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• Compared to muddy sediments, more DOC but less DIC is accumulated in porewaters of sandy sediments. • The remineralization of OC is more complete in muddy areas than in sandy areas. • The sediment porewater in stable sedimentary environments is a significant transient DOC pool. The organic carbon (OC) cycle at the land-ocean interface is an important component of the global carbon budget, yet the processes that control the transfer, transformation, and burial of OC in these regions remain poorly understood. In this work, we examined sedimentary OC (SOC) in short core sediments, dissolved inorganic carbon (DIC), dissolved organic carbon (DOC), and chromophoric dissolved organic matter (CDOM), as well as other solutes in sediment porewaters of the Changjiang Estuary and adjacent East China Sea (ECS) shelf. The main goal of this work is to investigate the variation of the sources and composition of different forms of carbon in estuarine sediments associated with different sedimentary regimes, to further understand the role of sediment porewater in carbon sequestration at the land-ocean interface. Concentrations of Fe2+ and Mn2+ in porewaters of the muddy sediments are much higher than those in the sandy sediments, and SO 4 2− decreases with depth in the deep sediment layer, indicating the degradation of SOC in mobile muds is mainly driven by suboxic and/or anoxic diagenetic processes (e.g., iron-manganese reduction). The accumulation of DIC in the muddy sediment is higher compared to the sandy sediment, indicating relatively complete SOC remineralization. The DOC in porewaters of the muddy areas is mainly composed of highly degraded and low molecular weight humic-like substances (C1), whereas in the sandy area, porewater DOC is mainly composed of less degraded and high molecular weight protein-like substances (C2 and C3). The average DOC stock (28.5 t/km2) in the upper 30 cm sediment porewaters is significantly higher than that of DIC (12.5 t/km2) in sandy area, but less in muddy areas (17.0 t/km2 of DOC vs. 25.4 t/km2 of DIC). The total DOC stock in sediment porewaters of the sandy area accounted for ∼61 % of DOC stock in water column of the ECS, indicating that the porewater is an important DOC pool in the ECS. However, this DOC pool is rather transient due to its high reactivity and mobility, especially in sandy area. Nevertheless, compared with other marine environments, the carbon stock of DOC (average of 43.8 t/km2) in porewaters of stable sedimentary environments is much higher than that of DIC (average of 21.7 t/km2). This work further supports the notion that sedimentary regime plays an important role in OC cycling at the land-ocean interface and highlights the significance of sediment porewaters as a vast carbon pool in marine ecosystems. [Display omitted] [ABSTRACT FROM AUTHOR]

• Denitrification promoted oxidation of As(III) in the estuarine sediments. • Denitrification promoted transformation of FeS/FeS 2 -bound As into Fe oxide-bound As. • Continuous NO 3 − addition ensured As and Fe oxidation, inhibiting subsequent reduction. Microbially-mediated redox processes involving arsenic (As) and its host minerals significantly contribute to the mobilization of As in estuarine sediments. Despite its significance, the coupling between As dynamics and denitrification processes in these sediments is not well understood. This study employed sequential sediment extractions and simultaneous monitoring of dissolved iron (Fe), nitrogen (N), and sulfur (S) to investigate the impact of nitrate (NO 3 −) on the speciation and redistribution of As, alongside changes in microbial community composition. Our results indicated that NO 3 − additions significantly enhance anaerobic arsenite (As(III)) oxidation, facilitating its immobilization by increased adsorption onto sediment matrices in As-contaminated estuarine settings. Furthermore, NO 3 − promoted the conversion of As bound to troilite (FeS) and pyrite (FeS 2) into forms associated with Fe oxides, challenging the previously assumed stability of FeS/FeS 2 -bound As in such environments. Continuous NO 3 − additions ensured As and Fe oxidation, thereby preventing their reductive dissolution and stabilizing the process that reduces As mobility. Changes in the abundance of bacterial communities and correlation analyses revealed that uncultured Anaerolineaceae and Thioalkalispira may be the main genus involved in these transformations. This study underscores the critical role of NO 3 − availability in modulating the biogeochemical cycle of As in estuarine sediments, offering profound insights for enhancing As immobilization techniques and informing environmental management and remediation strategies in As-contaminated coastal regions. [Display omitted] [ABSTRACT FROM AUTHOR]

