.18 ± 0.51, unimodal distribution of n-alkanes with main carbon peak at nC17/nC18/nC19, and low TAR (0.41 ± 0.32)). This research has significant implications for understanding the variations in Antarctic OC sources and their climatic impacts in the context of accelerated glacier melting.

Accounting of weathering enhancement by mafic mineral spreading for CO 2 storage

The reduction of atmospheric CO 2 is an urgent global issue in the mitigation of global warming. Carbonate acts as a carbon sink in Earth's surface layer, and the weathering of terrestrial silicates and the deposition of oceanic calcium carbonate and organic matter mainly determine atmospheric and oceanic carbon dynamics on geological time scales. Various CO 2 reduction approaches have been evaluated, and the weathering acceleration method is expected to be a low-cost approach. This study attempts to estimate carbonate precipitation potential and dissolution rate from alkali leaching rates using weathering tests on mafic rocks. Based on Japan's annual average rainfall, the in situ carbonate precipitation potential obtained by spreading an olivine mineral or basalt rock powder at 40 ton-powder/ha was on the order of 10 -3 ton/year/ton-rock. This weathering rate could not be greatly accelerated under natural temperature conditions and fine granulation of the minerals.

Deciphering Permian wetland deposits of the Parnaíba Basin through an integrated study of lithofacies and palynofacies in Western Gondwana

During the Permian, the northwestern portion of the supercontinent Gondwana experienced significant climate changes, among which the increasing aridity in the Parnaíba Basin, located between Brazil's northern and northeastern regions. The marine influence associated with the Panthalassa Ocean, evident in the Silurian and Devonian deposits, was progressively attenuated in the late Carboniferous, culminating in extensive continental deposits during the Permian and the Early Triassic in this region. In this paper, we present the first palynofacies analysis of the Permian Pedra de Fogo Formation, conducted concurrently with the description and association of sedimentary facies from outcrops located in the state of Maranhão, southwest of the Parnaíba Basin. A total of 15 m of sedimentary succession was described, and 28 samples were selected for palynofacies analysis. As a result, we identified six sedimentary facies, which were grouped into two distinct facies associations: Fa1 – Central Lake and Fa2 – Playa Lake. The palynofacies analysis considered the sedimentary organic matter, classifying it into amorphous organic matter, phytoclasts (subdivided into eight subgroups), and palynomorphs (with six subgroups). Integrating the results enabled an understanding of the depositional context, which is closely related to water dynamics and climate seasonality. The shallow lake system interpreted during the wet phases recorded interruptions in the normal sedimentation of the central lake due to turbidite deposits associated with ephemeral rivers. Conversely, during dry phases, salt precipitation occurred with subsequent substitution and aerial exposure of the surface when the water balance was negative. Eodiagenetic events were inferred and are considered throughout the article. The alternation of the hydrological regime allowed the deposition in proximal, transitional, and distal environments, creating a distinctive mosaic of wetland landscapes. The data presented indicate humid conditions within a context of increasing aridity in the studied location, particularly in the upper part of the Pedra de Fogo Formation.

Sedimentary organic matter and paleoenvironmental reconstruction of the Santana Group (Lower Cretaceous), Araripe Basin, Northeast Brazil

Depositional controls of the Santana Group in the Araripe Basin are still being debated. The main controversial subject is their marine influence and paleoenvironmental evolution. In this study, palynofacies analysis was performed on 59 samples from one core drilled at Sítio Romualdo in the Araripe Basin to investigate sedimentary organic matter. Three palynofacies associations (structureless, continental particles, and aquatic + opaque) were identified. The Santana Group consist of Barbalha, Crato, Ipubi and Romualdo formations. Based on palynofacies associations we conclude that the depositional setting of the Barbalha Formation reflects a fluvially-fed lacustrine system under oxic conditions. The Crato Formation, associated with tidal flats, coastal lakes, and lagoons within an open bay environment, represents a bayhead delta system. The Ipubi Formation corresponds to a coastal plain typical of sabkha paleoenvironments, characterized by low energy under reducing conditions, during drier climate conditions. The Romualdo Formation records mainly an estuarine paleoenvironment characterized by dysoxic to anoxic conditions. The presence of palynomorph groups typifies a late Aptian age for the Santana Group, which is based on the range of guide species marked mainly by the presence of Sergipea variverrucata biozone (P-270), as well as the occurrence of Complicatisaccus cearensis and Equisetosporites maculosus. The identification of marine palynomorphs (dinoflagellate cysts Subtilisphaera and foraminiferal test linings) are indicative of several, local marine incursions.

