Sediment Solid Phase Research Articles

Performance and mechanism of organic solid-phase sediment composite plugging agent

The surface pipeline sediments of the Yingmai and Hade oil fields mainly contain substances such as asphalt and paraffin. The formation of sediment can increase the backpressure during pipeline transportation, and in severe cases, it can also lead to pipeline blockage. In order to solve this on-site situation, indoor experiments were conducted in the early stage, and an efficient organic unblocking system LXW was optimized and formulated. Based on this system, this article selects the wire mesh filtration method to evaluate the unblocking performance of LXW and on-site unblocking agents in the study and comparison of three evaluation methods. At the same time, based on the analysis of the chemical composition, microstructure, and melting point of organic sediments, from the perspectives of safety, environmental protection, and economic factors, further compares the performance and universality of the three unblocking systems, optimizes the process parameters of the LXW unblocking system, explores its stability and impact on the demulsification and dehydration of crude oil emulsions, and evaluates its safety performance. The LXW unblocking system has a more efficient unblocking effect and better universality, which can solve the problem of multiple block blockages on site. In addition, compared with existing unblocking agents, it has better economic benefits and is in line with the characteristics of low cost on site. On this basis, the dissolution and dispersion mechanism of the blockage system on sediment was studied through laser scattering system and fluorescence microscope, and its microscopic mechanism was further verified. At the same time, the oil-water interfacial tension under the action of the unblocking system was studied, and it was found that adding the agent can significantly reduce the equilibrium interfacial tension, which is of great significance for increasing production and injection.

The influence mechanism of environmental factors on DGT adsorbing sulfonamides and the migration between water and sediment

Obtaining the sulfonamides (SAs) concentrations in the water body and sediment bulk was a prerequisite to reveal their transport and partitioning behavior in sediment-water environments and accurately assess their ecological risk. In the present study, the influences of multifactor interactions on the performance of o-DGTs with XAD-18 binding gels were analyzed by central combination experiments and response surfaces analysis, in which the target compounds were 9 SAs. The results indicated that dissolved organic matter (DOM), pH, and suspended particulate matter (SS) had significant effects on the o-DGT sampling, whereas this o-DGT was independent of the ionic strength (IS). Concentning the composite influence of the four factors, the interaction between DOM and SS posed the most significant effect on all 9 SAs compounds. Subsequently, an o-DGT and DIFS model was applied to explore the SAs migration between the water-sediments interface. The difference between desorption rate (kb) and adsorption rates (kf) values suggested that the kinetics of SAs was dominated by adsorption. Moreover, the short-term sediment-water partitioning of SAs was clarified on the basis of distribution coefficient (Kdl) for the labile SAs, among which the sulfadiazine (SDZ) had the largest labile pool. The ability of sediments to release SAs to the liquid phase as a sink was determined by response time (Tc). Among the 9 SAs, the long-term release of soseulfamethoxypyridazine (SMP) from the solid phase of sediments would have a potential risk to the aquatic environment, to which more attention should be paid in the future.

Mercury distribution, mobilization and bioavailability in polluted sediments of Scheldt Estuary and Belgian Coastal Zone

In this study, the vertical distribution of mercury (Hg) in estuarine and marine sediment porewaters and solid phases was assessed by conventional and passive sampling techniques in the historically polluted Scheldt Estuary and Belgian Coastal Zone (BCZ). The Diffusive Gradients in Thin-films (DGT) measured labile Hg concentrations (HgLA) were mostly lower than the porewater Hg concentrations (HgPW), and they also presented different vertical distribution patterns. Still high Hg concentrations in the sediment solid phases, comparable to the historical ones, were observed. Even though pH, redox potential and dissolved sulfide concentration could influence the Hg biogeochemical behaviour, organic matter (OM) played a key role in governing Hg mobilization from sediment solid phase to porewater and in its partitioning between porewater and solid phase over depth. In the marine sediments, where OM had a marine signature, higher labile Hg concentrations in the porewater and faster resupply from the solid phase were observed. The DGT technique showed significant potential not only for the measurement of bioavailable Hg fractions in porewater, but also for the assessment of kinetic parameters governing the release of labile Hg species from the solid phase with the assistance of the DGT Induced Fluxes in Sediments (DIFS) model.