• Fine particles control the exchangeable silica mobilization in the river. • Current sediment in the estuary contain less reactive silica than historical level. • Increased fine particle fraction affect silica sediment with forms variation in estuary. Changes in riverine sediment transport are an important part of land-sea geochemical cycling and further impact geochemical element fluxes in turbid rivers. However, as a vital nutrient element supporting primary productivity, silica mobilization from drainage in turbid rivers is overlooked. The turbid Yellow River has a strong ability to adsorb reactive silica, thereby exerting a substantial impact on the estuarine deposition of silica. Through an integration of monitoring databases, field sampling and historical hydrological data, we concluded that riverine fine particles control the exchangeable silica in the river and its estuary under soil erosion. Indoor simulation further revealed that the adsorbed content of exchangeable silica (ex-Si) in fine sediment constituted 35 % of total sediment matter. In addition, the transport of phosphorus and ex-Si was jointly regulated by fine sediment in global fluvial sediment transport, thereby exerting additional influence on the trophic structure of estuarine ecosystems. Against the backdrop of sediment budget deficit in the estuary, the heightened content of fine particles is depleting the silica storage from estuarine sediments. [Display omitted] [ABSTRACT FROM AUTHOR]

• The response of denitrification to MPs is spatially heterogeneous in coastal areas. • The response of N 2 O emission to MPs is not affected by coastal heterogeneity. • Denitrification response patterns to MPs are controlled by sulfide and NO 3 −. • MPs cause distinct SRB-DNB interactions under distinct sulfide and NO 3 − scenarios. • Altered microbial interactions by MPs have vital effects on biogeochemical cycles. Global estuarine and coastal zones are facing severe microplastics (MPs) pollution. Sulfate reducers (SRB) and denitrifiers (DNB) are two key functional microorganisms in these zones, exhibiting intricate interactions. However, whether and how MPs modulate the interactions between SRB and DNB, with implications for denitrification and associated N 2 O emissions, remains poorly understood. Here, we simultaneously investigated the spatial response patterns of SRB-DNB interactions and denitrification and associated N 2 O emissions to different MPs exposure along an estuarine gradient in the Yangtze Estuary. Spatial responses of denitrification to polyvinyl chloride (PVC) and polyadipate/butylene terephthalate (PBAT) MPs exposure were heterogeneous, while those of N 2 O emissions were not. Gradient-boosted regression tree and multiple regression model analyses showed that sulfide, followed by nitrate (NO 3 −), controlled the response patterns of denitrification to MPs exposure. Further mechanistic investigation revealed that exposure to MPs resulted in a competitive and toxic (sulfide accumulation) inhibition of SRB on DNB, ultimately inhibiting denitrification at upstream zones with high sulfide but low NO 3 − levels. Conversely, MPs exposure induced a competitive inhibition of DNB on SRB, generally promoting denitrification at downstream zones with low sulfide but high NO 3 − levels. These findings advance the current understanding of the impacts of MPs on nitrogen cycle in estuarine and coastal zones, and provide a novel insight for future studies exploring the response of biogeochemical cycles to MPs in various ecosystems. [Display omitted] [ABSTRACT FROM AUTHOR]

• Antibiotics inhibited potential sedimentary N removal and increased N 2 O yield. • Antibiotics had different effect on in situ sedimentary N removal along estuary. • Permeability of sediment determines the effect of antibiotics on N removal. • ARGs can't resist the inhibition of antibiotics on microbe related to N removal. Sedimentary denitrification takes place beneath the oxic layer at the sediment-water interface, where nitrate and antibiotics need to diffuse through the overlying water. However, the antibiotics' effect on sedimentary N removal and associated N 2 O production has not been adequately investigated under in situ conditions. Here, isotope pairing techniques, including slurry incubations (potential) and intact core incubations (in situ), combined with metagenomic analysis were applied to investigate the impacts of two protein-inhibiting antibiotics (oxytetracycline and thiamphenicol) on sediment nitrogen removal in a subtropical estuary. Slurry incubations showed that the two antibiotics significantly inhibited denitrification (67–98%) and anammox (49–99%), while intact core incubations presented no antibiotic effect at upstream but significant inhibition (23%-52%) at downstream. Meanwhile, N 2 O yields were stimulated up to 20 folds in slurry incubations yet showing insignificant response in intact cores. Such contrasting results between up- and down-stream and between slurry and intact core incubations strongly indicated that permeability, which determines diffusion of antibiotics to microbes, is the key to exert the effect of antibiotics on in situ sedimentary nitrogen removal processes regardless the existence of antibiotics resistance genes. This diffusive obstruction may mitigate the toxic effect of antibiotics on nitrogen removal related microbes in natural environments. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract Estuarine and coastal regions are often characterized by a high variability of suspended sediment concentrations in their waters, which influences dredging projects, contaminant transport, aquaculture and fisheries. Although various three-dimensional open source software are available to model the hydrodynamics of coastal water with a sediment module, the prediction of the fate and transport of cohesive sediments is still far from satisfied due to the lack of an efficient and robust flocculation model to estimate the floc settling velocity and the deposition rate. Single-class and sometimes two-class flocculation models are oversimplified and fail to examine complicated floc size distributions, while quadrature-based or multi-class based flocculation models may be too complicated to be coupled with large scale estuarine or ocean models. Therefore, a three-class population balance model was developed to track the sizes and number concentrations of microflocs, macroflocs and megaflocs, respectively. With the assumption of a fixed size of microflocs and megaflocs, only four tracers are needed when coupled with the open-source TELEMAC system. It enables better settling flux estimates and better addresses the occurrence and concentration of larger megaflocs. This tri-modal flocculation model was validated with two experimental data sets: (1) 1-D settling column tests with the Ems mud and (2) in-situ measurements at the WZ Buoy station on the Belgian coast. Results show that the flocculation properties of cohesive sediments can be reasonably simulated in both environments. It is also found that the number of macroflocs created, when a larger macrofloc breaks up, is a statistical mean value and may not be an integer when applying the model in the field. Graphical abstract Image Highlights • The sizes of flocs are dynamically altered because of particle aggregation and breakage. • A three-class population balance flocculation model was developed. • This flocculation model has been successfully implemented in the open source TELEMAC. • Four tracer variables, representing the floc size distributions, were included in TELEMAC. • The model was validated with settling column tests and field measurements. [ABSTRACT FROM AUTHOR]