Constraints on vertical variability of geogenic ammonium in multi-layered aquifer systems

The elevated levels of geogenic (natural) ammonium in groundwater have been frequently documented in recent years. Although improving insights have been achieved in understanding the genesis of ammonium in the subsurface environment, the vertical variability of the geogenic ammonium in groundwater remains poorly understood. Here, we selected typical multi-layered aquifer systems in the central Yangtze River plain and characterized the vertical heterogeneity of geogenic ammonium through the hydrogeochemical analysis. Subsequently, the controlling factors were identified by examining the molecular composition of dissolved organic matter (DOM) and aquifer sediment features. The results indicated that the ammonium concentration in groundwater increased from the deep to shallow aquifers (2.13 to 9.88 mg/L as N), accompanied by a transition in organic matter (OM) degradation towards the methanogenic stage (δ13C-DIC: -23.07 to -0.34‰). Compared to the deeper aquifers, the DOM in the shallow aquifer was characterized by a higher abundance of the N-containing OM (15.1% > 13.13% > 12.76%) with a lower molecular lability index, corresponding to more thorough degradation extent. The characteristics of the soluble OM in depth-matched sediments were similar to those of the DOM in groundwater, suggesting the persistent water-rock interactions. Besides, the pumping tests revealed that the hydraulic conductivity decreased from deep to shallow aquifers (2.28 to 0.62 m/d), which further facilitated the more retention of geogenic ammonium in the shallow aquifer. That is, the combined effects of the abundant N-containing OM in sediments, strong degradation of the bioactive DOM, and long retention governed by hydrodynamics contributed to the increased ammonium enrichment in the shallow aquifer, thereby generating the vertical variability. The findings underscore the significance of the complex coupled factors in controlling the vertical distribution of geogenic ammonium in multi-layered aquifer systems, which was crucial for understanding the spatial heterogeneity of geogenic contaminated groundwater.

Carbon and nitrogen sources in tropical coastal lagoon food webs under variable hydrological conditions

Whilst the impact of continental and marine nutrient sources on the ecological functioning of coastal food webs is well investigated in temperate regions, tropical ecosystems remain less well understood, in particular coastal lagoons. In this study, the sources of carbon and nitrogen in a coastal lagoon system in the southeast of Madagascar are traced using stable isotopes of carbon (δ13C) and nitrogen (δ15N). Three interconnected coastal lagoons with different degree of river influence and eutrophication are investigated. Their food webs are assessed with respect to spatial and seasonal (wet and dry seasons) variations in lagoon water conditions, as well as with respect to the sources of nutrients and organic matters. Results show that river input is the main source of NO3−, and that NO3− supply is significantly higher during the wet season. In contrast, NH4+ is produced internally in the lagoon, and concentrations are higher during the dry season. A lower δ13C value observed in particulate organic matter (POM; proxy of phytoplankton) indicates terrestrial-riverine carbon inputs, which generally have low δ13C values. During the dry season, exceptionally high δ15N values of lagoon POM suggest the uptake of newly produced lagoon water NH4+ and/or the 15N enrichment of lagoon POM pool due to mineralization, resulting in 15N enrichment in consumers. Moreover, δ13C and δ15N values of consumers (fishes and invertebrates) reflect predominantly those of lagoon POM and sediment organic matter (SOM), suggesting that consumers primarily depend on lagoon POM and SOM as sources of carbon and nitrogen. The δ15N values in consumers further indicate that some species feed on more than one trophic level, suggesting flexible foraging strategy of consumers as a function of food source availability. This study demonstrates the roles of both river inflow and sediment in supplying carbon and nitrogen to a coastal lagoon food web, documenting the ecological implications of seasonal variations in lagoon hydrological conditions.