Seasonal variations in spatial distribution, mobilization kinetic and toxicity risk of arsenic in sediments of Lake Taihu, China

This study investigated seasonal variations in spatial distribution, mobilization kinetic and toxicity risk of arsenic (As) in sediments of three representative ecological lakes in Lake Taihu. Results suggested that the bioavailability and mobility of As in sediments depended on the lake ecological types and seasonal changes. At the algal-type zones and macrophyte-type zones, elevated As concentrations were observed in April and July, while these occurred at the transition areas in July and October. The diffusion flux of soluble As ranged from 0.03 to 3.03 ng/cm2/d, indicating sediments acted as a source of As. Reductive dissolution of As-bearing iron/manganese-oxides was the key driver of sediment As remobilization. However, labile S(-II) caused by the degradations of algae and macrophytes buffered sediment As release at the algal-type and macrophyte-type zones. Furthermore, the resupply ratio was less than 1 at three ecological lakes, indicating the resupply As capacity of sediment solid phase was partially sustained case. The risk quotient values were higher than 1 at the algal-type zones and transition areas in July, thereby, the adverse effects of As should not be ignored. This suggested that it is urgently need to be specifically monitored and managed for As contamination in sediments across multi-ecological lakes.

Sedimentary phosphorus burial in three contrasting boreal lakes in Finland

AbstractPermanent phosphorus (P) burial in sediment regulates lake trophic state over long timescales, but the controls on P burial are only partially understood. A diversity of biogeochemical settings may be found in lake sediments, which may have a strong impact on the processes controlling P burial from one location to another. Here, we investigate early diagenesis of P in three contrasting lakes in Southwest Finland. Eutrophic Lake Köyliönjärvi and mesotrophic Lake Pyhäjärvi have a history of nutrient loadings from agriculture, while Lake Vähäjärvi is an oligotrophic small forest lake, leading to potentially contrasting sediment biogeochemical dynamics. We combined porewater data and solid-phase sediment geochemical data to identify P phases in each system and investigate the dominant processes controlling P burial. Porewater profiles showed opposite gradients between the oligotrophic and the mesotrophic/eutrophic systems, implying net diffusive fluxes into and out of the sediments, respectively. Furthermore, sediment P data showed contrasting P speciation. Reactive P is buried in all systems, but the role of reducible iron (Fe) oxides in P retention is greater in mesotrophic/eutrophic lakes. In the oligotrophic system, aluminium (Al) oxides controlled P sorption into the sediment after diffusion from lake water. Evidence for vivianite formation was found only in the mesotrophic Lake Pyhäjärvi sediment, where 42–47% of total P was released in a Fe(II)-P specific extraction from the deeper part of the sediment column and vivianite crystals could be isolated from sediment samples.

Remobilization characteristics and diffusion kinetic processes of sediment zinc (Zn) in a tidal reach of the Pearl River Estuary, South China

Exploration of the remobilization mechanism of trace metals in estuarine sediments remain challenging because of dynamic hydrochemical conditions. This study integrated a chemical sequential extraction procedure (BCR), the diffusive gradient in thin films (DGT) and high-resolution dialysis techniques, and Visual MINTEQ ver.3.1 to identify the seasonal mobilization characteristics of sediment Zn within a tidal reach, South China. The mobility of sediment Zn based on the BCR procedure contradicted the results of DGT analysis. In summer, reductive dissolution of Fe/Mn oxides was the key driver of sediment Zn remobilization; during winter, cation exchange reactions facilitated the mobilization of Zn in the brackish water zone. The time-dependence ratios of DGT-labile Zn and dissolved Zn concentrations (mean: 0.34–0.81) indicated the sediment solid phase had partially sustained capacity to resupply Zn to the porewater in both seasons. Sediments generally functioned as a source of Zn in the freshwater zone with organically complexed Zn being diffusively released into the water column at rates of 0.3–15.5 μg·m−2·d−1. In the brackish water zone, the dominant Zn species were transformed into free Zn ions and Zn–inorganic complexes and migrated into sediment, with respective influxes of 18.9–70.7 μg·m−2·d−1 and 18.9–68.3 μg·m−2·d−1, which shifted to a sink of Zn.