• P fractions, geochemical behavior, and source-sink patterns were investigated in a shrimp pond enclosed by mangroves. • Depth profiles of P, Fe, Mn, and as were obtained using an in-situ high-resolution dialysis device. • P kinetic resupply was first evaluated via the DIFS model using TDP rather than DRP. • Mangrove and pond sediments were important sources of DOP and DRP, respectively, for overlying water. • Fe(III) and sulfate reduction co-regulated p remobilization in pond sediments. Estuarine mangrove wetlands have gradually declined owing to the growing construction of aquaculture ponds. How the speciation, transition, and migration of phosphorus (P) adaptively change in the sediments of this pond-wetland ecosystem remains unclear. In this study, we used high-resolution devices to explore the contrasting P behaviors associated with the redox cycles of Fe-Mn-S-As in estuarine and pond sediments. The results showed that the construction of aquaculture ponds increased the content or percentage of the silt, organic carbon, and P fractions in sediments. Dissolved organic P (DOP) concentrations in pore water were fluctuant with depths, accounting for only 18±15% and 20±11% of total dissolved P (TDP) in estuarine and pond sediment, respectively. Furthermore, DOP was less strongly correlated with other P species, including Fe, Mn, and sulfide. The coupling of dissolved reactive P (DRP) and TDP with Fe and sulfide confirmed that P mobility is regulated by Fe redox cycling in estuarine sediments, whereas Fe(III) reduction and sulfate reduction co-regulate P remobilization in pond sediments. The apparent diffusion flux revealed all sediments acting as sources for TDP (0.04–0.1 mg m−2 d−1) to the overlying water, while mangrove sediments were sources of DOP, and pond sediments were major sources of DRP. The DIFS model overestimated the P kinetic resupply ability, which was evaluated using DRP rather than TDP. This study improves our understanding of P cycling and budget in aquaculture pond-mangrove ecosystems and has important implications for understanding water eutrophication more effectively. [Display omitted] [ABSTRACT FROM AUTHOR]

• A new approach for determining the settling velocity of microplastic particles. • Microplastic-fine sediment interaction through five settling velocity regions. • 3D-numerical Modelling of microplastic transport in the tidal Weser river. • Higher probability of small microplastic to pass the estuary and reach the open sea. • Higher microplastic concentration in the estuarine turbidity zone. Microplastic (MP) pollution is an important challenge for human life which has consequently affected the natural system of other organisms. Mismanagement and also careless handling of plastics in daily life has led to an accelerating contamination of air, water and soil compartments with MP. Under estuarine conditions, interactions with suspended particulate matter (SPM) like fine sediment in the water column play an important role on the fate of MP. Further studies to better understand the corresponding transport and accumulation mechanisms are required. This paper aims at providing a new modeling approach improving the MP settling velocity formulation based on higher suspended fine sediment concentrations, as i.e. existent in estuarine turbidity zones (ETZ). The capability of the suggested approach is examined through the modeling of released MP transport in water and their interactions with fine sediment (cohesive sediment/fluid mud). The model results suggest higher concentrations of MP in ETZ, both in the water column as well as the bed sediment, which is also supported by measurements. The key process in the modeling approach is the integration of small MP particles into estuarine fine sediment aggregates. This is realized by means of a threshold sediment concentration, above which the effective MP settling velocity increasingly approaches that of the sediment aggregates. The model results are in good agreement with measured MP mass concentrations. Moreover, the model results also show that lighter small MP particles can easier escape the ETZ towards the open sea. [ABSTRACT FROM AUTHOR]