Organic matter in geothermal springs and its association with the microbial community

Organic matter (OM) plays an important role in the biogeochemical cycles of carbon, nitrogen, and other elements, shaping the structure of the microbiome and vice versa. However, the molecular composition of OM and its impact on the microbial community in terrestrial geothermal environments remain unclear. In this study, we characterized the OM in water and sediment from a typical geothermal field using ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry. By combining high-throughput amplicon sequencing and multivariate analyses, we deciphered the association between OM components and microbial community. A surprisingly high chemodiversity of OM was observed in the waters (11,088 compounds) and sediments (7772 compounds) in geothermal springs. Sulfur-containing organic compounds, a characteristic molecular signature of geothermal springs, accounted for 21 % ± 5 % in waters and 33 % ± 4 % in sediments. Multivariate analyses revealed that both labile and recalcitrant fractions of OM (e.g., carbohydrates intensity and tannins chemodiversity) influenced the structure and function of the microbial community. Co-occurrence networks showed that Proteobacteria and Crenarchaeota accounted for most of the connections with OM in waters (33 % and 15 %, respectively) and sediments (15 % and 12 %, respectively), highlighting their key roles in carbon cycling. This study expands our understanding of the molecular compositions of OM in geothermal springs and highlights its potentially important role in global climate change through microbial carbon cycling.

Organic petrographic and geochemical insights into organic matter derived from land plants and marine algae in the Lark Formation, Danish North Sea

Climatic fluctuations from the Eocene to the Miocene highlight the importance of investigating the paleoenvironment of the latest Eocene to the Middle Miocene Lark Formation in the Danish North Sea. This study investigates immature sedimentary organic matter in the Lark Formation using 54 cuttings samples and one core sample collected from seven wells in the eastern North Sea Basin. Organic petrography and molecular geochemistry analyses were performed to determine the variations in the quantity and origin of allochthonous and autochthonous organic matter. Additionally, the study assesses the impact of climate fluctuations on marine productivity in the eastern North Sea Basin and land plant vegetation at the basin margins during the latest Eocene to the Middle Miocene.The organic matter in the Lark Formation originated from mixed sources, primarily land plants, with a secondary contribution from marine algae. This is indicated by the maceral composition and the types and abundance of aliphatic and aromatic hydrocarbon biomarker compounds. Moreover, the presence of diterpenoids (gymnosperm biomarkers) and non-hopanoid triterpenoids (angiosperm biomarkers) reveals that the allochthonous organic matter originated from conifers and angiosperms.Climatic impacts on land plants and marine algae during the latest Eocene to the Middle Miocene are revealed by several parameters: the Averaged Chain Length (ACL) of land plant waxes, the proportion of coniferous contribution (C/(C + A)), and the whole rock volume percentages of huminite, inertinite (H + I, vol%) and liptinite (L, vol%). The shifts to cooler and drier climates highlighted the cold adaptation of onshore conifers and resulted in the input of higher molecular weight waxy components into the sediments. However, under these conditions, reduced precipitation and runoff resulted in lower amounts of terrigenous organic matter supplied to the basin. Additionally, the drop in water temperature and the warm-affinity of local algae assemblage led to reduced marine productivity. Together, these factors contributed to an overall decrease in organic richness. In contrast, during shifts to warmer and more humid climates, the trend reversed. The contribution of conifers to the floral assemblage diminished, but higher amounts of terrigenous organic matter were transported to the basin due to increased precipitation and runoff. This was accompanied by warmer water temperatures, boosting the productivity of organic-walled microplankton in the marine environment and contributing to greater organic richness.

The geothermal gradient shapes microbial diversity and processes in natural-gas-bearing sedimentary aquifers

