Pore Water Concentration Profiles Research Articles

Pockmarks and associated fresh submarine groundwater discharge in the seafloor of Puck Bay, southern Baltic Sea

This is the first well-documented report on the occurrence of pockmarks in Puck Bay. Pockmarks in the seafloor of Puck Bay were discovered during a hydroacoustic survey carried out in 2020. They are located at a depth of 25–27 m in the southwestern part of the bay. Significant depletion of chloride (Cl−) concentrations in sediment pore water was found within the depressions. Most likely, the formation of pockmarks was due to groundwater flow through the Miocene–Pleistocene system of aquifers, which extends from land to the bay area. One-dimensional modeling of vertical Cl− concentration profiles in pore water revealed the upward flow of freshened groundwater within the pockmarks. The magnitude of submarine groundwater discharge (SGD) was estimated to vary from 1.53·10−2 to 18·10−2 L·m−2·h−1. The effect of groundwater seepage was also observed at 3 cm above the seafloor within the pockmarks, which was identified as a decrease in salinity of approximately 0.12 PSU compared to reference sites.Furthermore, due to the effect of water advection, SGD can be detected even several meters above the seafloor as a decrease in salinity values within the thermocline layer.

Substantially excess uranium in the waters of an intertidal salt marsh: A case study of eastern Chongming Beach

Knowledge of the geochemical behavior of uranium is key to an accurate tracing of the decay chain of the uranium series nuclides for material transportation processes on different temporal scales. However, direct observations for understanding dissolved uranium input in tidal water are very limited. Therefore, dissolved uranium was measured in tidal creek water, overlying water, and pore water collected from the central cross section of eastern Chongming Beach, Changjiang Estuary, from November 2012 to October 2013, to observe the spatiotemporal distribution of uranium. The results indicated that the behavior of dissolved uranium is conservative in the tidal creek waters during the flooding process, and an excess of dissolved uranium is observed during the ebbing process; excess uranium phenomena are dominant in the overlying and pore waters throughout the year, particularly at the middle and high tidal flats. The element concentration profiles in pore water showed that uranium release follows Mn oxide reduction in the subsurface suboxic zone. Hence, the exchange process between tidal water and pore water, coupled with ebb tide, represents a potential path for uranium release into the estuary. The three-end-member (Changjiang River, seawater, and pore water) model estimates that 35% of the amount of uranium in ebbing water is derived from pore water. The exchange rate between tidal water and pore water is 196.4 nmol/(cm2·d), with an export flux of 2.34 × 104 mol/a. We suggest that the release of uranium from intertidal salt marshes is an important uranium source in estuarine and coastal regions.

Seasonal iron fluxes and iron cycling in sandy bioirrigated sediments

Permeable sediments, which represent more than 50% of the continental shelves, have been largely neglected as a potential source of Fe in current global estimates of benthic dissolved iron (Fed) fluxes. There are open questions regarding the effects of a range of factors on Fed fluxes from these deposits, including seasonal dynamics and the role of bioirrigation. To address these gaps, we performed laboratory-based sediment incubation experiments with muddy sands during summer (21 °C) and winter (7 °C). We used bioirrigation mimics to inject overlying water into the permeable sediment with patterns resembling the bioirrigation activity of the prolific bioturbating polychaete, Clymenella torquata. Newly developed in-line Fe accumulators were used to estimate Fe fluxes with a recirculating set-up. We found high Fed fluxes from sandy sediments, especially in benthic chambers with simulated bioirrigation. In the winter fluxes reached >200 µmol Fed m-2 d-1 at the onset of irrigation and then decreased over the course of a 13-day experiment while in the summer fluxes from irrigated sediments reached >100 µmol Fed m-2 d-1 and remained high throughout a 7-day experiment. Despite different geochemical expressions of Fe-S cycling and resulting porewater Fed concentrations in winter and summer, large Fed fluxes were sustained during both seasons. Solid-phase and porewater concentration profiles showed that maximum concentrations of key constituents, including total solid-phase reactive Fe, and porewater Fed and ammonium, were located closer to the sediment water interface (SWI) in irrigated cores than in non-irrigated cores due to the upward advective transport of dissolved porewater constituents. This upward transport also facilitated Fed fluxes out of the sediments, especially during times of active pumping. Our study demonstrates the potential for large Fed fluxes from sandy sediments in both summer and winter, despite relatively low standing stocks of labile organic matter and porewater Fed. The primary driver of these high fluxes was advective porewater transport, in our study induced by the activity of infaunal organisms. These results suggest that permeable sediments, which dominate shelf regions, must be explicitly considered in global estimates of benthic Fed fluxes, and cannot be simply extrapolated from estimates based on muddy sediments.