Geochemical conditions regulating chromium preservation in marine sediments

In the marine sediment record, concentrations and isotope ratios of chromium (Cr) can be used to reconstruct ocean biogeochemical conditions. These reconstructions rely on a detailed understanding of the chemical pathways that Cr undergoes as it is transferred from the water column to the sediment record. We examined Cr concentrations in marine pore fluids and sediments from six continental margin sites, which can be grouped into two basic environments: (1) sites where sediments are oxygenated and rich in solid phase Mn (herein termed oxic), and (2) sites where sediments are organic C (Corg)-rich and oxygen is depleted (anoxic). We found Cr concentrations to be lower (maximum of 12 nM in pore fluids and 124 ppm sediment solid phase) at oxic sites compared with anoxic sites (maximum of 77 nM and 184 ppm). Our findings confirm previously published interpretations of dissolved Cr in pore fluids (Brumsack and Gieskes, 1983; Shaw et al., 1990). In oxic surface sediments, particulate Cr(III) can be oxidised by Mn oxides, which leads to elevated concentrations of dissolved Cr co-occurring at the same depth as elevated Mn concentrations in the sediment. Under these oxidising conditions, down-core sediments contain relatively low solid-phase Cr concentrations. In oxic sediments, Cr speciation reveals that most of the pore fluid Cr is in the Cr(VI) state. At the site where Mn oxide-rich sediments rest below an oxic water column, oxidative loss of Cr from the sediment to the bottom water leads to the lowest estimated Cr burial efficiency of the sites examined here. Under anoxic Corg-rich conditions, both pore fluids and sediment solid phases contain high Cr concentrations, with 40–80% of dissolved pore fluid Cr present as Cr(III). This enrichment of Cr appears to be tightly linked to the presence of high total organic carbon (TOC) content and scavenging of Cr by (organic) particles in the water column. Combined, these data highlight the strong dependence of Cr on both sedimentary redox conditions as well as biological productivity. Based on the data from modern continental margin sediments, we propose that Cr concentrations and isotope compositions of the authigenic sediment fraction may record a combination of redox conditions and biological productivity in the water column. If confirmed by Cr isotope analyses, these findings will add support for the notion that Cr may serve as a proxy for ocean biological and chemical sedimentological conditions. Thus, careful assessment of the impact of organic matter on Cr is required for reconstructions of redox conditions with sedimentary records.

Desorption kinetics of antipsychotic drugs from sandy sediments by diffusive gradients in thin-films technique

Dynamic processes of organic contaminants in sediments can have important toxicological implications in aquatic systems. The current study used diffusive gradients in thin-films (DGT) devices in sandy sediments spiked with nine antipsychotics and in field sandy sediments. Samplers were deployed for 1 to 30 days to determine the flux of these compounds to DGT devices and the exchange rates between the porewater and sediment solid phase. The results showed a continuous removal of antipsychotics to a binding gel and induced a mobile flux from the DGT device to the adjacent sediment solution. A dynamic model, DGT-induced fluxes in soils and sediments, was used to derive rate constants of resupply of antipsychotics from solid phase to aqueous phase (response time, Tc) and distribution coefficients for labile antipsychotics. The largest labile pool was found for lamotrigine and carbamazepine in spiked sediments. Carbamazepine, clozapine, citalopram, and lamotrigine were resupplied rapidly by sediments with Tc (25–30 min). Tc values of bupropion and amitriptyline were the longest (≈5 h), which exhibited slow desorption rates in sediments. In field sediments, high resupply was found for carbamazepine and lamotrigine, which did not show higher labile pool. The Tc values were obviously higher in the filed sediments (52–171 h). Although the adsorption process is dominant for most studied antipsychotics in both spiked sediments and field sediments, the kinetic resupply of antipsychotic compounds may not be accurately estimated by laboratory-controlled incubation experiments. More studies are needed to explore the mechanisms of desorption kinetics by using in situ DGT technique in the field.