Abstract. Deep subsurface microorganisms constitute over 80 % of Earth's prokaryotic biomass and play an important role in global biogeochemical cycles. Geochemical processes driven by geothermal heating are key factors influencing their biomass and activities, yet their full breadth remains uncaptured. Here, we investigated the microbial community composition and metabolism in microbial-natural-gas-bearing aquifers at temperatures ranging from 38 to 81 °C, situated above nonmicrobial-gas- and oil-bearing sediments at temperatures exceeding 90 °C. Cultivation-based and molecular gene analyses, including radiotracer measurements, of formation water indicated variations in predominant methanogenic pathways across different temperature regimes of upper aquifers: high potential for hydrogenotrophic–methylotrophic, hydrogenotrophic, and acetoclastic methanogenesis at temperatures of 38, 51–65, and 73–81 °C, respectively. The potential for acetoclastic methanogenesis correlated with elevated acetate concentrations with increasing depth, possibly due to the decomposition of sedimentary organic matter. In addition to acetoclastic methanogenesis, in aquifers at temperatures as high as or higher than 65 °C, acetate is potentially utilized by microorganisms responsible for the dissimilatory reduction of sulfur compounds other than sulfate because of their high relative abundance at greater depths. The stable sulfur isotopic analysis of sulfur compounds in water and oil samples suggested that hydrogen sulfide, generated through the thermal decomposition of sulfur compounds in oil, migrates upward and is subsequently oxidized with iron oxides present in sediments, yielding elemental sulfur and thiosulfate. These compounds are consumed by sulfur-reducing microorganisms, possibly reflecting elevated microbial populations in aquifers at temperatures as high as or higher than 73 °C. These findings reveal previously overlooked geothermal-heat-driven geochemical and microbiological processes involved in carbon and sulfur cycling in the deep sedimentary biosphere.

Water Column Nitrogen Removal During Storms in a Low‐Order Watershed

AbstractWater column removal in streams is a nitrogen (N) cycling pathway that has been historically overlooked. Studies filling this knowledge gap have focused on the role of water column N removal in mid‐to‐large‐order rivers with consistently high suspended sediment concentrations. However, smaller streams may provide comparable suspended sediment concentrations during and after storm events, creating favorable conditions for water column N removal. To assess the presence, magnitude, and control of water column N removal during storms in low‐order watersheds, we measured water column denitrification and heterotrophic assimilatory N uptake rates at three locations in a Mid‐Atlantic watershed during five storm events of different magnitude, sediment loads, and nutrient availability. We found large variations in water column denitrification (0–5.56 mg N g−1 d−1) and assimilatory uptake (0.003–1.67 mg N g−1 d−1). Higher rates of N removal occurred during flow recession, with a correlation between suspended sediment organic matter content and denitrification. On average, denitrification rates in the water column were higher when flashy responses to storm events occurred. In contrast to denitrification, water column N removal rates (as both denitrification and heterotrophic assimilation) during storm events were comparable to those measured at baseflow in larger rivers. However, water column denitrification could only account for less than 10% of potential reach‐scale N removal during most of the storm events. Our findings provide insight into the ecological relevance of small stream water columns and suggest that more research is needed to understand the magnitude of stream water column processing on watershed‐scale N removal.

Sediment properties control riverine methane emissions: A case study of the Liao River in northern China

River and stream sediments act as biogeochemical reactors for greenhouse gases, particularly methane. However, understanding how riverbed sediment properties influence river carbon emissions remains relatively unclear. The Liao River in northern China is a typical watershed with heterogeneous water and sediment sources, characterized by varying sediment properties. In this study, we surveyed CH4 and CO2 emissions from its mainstem and tributaries during flood and dry seasons. We found consistent seasonal patterns in CH4 and CO2 emissions, with peaks occurring during the flood season. The average CH4 and CO2 fluxes were 1.64 ± 1.80 mmol·m−2·d−1 and 59.66 ± 44.60 mmol·m−2·d−1, respectively. Notably, the percentage of sediment silt was significantly correlated with CH4 concentration and flux (R2 = 0.12−0.30, p < 0.05). Fine particles dominated the availability of sediment organic matter and redox conditions, which were related to riverine CH4 production and emissions. Structural equation modeling revealed that both grain size and the percentage of TOC (total organic carbon) directly influenced riverine CH4 and CO2 emissions. The organic content and redox conditions of the riverbed sediment collectively explained 65% of riverine CH4 emissions, while grain size composition indirectly controlled CH4 emissions by altering sediment substrate quality and redox conditions. In contrast, river CO2 emissions were only weakly dependent on anaerobic metabolism in riverbed sediments. These findings enhance our understanding of the sources and metabolic mechanisms of riverine CH4 and CO2 emissions and offer potential improvements for estimating carbon fluxes in regional or global riverine networks by considering riverbed sediment properties.