Novel insight into ammonium, phosphate, and iron(II) dynamics in the sediment porewater of a constructed wetland under artificial aeration through the diffusive equilibrium in thin films technique

The analysis of porewater concentrations in constructed wetland sediments could help to understand biogeochemical processes, the sources and sinks of nutrients, and their effect on overlying water quality. In this study, we measured high-resolution porewater concentration profiles of ammonium (NH4+-N), nitrate (NO3N), phosphate (PO43--P), and ferrous iron (Fe(II)) in-situ in the Laratinga constructed wetland in Mount Barker (South Australia) using diffusive equilibration in thin films (DET) techniques. Measurements were taken under light and dark conditions, and non-aerated and aerated conditions to determine the effect on sediment porewater nutrient concentrations. Baseline surface water nutrient concentrations (NH4+-N > 36 mg L-1, PO43--P > 0.43 mg L-1) greatly exceeded water quality guideline criteria. Aeration of the water column alleviated night-time hypoxic conditions (i.e. dissolved oxygen increased from a minimum of 0.7 mg L-1 to a minimum of 4 mg L-1), and increased the redox potential in the sediment. Significant differences were present for NH4+-N, PO43--P, and Fe(II) concentrations with depth in the sediment. Ammonium concentrations in the sediment reduced under aerated conditions, presumably due to enhanced nitrification. However it was observed that PO43--P and Fe(II) concentrations increased significantly with aeration, especially under dark conditions, and were strongly correlated (R2>0.8). This was not what was hypothesised and points to complex interactions between Fe and P in the sediment. Nitrate concentrations in the sediment were below the detection limit (<0.9 mg L-1) which suggests limited nitrification-denitrification is occurring. Overall the results suggest that DET techniques are useful tools for quantifying porewater concentrations of nutrients in constructed wetlands under various environmental conditions.

Understanding the isotopic composition of sedimentary sulfide: A multiple sulfur isotope diagenetic model for Aarhus Bay

Measurement of the multiple sulfur isotopes (³²S/³³S/³⁴S) enables the calibration of microbial biosignatures and provides a unique diagnosis of S-based metabolic processes: sulfate reduction, disproportionation, and sulfide oxidation. All three metabolisms carry distinct geochemical consequences for S cycling in modern systems, and are particularly powerful for paleoenvironmental interpretations if their respective contributions can be separated. To hone those interpretations and to further develop a quantitative context for understanding early diagenetic sulfur cycling, we constructed a multiple S isotope reactive transport model for the sediments of a geochemically well-characterized system (Aarhus Bay, Denmark). The model reconciles pore water and solid phase concentration profiles of the major species associated with Fe/S/C cycling, and uses multiple S isotope systematics to predict the isotope profiles of the major S species, including pore water sulfate, free sulfide and solid phase pyrite. We note that very large fractionations associated with sulfate reduction (³⁴ε_sr = 70‰) are required to reproduce the observed pore water profiles, and we reconcile these fractionations with low temperature theoretical predictions for isotope equilibrium fractionation. The minor sulfur isotope values (noted as Δ³³S) of sulfate increase at shallow depths within the Aarhus Bay core, and decrease when sulfate drops below 10 mM. Values (Δ³³S) for sulfide decrease nearly monotonically towards seawater sulfate values near the zone of sulfate depletion. Pyrite Δ³³S values are nearly uniform downcore (0.170 ± 0.010‰) despite a ∼10‰ enrichment in surface versus deep pyrite δ³⁴S values. Sulfate reduction is the most important process controlling S isotope pore water distributions, with modest contributions from oxidative S cycling. Further, microbial sulfate reduction demonstrates large fractionations typically not expected for shallow, organic rich (TOC ∼ 4%) continental margin systems.