Chemical speciation of mercury, sulfur and iron in a dystrophic boreal lake sediment, as controlled by the formation of mackinawite and framboidal pyrite

The chemical speciation of mercury (Hg), methyl mercury (MeHg), sulfur and iron was investigated in the sediment and porewater of Lake Ängessjön, a boreal, shallow (maximum depth 2.5 m), oligo-/dystrophic lake in northern Sweden. The lake receives terrestrial stream runoff from surrounding coniferous forest soils and peatlands having a low pH (4.6) and high concentrations of dissolved organic matter (DOM, annual average: 45 mg L−1), Fe (60 µM), sulfate (105 µM), inorganic Hg (1200 pM) and MeHg (250 pM). Sulfur K-edge XANES and Hg LIII-edge EXAFS spectroscopic measurements were used to characterize and quantify the sulfur speciation in the lake sediment at nine occasions, covering different seasons in the years of 2007 and 2009. In the surface sediment (0–3 cm) sulfate is reduced to zero-valent S and inorganic sulfide, that in turn reacts with Fe to form FeSm (mackinawite) and FeS2 (framboidal pyrite). The latter mineral becomes increasingly dominant by depth in the sediment. Thermodynamic modeling successfully predicted measured porewater concentrations of Hg in the sediment. Metacinnabar (β-HgS) and Hg(NOM-RS)2 complexes (the latter formed as a reaction between Hg(II) and thiol groups associated with natural organic matter, NOM-RSH) were the dominant forms of Hg(II) in the solid phase of sediments and Hg(II)-polysulfides (aq) dominated in the porewater. We argue that FeSm is a key component that indirectly controlled the Hg(II) speciation in the sediment by keeping the aqueous phase concentration of inorganic sulfide in the 0.5–2 µM range throughout the year. Besides providing a pool of readily soluble inorganic sulfide for formation of β-HgS(s), as demonstrated by previously reported EXAFS experiments, we further suggest FeSm may serve as a precursor for the formation of a more crystalline (less soluble) β-HgS(s) phase than present in environments devoid of FeSm. Support for this was provided by comparing our results with previously reported thermodynamic modelling results of Hg(II) and MeHg solubility in organic soils devoid of FeSm. In more general terms, we suggest the presence or absence of FeSm, through its influence on the chemical speciation of Hg and MeHg, may be a key factor behind the variability in rates of Hg(II) and MeHg transformation processes, such as methylation, reduction and demethylation, reported for different environmental settings.

Ampacity Estimation for Submarine Power Cables Installed in Saturated Seabed—Experimental Studies

The maximum current carrying capacity (ampacity) of power cables depends on the heat transferability of its surrounding medium. Submarine power cable ampacity is calculated conventionally following the international standards defined for underground cables. In reality, the thermal behavior of submarine environments differs significantly from its underground counterpart as the porous sediments are constantly water saturated. In this article, finite element method (FEM) results were used to determine the factors affecting the ampacity in the submarine environment. A method to calculate the ampacity using external thermal resistance considering two series resistances—conductive resistance (of the solid phase sediment) and convective resistance (due to the natural convection in the pore fluid, water) is proposed. An experimental setup was developed to validate the FEM simulations and the numerical method. The results indicated that the inclusion of convective heat transfer in the proposed method obtained a more precise ampacity estimate compared to that of the standard methods.

The control of hydrogen sulfide on benthic iron and cadmium fluxes in the oxygen minimum zone off Peru