• Effects of periodic drying-wetting on n-DAMO in intertidal wetlands were explored. • Tidal dynamics affect n-DAMO activity and its contribution to reducing CH 4 emission. • Reflooding of intertidal wetlands generally intensifies n-DAMO rates. • Higher biodiversity of n-DAMO microbes was observed under reflooded conditions. Nitrite/nitrate-dependent anaerobic methane oxidation (n-DAMO) plays an important role in methane (CH 4) consumption in intertidal wetlands. However, little is known about the responses of n-DAMO in intertidal wetlands to periodic drying-wetting caused by tidal cycling. Here, comparative experiments (waterlogged, desiccated, reflooded) with the Yangtze estuarine intertidal sediments were performed to examine the effects of periodic tidal changes on n-DAMO microbial communities, abundances, and potential activities. Functional gene sequencing indicated the coexistence of n-DAMO bacteria and archaea in the tide-fluctuating environments and generally higher biodiversity under reflooded conditions than consecutive inundation or emersion. The n-DAMO microbial abundance and associated activity varied significantly during alternative exposure and inundation, with higher abundance and activity under the waterlogged than desiccated conditions. Reflooding of intertidal wetlands might intensify n-DAMO activities, indicating the resilience of n-DAMO microbial metabolisms to the wetting-drying events. Structural equation modeling and correlation analysis showed that n-DAMO activity was highly related to n-DAMO microbial abundance and substrate availability under inundation, whereas salt accumulation in sediment was the primary factor restraining n-DAMO activity under the desiccation. Overall, this study reveals tidal-induced shifts of n-DAMO activity and associated contribution to mitigating CH 4 , which may help accurately project CH 4 emission from intertidal wetlands under different tidal scenarios. [Display omitted] [ABSTRACT FROM AUTHOR]

The bar-built Pescadero Estuary in Northern California is a major fish rearing habitat, though recently threatened by near-annual fish kill events, which occur when the estuary transitions from closed to open state. The direct and indirect effects of hydrogen sulfide are suspected to play a role in these mortalities, but the spatial variability of hydrogen sulfide production and its link to fish kills remains poorly understood. Using flow-through reactors containing intact littoral sediment slices, we measured potential sulfate reduction rates, kinetic parameters of microbial sulfate reduction (R max , the maximum sulfate reduction rate, and K m , the half-saturation constant for sulfate), potential sulfide precipitation rates, and potential hydrogen sulfide export rates to water at four sites in the closed and open states. At all sites, the Michaelis–Menten kinetic rate equation adequately describes the utilization of sulfate by the complex resident microbial communities. We estimate that 94–96% of hydrogen sulfide produced through sulfate reduction precipitates in the sediment and that only 4–6% is exported to water, suggesting that elevated sulfide concentrations in water, which would affect fish through toxicity and oxygen consumption, cannot be responsible for fish deaths. However, the indirect effects of sulfide precipitates, which chemically deplete, contaminate, and acidify the water column during sediment re-suspension and re-oxidation in the transition from closed to open state, can be implicated in fish mortalities at Pescadero Estuary. [ABSTRACT FROM AUTHOR]

• Denitrification dominate nitrogen removal in sediments from subtropical estuary. • Particulate organic matter links nitrogen transform between water and sediments. • Estuarine sediments are weak in eliminating riverine nitrogen due to limited area. • Sedimentary denitrification directs a more than half of daily sea-air N 2 O flux. Sedimentary denitrification and anaerobic ammonium oxidation (anammox) are two microbially-mediated nitrogen removal pathways with distinct climatic feedbacks. Estuaries receive large fluxes of anthropogenic nitrogen and serve as hotspots for nitrogen loss. Applying 15N isotope pairing technique and sediment intact core incubation in two subtropical estuaries, the Yangtze River Estuary (YRE) and Jiulong River Estuary (JRE), we show that denitrification predominates the sedimentary nitrogen loss with a minor contribution (8.6 ± 7.5%) from anammox. Particulate organic matter degradation sustains the sedimentary nitrogen removal linking the nitrogen transformations between water column and sediment. Our results indicate that estuarine sediments exhibit high areal nitrogen removal rate, but play a relatively weak role in eliminating the nitrogen inputted from river basin due to the limited area. The riverine excess nitrogen will eventually enter into the adjacent continental shelf and be removed via phytoplankton assimilation-sedimentation-degradation-coupled nitrification-denitrification. In addition, sedimentary denitrification causes 1.8 ± 2.2% of nitrogen flow towards nitrous oxide (N 2 O) production and the derived N 2 O release flux accounts for 59% and 65% of the daily sea-air N 2 O emission in the YRE and JRE, respectively. These findings contribute to a better understanding of estuarine sedimentary nitrogen removal and associated climate feedbacks, and to the parameterization of Earth system models. [Display omitted] [ABSTRACT FROM AUTHOR]