Lumped Approach for Reactive Transport of Organic Compound Mixtures through Simulated Aquifer Sands in Lab-Scale Column Tests

The feasibility of the lumped approach for reactive transport of 12 organic compounds in mixtures through simulated aquifer sands with different organic carbon content (foc) within soil columns was evaluated. From direct measurements of effluent samples and temporal and spatial pore-water concentration profiles within soil columns, 12 organic compounds in mixtures were sorbed to different extents due to the different dependence of sorption on foc. Considering the tradeoff between accuracy and simplicity, four, five, and six pseudocompounds were determined for simulated aquifer sands with foc of 0.006%, 0.051%, and 0.221%, respectively, to approximate the reactive transport of 12 organic compounds in mixtures. Each pseudocompound presented obviously different reactive transport behavior in terms of both sorption capacity and nonlinearity, indicating that each pseudocompound contained components with relatively similar sorption capacities and nonlinearity. Similar to the results from batch equilibrium sorption tests, log Koc can be used as the a priori grouping criterion, although the relative contributions of different forces to the overall sorption may differ for different composition of organic mixtures and foc values of aquifer sands. Finally, the assignment of the Freundlich sorption parameters of pseudocompounds using averages of Freundlich sorption parameters of their components led to reasonable prediction for reactive transport of organic compounds in mixtures through the soil columns. Further study is warranted to evaluate the effective coupling between lumped approach and reactive transport model using complex multicomponent mixtures within heterogeneous subsurface systems.

Impact of passive sampler protection apparatus on sediment porewater profiles of hydrophobic organic compounds

Passive sampling techniques have been widely used to determine the dissolved concentration profiles of hydrophobic organic compounds (HOCs) in sediment porewater. However, the effects of having a protection for the passive sampler on profiling HOCs concentrations in sediment porewater, especially in deep sediment, have remained unclear. To address this issue, low density polyethylene passive samplers with and without protectors, which consisted of glass fiber filter and porous stainless steel shield, were simultaneously deployed in sediment of the Dongjiang River, South China. The results showed that the protectors retarded the dissipation of performance reference compounds (PRCs) from the sampler by a factor of 2–9. The protectors seemed to exert a negligible effect on the measured concentrations of PAHs, BDE-47, and BDE-99 in surficial sediment porewater (0–14 cm depth) from both samplers. However, the sediment porewater concentration profiles of PAHs and BDE-47 from the sampler with protectors were in agreement with those normalized by dry weight in deep sediment (16–34 cm depth), indicating that a diffusion layer established by the protectors may minimize the probability of local depletion of the target analytes in deep sediment. In addition, the log Koc values of PAHs, BDE-47, and BDE-99 exhibited a slight increasing trend with sediment depth. This finding suggested that in situ passive sampling techniques could be a feasible tool in determining the site-specific log Koc values of HOCs at different sediment depths.

Estimates of the remineralization and burial of organic carbon in Lake Baikal sediments

Sediment cores collected from several stations throughout Lake Baikal in water depths from 100 m off the Selenga River delta to the deepest basin of the lake (~1640 m), have been analyzed for sedimentary organic carbon, nitrogen, and the remineralized components in pore water. The organic carbon content of surface sediments generally varied from 2.3 to 3.2% by weight, and profiles typically showed an exponential decrease in both organic carbon and nitrogen in the upper 20–30 cm of the sediment column. Steady state models of organic matter diagenesis yield first order decomposition rate constants which range from 0.0009 to 0.022 y−1. The calculated residence times for the metabolizable fraction of the organic matter in these sediments increases roughly with increasing water depth and is on the order of 50–300 years. Pore water concentration profiles were determined for dissolved inorganic carbon, dissolved organic carbon (DOC), methane, and dissolved ammonium. At depth (25–30 cm) methane concentrations ranged from 50 to 800 μmol Lpw−1 and DOC from 400 to 900 μmol Lpw−1. Estimation of carbon recycling rates based upon diffusion along pore water concentration gradients at the sediment-water interface, indicate that combined DOC and methane fluxes generally contribute <15% of the overall turnover of sedimentary organic carbon. Comparisons to Laurentian Great Lakes environments show trends in sediment deposition, organic matter remineralization, and the time scales of carbon recycling across nearly two orders of magnitude with the fraction of organic content buried generally decreasing with decreasing sedimentation rates.