Abstract. Sediments in oxygen-depleted marine environments can be an important sink or source of bio-essential trace metals in the ocean. However, the key mechanisms controlling the release from or burial of trace metals in sediments are not exactly understood. Here, we investigate the benthic biogeochemical cycling of iron (Fe) and cadmium (Cd) in the oxygen minimum zone off Peru. We combine bottom water and pore water concentrations, as well as benthic fluxes determined from pore water profiles and from in situ benthic chamber incubations, along a depth transect at 12∘ S. In agreement with previous studies, both concentration–depth profiles and in situ benthic fluxes indicate a release of Fe from sediments to the bottom water. Diffusive Fe fluxes and Fe fluxes from benthic chamber incubations (−0.3 to −17.5 mmol m−2 yr−1) are broadly consistent at stations within the oxygen minimum zone, where the flux magnitude is highest, indicating that diffusion is the main transport mechanism of dissolved Fe across the sediment–water interface. The occurrence of mats of sulfur-oxidizing bacteria on the seafloor represents an important control on the spatial distribution of Fe fluxes by regulating hydrogen sulfide (H2S) concentrations and, potentially, Fe sulfide precipitation within the surface sediment. Rapid removal of dissolved Fe after its release to anoxic bottom waters hints at oxidative removal by nitrite and interactions with particles in the near-bottom water column. Benthic flux estimates of Cd suggest a flux into the sediment within the oxygen minimum zone. Fluxes from benthic chamber incubations (up to 22.6 µmol m−2 yr−1) exceed diffusive fluxes (<1 µmol m−2 yr−1) by a factor of more than 25, indicating that downward diffusion of Cd across the sediment–water interface is of subordinate importance for Cd removal from benthic chambers. As Cd removal in benthic chambers covaries with H2S concentrations in the pore water of surface sediments, we argue that Cd removal is mediated by precipitation of cadmium sulfide (CdS) within the chamber water or directly at the sediment–water interface. A mass balance approach, taking the contributions of diffusive and chamber fluxes as well as Cd delivery with organic material into account, suggests that CdS precipitation in the near-bottom water could make an important contribution to the overall Cd mass accumulation in the sediment solid phase. According to our results, the solubility of trace metal sulfide minerals (Cd ≪ Fe) is a key factor controlling trace metal removal and, consequently, the magnitude and the temporal and spatial heterogeneity of sedimentary fluxes. We argue that, depending on their sulfide solubility, sedimentary source or sink fluxes of trace metals will change differentially as a result of declining oxygen concentrations and the associated expansion of sulfidic surface sediments. Such a trend could cause a change in the trace metal stoichiometry of upwelling water masses with potential consequences for marine ecosystems in the surface ocean.

Organic Carbon and Carbonate System in the Bottom Sediments of Shallow Bights of the Peter the Great Bay (Sea of Japan)

Abstract—The diagenesis of organic matter (OM) is studied in bottom sediments taken in February, 2018 from therapeutic mud deposits of the Uglovoi Bay and Voevoda and Ekspeditsiya bights (Peter the Great Bay, Sea of Japan). The carbonate system of bottom sediments and pore water were analyzed for the contents of nutrients, dissolved organic carbon, humic substance, and concentrations of sulfates and chlorides. The concentrations of organic carbon, chlorophyll-a, humic and fulvic acids, and mobile sulfide species are measured in a solid phase of sediment. Underwater photographing shows that sampling localities are covered by Zostera marina meadows in the Voevoda and Ekspeditsiya bights and by diatom mats in Uglovoi Bay. The proportions between dissolved inorganic carbon and alkalinity, as well as data on sulfate–chlorine ratios and mobile sulfide species indicate that the OM degradation in bottom sediments is mainly controlled by sulfate reduction. The Uglovoi Bay and Voevoda and Ekspeditsii bights are characterized by different values of bioturbation coefficients: 3.0, 107.6, and 14.5 cm2/day, respectively. The estimated fluxes of organic carbon from water into sediment and of dissolved inorganic carbon from sediment into water significantly differ. The disbalance between organic and inorganic carbons can be caused by the following reasons: (a) ignored CO2 flux released by marine organisms from bottom sediments through their siphonal system; (b) partial OM consumption in food with its subsequent deposition in it.