• The presence of MPs significantly altered sedimentary nitrogen turnover. • Biodegradable MPs impacted bacterial community more profoundly. • Nitrogen cycling functional microbes had different responses to MPs. • Petroleum-based and biodegradable MPs promoted N 2 O production via varied avenues. • Biodegradable MPs have a greater potential to enhance global warming. Increasing microplastics (MPs) pollution in estuaries profoundly impacts microbial ecosystems and biogeochemical processes. Nitrous oxide (N 2 O), a powerful greenhouse gas, is an important intermediate product of microbial nitrogen cycling. However, how MPs regulate N 2 O production and its pathways remain poorly understood. Here, impacts of traditional petroleum-based and emerging biodegradable MPs on microbial N 2 O production and its pathways were studied through dual-isotope (15N–18O) labeling technique and molecular methods. Results indicated that both traditional petroleum-based and emerging biodegradable MPs promoted sedimentary N 2 O production, whereas pathways varied. Biodegradable polylactic acid (PLA) MPs displayed greater promotion of N 2 O production than petroleum-based MPs, polyvinyl chloride (PVC) and polyethylene (PE), of which PLA promoted through nitrifier nitrification (NN) and heterotrophic denitrification (HD), PE through nitrifier denitrification and HD, and PVC through NN. By combining the analysis of N 2 O production rates with sediment chemical and microbiological properties, we demonstrated that the enrichment of nitrifying and denitrifying bacteria, as well as related functional genes directly and/or indirectly increased N 2 O production primarily by interacting with carbon and nitrogen substrates. Different response of nitrogen cycling microbes to MPs led to the difference in N 2 O increase pathways, of which nitrifying bacteria significantly enriched in all MPs treatments due to the niches provided by MPs. However, part of denitrifying bacteria significantly enriched in treatments containing PLA and PE MPs, which may serve as organic carbon substrates. This work highlights that the presence of MPs can promote sedimentary N 2 O production, and the emerging biodegradable MPs represented by PLA may have a greater potential to enhance estuarine N 2 O emissions and accelerate global climate change. [Display omitted] [ABSTRACT FROM AUTHOR]

• Dark carbon fixation (DCF) is an important organic C source in intertidal wetlands. • Reductive sulfur in intertidal sediments was a key factor controlling DCF. • cbbM -harboring bacteria were the dominant DCF microbes in intertidal sediments. • DCF may play an important role in linking C-N-S cycles in intertidal wetlands. Dark carbon fixation (DCF) contributes approximately 0.77 Pg C y−1 to oceanic primary production and the global carbon budget. It is estimated that nearly half of the DCF in marine sediments occurs in estuarine and coastal regions, but the environmental factors controlling DCF and the microorganisms responsible for its production remain under exploration. In this study, we investigated DCF rates and the active chemoautotrophic microorganisms in intertidal sediments of the Yangtze Estuary, using 14C-labeling and DNA-stable isotope probing (DNA-SIP) techniques. The measured DCF rates ranged from 0.27 to 3.37 mmol C m−2 day−1 in intertidal surface sediments. The rates of DCF were closely related to sediment sulfide content, demonstrating that the availability of reductive substrates may be the dominant factor controlling DCF in the intertidal sediments. A significant positive correlation was also observed between the DCF rates and abundance of the cbbM gene. DNA-stable isotope probing (DNA-SIP) results further confirmed that cbbM -harboring bacteria, rather than cbbL -harboring bacteria, played a dominant role in DCF in intertidal sediments. Phylogenetic analysis showed that the predominant cbbM -harboring bacteria were affiliated with Burkholderia, including Sulfuricella denitrificans, Sulfuriferula, Acidihalobacter, Thiobacillus , and Sulfurivermis fontis. Moreover, metagenome analyses indicated that most of the potential dark-carbon-fixing bacteria detected in intertidal sediments also harbor genes for sulfur oxidation, denitrification, or dissimilatory nitrate reduction to ammonium (DNRA), indicating that these chemoautotrophic microorganisms may play important roles in coupled carbon, nitrogen, and sulfur cycles. These results shed light on the ecological importance and the underlying mechanisms of the DCF process driven by chemoautotrophic microorganisms in intertidal wetlands. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: Bimodal flocculation of marine and estuarine sediments describes the aggregation and breakage process in which dense microflocs and floppy macroflocs change their relative mass fraction and develop a bimodal floc size distribution. To simulate bimodal flocculation of such sediments, a Two-Class Population Balance Equation (TCPBE), which includes both size-fixed microflocs and size-varying macroflocs, was developed. The new TCPBE was tested by a model-data fitting analysis with experimental data from 1-D column tests, in comparison with the simple Single-Class PBE (SCPBE) and the elaborate Multi-Class PBE (MCPBE). Results showed that the TCPBE was the simplest model that is capable of simulating the major aspects of the bimodal flocculation of marine and estuarine sediments. Therefore, the TCPBE can be implemented in a large-scale multi-dimensional flocculation model with least computational cost and used as a prototypic model for researchers to investigate complicated cohesive sediment transport in marine and estuarine environments. Incorporating additional biological and physicochemical aspects into the TCPBE flocculation process is straight-forward also. [Copyright &y& Elsevier]