Geochemical Markers of Organic Matter Transformation in the Eastern Part of the Laptev Sea

The sources of supply and transformation of organic matter (OM) during the transition from the dissolved form to suspension, fluffy and bottom sediments on the meridional transect from the Lena River delta to the continental slope were described (depths from 10 to 2390 m, cruise 63 of the R/V Akademik Mstislav Keldysh, September 2015). The results of the study of OM molecular markers showed that dissolved and suspended OM of marine and terrigenous origin biodegrades in the water column and practically does not accumulate in bottom sediments. Thus, OM of the Lena river runoff does not contribute to the formation of OM in the bottom sediments in the summer period. On the outer shelf, an area of influence of ice bloom on the sedimentation process was revealed.

Characterization of sediment organic matter in the outer Yangtze River Estuary using stable isotopes, optical techniques, and FT-ICR-MS: Implications for the carbon burial mechanism

The burial of sediment organic matter (SOM) in the estuary and shelf plays an important role in the global carbon cycle. However, it is challenging to determine the source, composition, and burial of SOM in the coastal sea, especially at the molecular level. This was explored in the coastal area outside the largest Yangtze River of China with multiple techniques including elemental and stable isotopic analysis, absorption spectroscopy, fluorescence excitation-emission matrices coupled with parallel factor analysis (EEMs-PARAFAC), and ultra-high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The end-member mixing analysis based on δ13C and δ15N showed a dominance of marine contribution (up to 70%) at most stations while the terrestrial contribution increased to >55% nearshore in summer at a high fluvial sediment flux. This was consistent with the offshore decreasing humic-like C1 and C2, humification index (HIX), %lignin-like compounds, and %CHO but increasing tryptophan-like C3, biological index (BIX), %protein-like compounds, and %CHOS from EEMs-PARAFAC and FT-ICR-MS analysis. The %clay correlated positively with SOM content, HIX, %lignin-like compounds, O/C, and modified aromaticity index (AImod) but correlated negatively with %C3, H/C, and the relative abundance of labile formulas (MLBL), while %silt showed contrasting correlations. These results indicated the fine clay sediments adsorbed more humified, aromatic, oxygenated, and terrestrial compounds that were probably more resistant to biodegradation and thus had a higher burial efficiency than those on the silty sediments. Principal component analysis based on SOM indices further revealed different characteristics of SOM in the nearshore, northern offshore, and southern offshore regions, which were probably dependent on the delivery by local current systems. Overall, these findings contributed to unraveling the source and molecular composition of SOM associated with different grain size sediments and local current delivery, which are fundamental for understanding the factors underlying carbon burial in the complex coastal environment.

Sediment oxygen uptake and hypoxia in coastal oceans, the Pearl River Estuary region

Hypoxia is increasing in coastal oceans due to high oxygen consumption and weak ventilation. Quantifying biological oxygen uptake and how its effects on hypoxia respond to stratification is important for management and predicting future trends. This work introduces a simple analysis to quantify and compare the biological and physical drivers of hypoxia, by using an example from the Pearl River Estuary (PRE) region (10–70 m deep). We show that in the PRE region, sediment respires ∼50 % of organic matter produced in the water column and oxidizes ∼88 % of the ammonium produced from sediment organic matter degradation. These processes lead to high sediment oxygen uptake (SOU; 41.1 ± 16.3 mmol m-2d-1). Under stratification, sediment's effect on the bottom oxygen is strongly regulated by the thickness of the bottom boundary layer (BBL), and the robust relationships can be used to parameterize SOU. We then construct a simple and generic mass-balance model to estimate the water column oxygen uptake in the BBL (WOUBBL) and quantify the total oxygen loss. By comparing model results to observations in the PRE and other similar systems, we show that the sensitivity of oxygen levels to SOU is largely controlled by the duration of stratification, while the organic matter settling velocity controls the contributions of SOU to total oxygen consumption. We further demonstrate how the model can help evaluate the primary drivers of hypoxia (stratification versus high oxygen consumption), determine the time scale of stratification required to develop hypoxia, and explain the within and across system variabilities.