Diagenesis of Organic Matter in Eelgrass (Zostera marina L.) Vegetated Sediments

In February and July 2014, multidisciplinary geochemical studies of the sediments were carried out at two stations. One of them was located in Voevoda Bight, which has a bottom depth of 4 m, covered by eelgrass (Zostera marina L.); the other one served as a background station, because it is devoid of seagrass and is located in the northern part of Amur Bay (near Rechnoj Island). This station has a bottom depth of 6 m. The chemical composition of sediment pore water was studied along the depth of the core (80 cm) for the following: concentrations of dissolved organic carbon, carbohydrates, humic substance, nutrients (inorganic phosphorus, silicon, ammonium), and the parameters of the carbonate system (pH, total alkalinity—TA, dissolved inorganic carbon—DIC, CO2 partial pressure—pCO2). Contents of organic carbon (OC), fulvic acids, humic acids, and water were measured in the sediment solid phase. It was established that that the OC concentration was more than 5 and 2% in Voevoda Bight and at the background station, respectively. The sum of the fulvic and humic acids was about 40% of the OC content. It was found that the OC content decreased by 50% within 40 cm of the top layer of the sediments in Voevoda Bight. Within the same layer, a sharply increased nutrient concentration, TA, and DIC and decreased pH and sulfate ion concentrations were observed, which were the opposite of the background station. Seasonal variability of the observed parameters was weak, except for the significant decrease in pH and increase in pCO2 observed in summer due to temperature effect on the constants of the carbonate system. The chemical composition of pore water suggests that sulfate reduction was an important process. However, it cannot explain the sharp decrease in OC; therefore, it was suggested that OC is transformed into infauna biomass by the food chain.

Rice waste biochars produced at different pyrolysis temperatures for arsenic and cadmium abatement and detoxification in sediment

The effectiveness of rice waste biochars on heavy metal and metalloid abatement and detoxification was investigated using comprehensive studies based on As and Cd immobilization, bioaccumulation in tubifex, and microbial community changes in contaminated sediment. The remediation effects of biochars produced at different pyrolytic temperatures (400–700 °C) were evaluated. Bioaccumulation of heavy metal and metalloid in the tubifex tissue and change of indigenous microbial community under treatment of different biochars were assessed. Biochars produced at 700 °C exhibited greater effect on decreasing the concentrations of As and Cd in aqueous phase, and TCLP extractable and bioavailable metal(loid) in solid phase of sediment. The concentration of As and Cd in water phase decreased by 26%–89% and 22%–71% under the treatment of straw biochar, and decreased by 13%–92% and 5%–64% under the treatment of rice husk biochar, respectively. As and Cd contents in the tubifex tissue were positively correlated with their concentrations in aqueous phase. High-temperature biochars significantly reduced metal(loid) bioaccumulation in tubifex. The richness and biodiversity of microbial community were both greater in all biochars remediated sediment compared to non-treated sediment. These results indicated that rice waste biochars could effectively inhibit the bio-availability and toxicity of heavy metal and metalloid in sediment, and the higher-temperature biochar exhibited better performance.

Potential availability of trace metals in sediments in southeastern and southern Brazilian shipyard areas using the DGT technique and chemical extraction methods

Speciation and partitioning of trace metals, from solid to solution phases of sediments, control their bioavailability and thus their potential ecological risk to organisms. Therefore, in order to obtain a broad evaluation of their risk, it is necessary to couple methodologies that are able to assess metal mobility in sediment. In this study, the Diffusive Gradients in Thin Films (DGT) technique and the application of 0.1 M HCl acid extraction methods, together with solid-state voltammetric sensors, were used with the objective of assessing mobility and potential availability of Cr, Cu, Ni, Pb, V and Zn in sediment porewaters and solid sediments in southeastern and southern Brazilian shipyard areas. The highest labile metal concentrations were found in shipyards with the longest histories of operations. Trace metal distributions in porewater and in the solid phase of sediments (labile metals) and significant correlations among metals enabled to distinguish the contribution of anti-fouling paint components. The diffusive flux of every metal measured at the surface of the sediment indicated that CuDGT had the highest flux (3.66E−03 mmol·m−2 d−1) in the shipyard with the longest operating time. Therefore, enrichment was observed for Cu, Pb and Zn in sediments, indicating a possible ecological risk level of ‘Effects Range Median’ to ‘Apparent Effects Threshold’ for oyster larvae (Mollusca) (Cu), bivalves (Pb) and the infaunal community (Zn). Probable Effect Concentrations (PEC) to sediment-dwelling biota can be expected as well, related to high concentrations of Cu and Zn in sediment. This study allowed a comprehensive evaluation of potential bioavailability and ecological risk of trace metals in aquatic systems where there is continuous and specific input of these elements. The use of the DGT technique with solid-state voltammetry in the sediment of distinct Brazilian estuarine systems demonstrated its potential to be applied in future environmental network programs.