In estuaries, frequent resuspension and deposition of sediment complicate bacterial transport model development by transporting particle-attached bacteria and possibly inducing bacterial responses, such as growth, degradation, or changes in attachment. In order to better characterize these dynamics, observations were made in the Neuse River Estuary (NRE) using the combination of an in situ sampler to monitor the water column and sediment cores to monitor sediment concentrations. Two allochthonous bacteria, Escherichia coli (EC) and Enterococcus sp. (ENT), were selected as proxies for fecal contamination from stormwater runoff. Vibrio sp. (VIB), native to the NRE, was also observed as an autochthonous bacterial group that includes potentially pathogenic species. Two sampling periods were identified as dominated by different suspension types: runoff and resuspension. Despite this difference, several bacterial measures remained comparable between sampling periods. In bottom water, VIB concentration was correlated with salinity and ENT concentration was correlated with turbidity. Differences were observed for EC, where higher concentrations were found in hypoxic waters and sediment during the resuspension period. In the sediment, EC and VIB concentrations significantly increased following the passage of Hurricane Ophelia in September 2005. Throughout this study, all bacterial groups showed evidence of persistence in sediment, suggesting that sediment resuspension represents a significant source of bacteria to the water column. [Copyright &y& Elsevier]

Dispersion of pollutants in aquatic environments depends on their uptake by suspended solids. This work deals with the uptake kinetics of 133Ba (γ-emitter and a good analogue of 226Ra) by suspended estuarine sediments (which can be resuspended into the water column under certain conditions). This study presents a wide set of tracing experiments, including second tracing, decantation and desorption processes. The purpose is to characterize 133Ba uptake by sediments and to investigate the use and limitations of box models in order to describe the uptake kinetics. Water and sediment samples were collected in the Huelva estuary (Spain), where environmental 226Ra concentrations have been increased by two phosphate fertilizer industries. Samples were characterized by granulometric, organic carbon content, cation exchange capacity and XRF-EP analyses. Results revealed three-step kinetics, with characteristic times of minutes, hours and days. These results enabled the selection and calibration of a suitable box model and facilitated the testing of its use as a fully predictive tool. [Copyright &y& Elsevier]

• Mineralogy affects adsorption and desorption of heavy metals. • Particulate organic carbon enhances adsorption of metals to riverine sediments. • Particulate phosphorus enhances adsorption of metals to estuarine sediments. • Dissolved phosphorus increases release of heavy metals in estuarine environments. • Increasing salinity promotes release of heavy metals to the water column. The adsorption-desorption behaviour of heavy metals in aquatic environments is complex and the processes are regulated by the continuous interactions between water and sediments. This study provides a quantitative understanding of the effects of nutrients and key water and sediment properties on the adsorption-desorption behaviour of heavy metals in riverine and estuarine environments. The influence levels of the environmental factors were determined as conditional regression coefficients. The research outcomes indicate that the mineralogical composition of sediments, which influence other sediment properties, such as specific surface area and cation exchange capacity, play the most important role in the adsorption and desorption of heavy metals. It was found that particulate organic matter is the most influential nutrient in heavy metals adsorption in the riverine environment, while particulate phosphorus is more important under estuarine conditions. Dissolved nutrients do not exert a significant positive effect on the release of heavy metals in the riverine area, whilst dissolved phosphorus increases the transfer of specific metals from sediments to the overlying water under estuarine conditions. Furthermore, the positive interdependencies between marine-related ions and the release of most heavy metals in the riverine and estuarine environments indicate an increase in the mobility of heavy metals as a result of cation exchange reactions. [Display omitted] [ABSTRACT FROM AUTHOR]