Solute Reservoirs Reflect Variability of Early Diagenetic Processes in Temperate Brackish Surface Sediments

Coastal marine sediments are a hotspot of organic matter degradation. Mineralization products of early diagenetic processes accumulate in the pore waters of the sediment, are subject of biological uptake and secondary biogeochemical processes and are released back into the water column via advective and diffusive fluxes across the sediment-water interface. Seven representative sites in the shallow coastal area of the southern Baltic Sea (15–45 m water depth), ranging from permeable sands to fine grained muds, were investigated on a seasonal basis for their key mineralization processes as well as their solid phase and pore water composition to identify the drivers for the variability of early diagenetic processes in the different sediment types. The sandy sediments showed about one order of magnitude lower organic carbon contents compared to the muds, while oxygen uptake rates were similar in both sediment types. Significantly higher oxygen uptake rates were determined in two near-shore muddy sites than in a deeper coastal muddy basin, which is due to higher nutrient loads and the corresponding addition of fresh algal organic matter in the near-shore sites. Pore water concentration profiles in the studied sediments were usually characterized by a typical biogeochemical zonation with oxic, suboxic, and sulfidic zones. An up to 15 cm thick suboxic zone was sustained by downward transport of oxidized material in which dissolved iron and phosphate indicate an intensive reduction of reactive Fe with the release of adsorbed phosphorus. While the geochemical zonation was stable over time in the muds of the studied deeper basin, high variability was observed in the muds of a near-coastal bay probably mainly controlled by sediment mixing activities. The sediments can be characterized by essentially two factors based on their near-surface benthic solute reservoirs: (1) their organic matter mineralization and solute accumulation efficiency and (2) their redox-state. Benthic solute reservoirs in the pore waters of the top decimeter were generally higher in the muddy than in the sandy sediments as the more permeable sands were prone to an intensive exchange between pore water and bottom water. The three studied muddy sites showed great dissimilarities with respect to their predominating redox-sensitive metabolites (dissolved iron, manganese, and sulfide). Surface-near advective transport like irrigation of permeable sands and rearrangement of cohesive muds had a particularly strong influence on early diagenetic processes in the studied sediments and were probably the most important cause for the spatiotemporal variability of their benthic solute reservoirs.

Bioturbation facilitates DDT sequestration by activated carbon against recontamination by sediment deposition

We evaluated bioturbation as a facilitator for in situ treatment with a thin layer of activated carbon to treat dichlorodiphenyltrichloroethane (DDT)-contaminated sediment and contaminant influx by sediment deposition. Using the freshwater worm Lumbriculus variegatus as a bioturbator, microcosm time-series studies were conducted for 4 mo and monitored for DDT flux and porewater concentration profiles by polyethylene passive samplers. With bioturbators present, the thin-layer activated carbon amendment reduced DDT flux by >90% compared with the same simulated scenario without activated carbon amendment. In contrast, a clean sediment cap without activated carbon was ineffective in reducing flux when bioturbation was present. In simulated scenarios with contaminant influx through deposition of contaminated sediment, bioturbation facilitated in situ activated carbon treatment, reducing 4-mo DDT flux by 77% compared with the same scenario without bioturbation. Porewater concentration profiles and activated carbon dose profiles confirmed effective mixing of activated carbon particles down to 1-cm depth. A mass transfer model was developed to predict flux with consideration of bioturbation and sediment deposition processes. Predicted flux values were consistent with experimental results and confirm that bioturbation activity helps reduce DDT sediment-to-water fluxes in activated carbon-treated sediment with recontamination by contaminated sediment deposition. To our knowledge, this is the first study to combine experimental and modeling results showing how bioturbation enhances activated carbon amendment effectiveness against ongoing contaminant influx by sediment deposition. Environ Toxicol Chem 2018;37:2013-2021. © 2018 SETAC.