Impacts of estuarine dissolved organic matter and suspended particles from fish farming on the biogeochemical cycling of mercury in Zhoushan island, eastern China Sea

Changes in the biogeochemical cycling of mercury (Hg) and Hg species were investigated in a typical marine aquaculture area located at Zhoushan island, Zhejiang province, east China. Mercury species were analyzed in different environmental samples collected during a field survey and a simulation batch experiment. The field work comprised both summer and winter collection of water and sediment samples from marine aquaculture sites (MAS) in a field survey and from corresponding reference sites (CRS) located 2500 m from the MAS. THg concentrations in water were 91.3 ± 70.3 and 115 ± 22.6 pmol L−1 in summer and winter, respectively. Particulate Hg accounting for ˃60% of THg and positively correlated with total suspended solid content in water. Dissolved organic carbon in water was positively correlated with dissolved Hg. Significantly higher (p < 0.001, F = 102) total methylmercury (TMeHg) contents were observed in MAS (0.31 ± 0.26 ng g−1) than in CRS (0.06 ± 0.03 ng g−1) in the sediment solid phase. Moreover, MeHg formation rate in MAS was clearly higher than in CRS in the simulation experiment. Both the field survey and the simulation experiment highlighted the readier formation of MeHg in MAS than in CRS. TMeHg levels in blackhead seabream (Acanthopagrus schlegelii), red snapper (Lutjanus campechanus) and perch (Perca fluviatilis) were only 52.7 ± 5.74, 23.7 ± 2.51 and 24.3 ± 3.86 ng g−1, values significantly lower than the safety guideline (1000 ng g−1) established by the World Health Organization.

Cumulative Sulfate Loads Shift Porewater to Sulfidic Conditions in Freshwater Wetland Sediment.

It is well established that sulfide can be toxic to rooted aquatic plants. However, a detailed description of the effects of cumulative sulfate loads on sulfide and iron (Fe) porewater geochemistry, plant exposure, and ecological response is lacking. Over 4 yr, we experimentally manipulated sulfate loads to self‐perpetuating wild rice (Zizania palustris) populations and monitored increases in the ratio of sulfur (S) to Fe in sediment across a range of sulfide loading rates driven by overlying water sulfate. Because natural settings are complicated by ongoing Fe and S loads from surface and groundwater, this experimental setting provides a tractable system to describe the impacts of increased S loading on Fe–S porewater geochemistry. In the experimental mesocosms, the rate of sulfide accumulation in bulk sediment increased linearly with overlying water sulfate concentration up to 300 µg‐SO4 cm–3. Seedling survival at the beginning of the annual life cycle and seed mass and maturation at the end of the annual life cycle all decreased at porewater sulfide concentrations between 0.4 and 0.7 µg cm–3. Changes to porewater sulfide, plant emergence, and plant nutrient uptake during seed production were closely related to the ratio of S to Fe in sediment. A mass balance analysis showed that porewater sulfide remained a small and relatively transient phase compared to sulfate in the overlying water and Fe in the sediment solid phase. The results illuminate the evolution of the geochemical setting and timescales over which 4 yr of cumulative sulfate loading resulted in a wholesale shift from Fe‐dominated to sulfide‐dominated porewater chemistry. This shift was accompanied by detrimental effects to, and eventual extirpation of, self‐perpetuating wild rice populations. Environ Toxicol Chem 2019;38:1231–1244. © 2019 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.

Calcium phosphate control of REY patterns of siliceous-ooze-rich deep-sea sediments from the central equatorial Pacific