• Seven emerging contaminants (ECs) were examined in dated intertidal saltmarsh cores • Similar mean EC concentrations were found in urbanised and non-urbanised systems • The ECs do not follow a temporal trend with core depth, and are relatively mobile • The "estuarine filter" here shows reduced potential to sequester the ECs studied The environmental occurrence, fate and ecotoxicity of emerging contaminants (ECs) has been the subject of increasing research, policy and public concern over the past two decades. While a wide range of publications have examined the environmental persistence and sediment/soil interactions of ECs following their discharge into aquatic environments, the extent to which ECs are sequestered in estuarine sediments, and the impact of this on their environmental persistence and supply to the ocean, in comparison remains unclear. This Article examines the environmental concentrations of seven, relatively water-soluble and environmentally mobile, ECs (including pharmaceuticals, perfluoroalkyl compounds, and plasticisers) in dated intertidal saltmarsh cores from two contrasting estuarine sites in the southern U.K. (one heavily urbanised/industrial, the other non-urbanised). Mean sediment EC concentrations are similar in both estuarine systems (in the range 0.1 (acetaminophen) to 17 (4-hydroxyacetophenone) ng/g dry weight). Despite their variable reported Log K ow values (from ca. 0.5 to > 7), the ECs are all apparently mobile in the marsh systems studied, and where subsurface concentration maxima are present these most likely relate to local flushing or diffusive processes and cannot be clearly linked to likely input trends or changes in sediment geochemistry (including sedimentary organic carbon content). The "estuarine filter" here, at least with respect to intertidal saltmarsh sediments, shows reduced potential to sequester the seven ECs examined and mediate their supply to coastal and shelf environments. Image, graphical abstract [ABSTRACT FROM AUTHOR]

• We applied dual isotopes (δ13C and Δ14C) of particulate organic carbon (POC). • POC characteristics were investigated in closed Geum and open Seomjin estuaries. • Environmental factors inducing seasonal differences in POC were assessed. • Stronger sediment resuspensions in winter induced the seasonal contrast in POC for both estuaries. In this study, we newly investigated surface water samples collected in two contrasting Korean estuary systems (i.e., closed Geum and open Seomjin estuaries) along a salinity gradient in winter (December) in 2016. The main objectives were to determine the source of particulate organic carbon (POC) in winter and to assess the environmental factors inducing seasonal differences in POC characteristics. Concentrations and dual carbon isotopes (δ13C and Δ14C) of POC were analyzed together with concentrations and stable carbon isotopes (δ13C) of dissolved inorganic carbon (DIC) and compared with those obtained in summer (August) in 2016. Our study provided a new insight that for both estuarine systems, the seasonal contrast in POC characteristics was associated with stronger wind-induced estuarine sediment resuspensions in winter than in summer providing a greater contribution of aged POC to the total POC pool in winter. Image, graphical abstract [ABSTRACT FROM AUTHOR]

This study aimed to determine the prevalence and abundance of sewage and animal fecal contamination of sediment at seven estuarine locations in Sydney, NSW, Australia. Sediment samples were tested for the occurrence of microbial targets including molecular marker genes of enterococci (ENT), Bacteroides HF183 (HF183), Methanobrevibacter smithii (nifH) , human adenovirus (HAdV) and emerging sewage-associated marker genes crAssphage (CPQ_056) and Lachnospiraceae (Lachno3) and animal feces-associated marker genes, including avian feces-associated Helicobacter spp. (GFD), canine-feces associated Bacteroides (DogBact), cattle-feces associated (cowM2) and horse feces-associated Bacteroides (HoF597). Results from this study showed that urban estuarine sediment can act as a reservoir of fecal indicator bacteria (FIB) and several microbial source tracking (MST) marker genes, including previously unreported Lachno3. The sewage-associated marker gene CPQ_056 was most prevalent, in 63.8% of sediment samples, while the avian associated marker gene GFD had the highest mean abundance. The GFD marker gene was highly abundant and widely detected in sediment samples from all seven locations compared to the other animal feces-associated marker genes. In all, 31 (44.9%) sediment samples were positive for at least two sewage-associated marker genes. However, the non-quantifiable detection of the HAdV marker gene did not always align with the detection of two or more sewage-associated marker genes. In addition, the most frequent wet weather overflow exposure occurred at locations that did not have a consistent pattern of detection of the sewage-associated marker genes, suggesting sediments may not be a suitable measure of recent sewage contamination. To assist water quality and public health managers better understand past microbial contamination of estuarine sediment, further studies seem justified to explore the role of decay of MST marker genes in sediment. Further work is also needed on the role of resuspension of MST marker genes from sediment during storm events to the water column as a source of contamination for both the GFD and sewage-associated marker genes. • The crAssphage marker gene was detected in 63.8% of sediment samples. • The avian marker was highly abundant and widely detected in sediment. • Adenovirus did not always align with the detection of two or more sewage markers. • The prevalence of the sewage marker genes did not align well with wet weather overflows. [ABSTRACT FROM AUTHOR]