Investigating the Effect of Bioirrigation on In Situ Porewater Concentrations and Fluxes of Polychlorinated Biphenyls Using Passive Samplers.

Polychlorinated biphenyl (PCB) fluxes from contaminated sediments can be caused by mechanisms including diffusion, bioirrigation, and resuspension, but it is often unclear which mechanisms are important. In the Lower Duwamish Waterway (Seattle, Washington), the presence of abundant benthic macrofauna suggests that porewater bioirrigation may be an important mechanism for PCB transport from the bed into the overlying water column. In this field study, the fluxes of PCBs due to bioirrigation were quantified by using (a) polyethylene (PE) samplers to quantify in situ and ex situ (i.e., equilibrium) PCB porewater concentration profiles and (b) measurements of the geochemical tracer 222Rn to quantify the rate of porewater exchange with overlying water. The results showed that bioirrigation caused sorptive disequilibrium with the surrounding sediment, which led to lower in situ porewater concentrations than expected from sediment concentrations. The combined fluxes of seven PCB congeners (Σ7PCBs) were 1.6-26 ng/m2/day for the three field sites, similar in magnitude to the upper limit estimates of diffusive fluxes calculated assuming water-side boundary layer control (Σ7PCBs = 1.3-47 ng/m2/day). Moreover, the depleted in situ porewater concentrations imply lower diffusive flux estimates than if the ex situ porewater concentrations had been used to estimate fluxes (Σ7PCBs = 89-670 ng/m2/day). These results suggest that nondiffusive PCB fluxes from the sediment bed are occurring and that quantifying in situ porewater concentrations is crucial for accurately quantifying both diffusive and nondiffusive PCB fluxes.

Potentially Active Iron, Sulfur, and Sulfate Reducing Bacteria in Skagerrak and Bothnian Bay Sediments

ABSTRACTIn many marine surface sediments, the reduction of manganese (Mn) and iron (Fe) oxides is obscured by sulfate reduction, which is regarded as the predominant anaerobic microbial respiration process. However, many dissimilatory sulfate and sulfur reducing microorganisms are known to utilize alternative electron acceptors such as metal oxides. In this study, we tested whether sulfate and sulfur reducing bacteria are linked to metal oxide reduction based on biogeochemical modeling of porewater concentration profiles of Mn2+ and Fe2+ in Bothnian Bay (BB) and Skagerrak (SK) sediments. Steady-state modeling of Fe2+ and Mn2+ porewater profiles revealed zones of net Fe (0–9 cm BB; ∼10 and 20 cm SK) and Mn (0–5 cm BB; 2–8 cm SK) species transformations. 16S rRNA pyrosequencing analysis of the in-situ community showed that Desulfobacteraceae, Desulfuromonadaceae and Desulfobulbaceae were present in the zone of Fe-reduction of both sediments. Rhodobacteraceae were also detected at high relative abundance in both sediments. BB sediments appeared to harbor a greater diversity of potential Fe-reducers compared to SK. Additionally, when the upper 10 cm of sediment from the SK was incubated with lepidocrocite and acetate, Desulfuromonas was the dominant bacteria. Real-time quantitative polymerase chain reaction (qPCR) results showed decreasing dsrA gene copy numbers with depth coincided with decreased Fe-reduction activity. Our results support the idea that sulfur and sulfate reducing bacteria contribute to Fe-reduction in the upper centimeters of both sediments.