Abstract Rare earth elements and yttrium (REY) are often used as proxies for (paleo)environmental conditions and for the reconstruction of element sources and transport pathways. Many geological systems are well described with respect to the behavior of REY but deep-sea sediments with their manifold processes impacting the sediment during early diagenesis leave some questions about the origin and development of the shale-normalized REY (REYSN) patterns unanswered. Here we report REY data for sediment solid phase and pore water from the upper 10 m of deep-sea sediments from the Clarion Clipperton Zone (CCZ) in the central equatorial Pacific. The solid-phase REY profiles show highest concentrations at depth below 5–8 m. The REYSN patterns show an enrichment in middle REY (MREY) (LaSN/GdSN between 0.35 and 0.60; GdSN/YbSN between 1.19 and 1.47) and either no or negative CeSN and YSN anomalies (i.e. chondritic to sub-chondritic Y/Ho ratios between 24.7 and 28.7). Based on correlation analyses of bulk sediment element concentrations and sequential extractions, we suggest that a Ca phosphate phase controls the distribution and the patterns of REY in these silty clay pelagic sediments rich in siliceous ooze. The MREY enrichment develops at the sediment-water interface and intensifies systematically with depth. The negative CeSN anomaly intensifies with depth possibly because Ce is mostly bound to Mn- and Fe-(oxyhydr)oxides. Therefore, Ce concentrations remain relatively constant throughout the sediment core, while its trivalent REY neighbors are mostly hosted by the Ca phosphate phase that continuously incorporates REY from ambient pore waters. The non-redox-sensitive trivalent REY concentrations increase with depth, producing or enhancing a negative CeSN anomaly through coupled substitution of REY3+ and Na+ for Ca2+. The solid-phase REYSN pattern is therefore determined by the pore-water REYSN pattern and not suitable for paleoceanographic interpretation. The similarity of the pore-water and solid-phase REYSN patterns suggests, however, that only minor fractionation occurs during REY incorporation into the Ca phosphate crystal structure.

Migration and Transformation of Mercury at Sediment-Water Interface of the Dahong Lake Reservoir in the Simian Mountains

The mercury production in forest ecosystems can be characterized by dynamic changes in forest lakes or reservoirs. Moreover, changes in the downstream mercury concentrations can also reflect the mercury output from forest ecosystems. Based on the analysis of distribution patterns and sediment profiles of mercury in DH1, DH2, DH3, and DH4 during the wet and dry seasons in the Dahong Lake Reservoir, the total mercury concentration of the Dahong Lake Reservoir increases significantly during the wet season (the average of the wet season is 4.33 ng·L-1, the average of the dry season is 1.85 ng·L-1), especially in the downstream. The content of total mercury and methylmercury in the water column of the Dahong Lake Reservoir is significantly higher than that of background lake levels, but it is much lower than that of contaminated lakes, indicating that evergreen broad-leaved forest in the Simian Mountains has characteristics of Hg sources and the sediments are also sources of methylmercury and inorganic mercury in the water column of the Dahong Lake Reservoir. The methylation process mainly occurs in the surface layer of sediments and the methylation process is more active during the wet season. During the wet season, it is more favorable for mercury and methylmercury to enter the sediment liquid phase from the sediment solid phase and thus the water column.

Organic carbon recycling in Baltic Sea sediments – An integrated estimate on the system scale based on in situ measurements

In situ measured benthic fluxes of dissolved inorganic carbon (DIC), a proxy for organic carbon (OC) oxidation or recycling rates, are used together with burial rates based on measured sediment accumulation rates (SAR) and vertical distribution of OC in the sediment solid phase to construct a benthic OC budget for the Baltic Sea system. The large variability in recycling rates (4.3 ± 0.87–33 ± 17 mmol C m−2 d−1) and burial rates (1.2 ± 0.8–5.9 ± 1.8 mmol C m−2 d−1) between different sub-basins and between different depositional areas within the basins is accounted for in the budget. Our results indicate that sediments in the Baltic Sea have much higher recycling rates and lower burial rates of OC than previously found. The sediment budget calculations show that 22 ± 7.8 Tg C yr−1 of OC is recycled to the water column due to organic matter oxidation, while long term burial amounts to 1.0 ± 0.3 Tg C yr−1. For the Baltic Sea as a whole, 96% of the particulate OC (POC) deposited on the sea floor (23 ± 7.8 Tg C yr−1; the sum of recycling and burial) is recycled back to the water column. However, the burial efficiency (i.e. the fraction buried of the total deposition) shows large variability between the different basins (2.5–16%). The total benthic POC deposition is approximately 20% higher than the estimated POC source originating from primary production in the water column and riverine input. This difference is likely within the uncertainty range of our budget calculations, however it indicates that the POC sources might be underestimated. The results from this study enhance the understanding of OC delivery, deposition and cycling in the Baltic Sea, and help improving existing Baltic OC budgets.