In this study, we investigated how the desorption and degradation processes of radiolabeled benzo[a]pyrene (BaP) that was aged in various marine sediments were influenced by sedimentary organic matter properties. The stable OC fraction (STOC) and the demineralized fraction (DM) were isolated and characterized via advanced solid-state 13C nuclear magnetic resonance spectroscopy (NMR) and a CO 2 gas adsorption technique, respectively. Sodium persulfate preferentially removed the unstable OC fractions (USOC) and the aromatic C groups, and the residual STOC fractions were enriched with aliphatic C groups. The aliphatic C showed stronger resistance to degradation by persulfate than that of the aromatic C. A first-order kinetic model described the degradation process by sodium persulfate solutions very well (R 2 > 0.997). The desorption percentages, degradation percentages and rates k (h−1) of BaP gradually decreased from the estuarine sediments to the offshore marine sediments and were highly significantly and negatively correlated with STOC-bulk, F aliph -bulk, and V o -bulk (R 2 >0.903, p < 0.01). It was demonstrated that sodium persulfate degraded not only desorbed BaP but also a portion of the bound BaP fraction that was difficult to desorb. The BaP fractions that sorbed on USOC were degraded initially; then, the fractions of BaP that were released from STOC were degraded. This study demonstrated the important roles of STOC, aliphatic moieties, and micropores in the degradation process of BaP during the Na 2 S 2 O 8 treatment of the sediments. Image 1 • The BaP degradation changed with the USOC and STOC contents in marine sediments. • The BaP degradation process was well described by the first order kinetics equation. • The BaP fraction in USOC and aromatic C structures was easily degraded by sodium persulfate. • The BaP fraction in STOC and aliphatic C was hardly degraded by sodium persulfate. • The micropore volumes in stable OC is crucial to the degradation of adsorbed BaP. [ABSTRACT FROM AUTHOR]

Internal phosphorus (P) mobility is crucially important to overlying water ecosystems, while its spatiotemporal variations and mechanisms remain to be studied, especially in dynamic estuarine sediments. In this study, in situ monthly field sampling and indoor experiments were combined to measure the soluble reactive P (SRP), soluble Fe and diffusive gradients in thin films (DGT)-labile P/S in the overlying water, sediment and porewater in the Jiuxi River Estuary by employing high-resolution dialysis (HR-Peeper), the DGT technique and a MicroRhizon sampler. The consistent tendency between DGT-labile S and P in most seasons indicates that P mobilization was dominated by intense dissimilatory sulfate reduction (DSR), causing high SRP concentrations and active exchange with the overlying water. The circannual cyclical pattern of P is summarized, where in addition to temperature, monthly changes in runoff and tidal range are crucial external factors to control long-term P cycling via changed redox environments and terrigenous materials inputs. The mobile P, Fe and S present higher values during flood tides and lower values during ebb tides in tidal simulation experiments, demonstrating that the short-term cycling of P, Fe and S in intertidal surface sediments is highly redox-sensitive and controlled by tidal processes. The results also reveal that DSR greatly facilitates P mobility and release, while sediment oxidation and the induced enhancement in DIR and Fe cycling can effectively control P immobilization. Image 1 • Intense DSR dominates P mobilization in spring and summer. • Intense DIR causes high soluble Fe to coprecipitate with SRP in autumn. • Fe–P minerals act as vital sources to resupply porewater P in winter. • The mobile P, Fe and S are highly tide-sensitive verified by indoor experiments. • DSR facilitates P mobility, while oxidation and Fe cycling adverse to P mobility. [ABSTRACT FROM AUTHOR]