Internal loading of phosphorus in western Lake Erie

Abstract This study applied eight techniques to obtain estimates of the diffusive flux of phosphorus (P) from bottom sediments throughout the western basin of Lake Erie. The flux was quantified from both aerobic and anaerobic incubations of whole cores; by monitoring the water encapsulated in bottom chambers; from pore water concentration profiles measured with a phosphate microelectrode, a diffusive equilibrium in thin films (DET) hydrogel, and expressed pore waters; and from mass balance and biogeochemical diagenetic models. Fluxes under aerobic conditions at summertime temperatures averaged 1.35 mg P/m2/day and displayed spatial variability on scales as small as a centimeter. Using two different temperature correction factors, the flux was adjusted to mean annual temperature yielding average annual fluxes of 0.43–0.91 mg P/m2/day and a western basin-wide total of 378–808 Mg P/year as the diffusive flux from sediments. This is 3–7% of the 11,000 Mg P/year International Joint Commission (IJC) target load for phosphorus delivery to Lake Erie from external sources. Using these average aerobic fluxes, the sediment contributes 3.0–6.3 μg P/L as a background internal contribution that represents 20–42% of the IJC Target Concentration of 15 μg P/L for the western basin. The implication is that this internal diffusive recycling of P is unlikely to trigger cyanobacterial blooms by itself but is sufficiently large to cause blooms when combined with external loads. This background flux may be also responsible for delayed response of the lake to any decrease in the external loading.

Hydrogeochemical models locating sulfate-methane transition zone in marine sediments overlying black shales: A new tool to locate biogenic methane?

Precise hydrogeochemical modeling of early diagenesis is a key in the reconstruction of sedimentary basin models. This determines the mineralogical evolution of the sediment and consequently the porosity of the rock. During early diagenesis also part of the initial organic matter is converted into biogenic gas: CH4 CO2, and H2S. These processes are part of complex reaction chains during sedimentation, and biogeochemical reactions leave different signals that can be observed today. In this work, we reproduce the early diagenetic processes as integrated signals over geological times in sediments of the Demerara Rise by applying chemical thermodynamics using the PHREEQC (version 2) computer code. The investigated sediments are characterized by the presence of black shales in 410–490 mbsf and by a diagenetic barite layer above in 300–350 mbsf at depth of sulfate-methane transition (SMT). We determine the parameters that influence the location of diagenetic barite peaks in sediments overlying black shales by means of a novel modeling approach. Crucial parameters are the amount of bacterial organic matter mineralization, sedimentation rates and bottom water sulfate concentrations. All parameters are intertwining and influence the sulfate-methane cycle. They affect the location of the SMT visualized by diagenetic barite peaks. However, our model approach opens a wide field in exploring early diagenetic reactions, processes and products (such as biogenic methane) over geological times mirrored by diagenetic minerals and pore water concentration profiles that can be detected in present-day sediments.

High-resolution profiles of dissolved reactive phosphorus in overlying water and porewater of Lake Taihu, China.

The diffusive gradients in thin films (DGT) technique was applied to obtain high spatial resolution of dissolved reactive phosphorus (DRP) concentrations in overlying water and sediment porewater in Lake Taihu. A strong positive correlation between total phosphorus (TP) in sediments and DRP concentrations using DGT was found in both of the sampled lake regions. For stations ZSW and DPG, which have high TP background values in sediments, DRP concentrations in overlying water and porewater were much higher than those at stations MLW, DPG, and HX. Also, a high potential for P release at the sediment-water interface was revealed at stations ZSW and DPG due to a significant concentration gradient between overlying water and porewater. In sediment cores from stations ZSW and DPG, DRP porewater concentration profiles using DGT with three diffusive gel thicknesses displayed a similar trend, increasing down to -2 cm or -4 cm, then decreasing down to -8 cm, and then becoming relatively stable in deeper layers. High-resolution profiles of DRP were related to dissolved oxygen concentrations and organic matter concentrations in different sediment layers at stations ZSW and DPG. For most sediment with low TP concentrations at stations MLW, DPG, and HX, DRP concentrations could not be determined at and near the sediment-water interface, then increased gradually down to -8 cm or -10 cm, and remained stable. At stations MLW, DPG, and HX, most DRPDGT (DRP concentrations measured by DGT) values were 10-30 % of the DRP concentrations in porewater, indicating a partial resupply of the sediments to porewater.

Gene expression in the deep biosphere

Scientific ocean drilling has revealed a deep biosphere of widespread microbial life in sub-seafloor sediment. Microbial metabolism in the marine subsurface probably has an important role in global biogeochemical cycles, but deep biosphere activities are not well understood. Here we describe and analyse the first sub-seafloor metatranscriptomes from anaerobic Peru Margin sediment up to 159 metres below the sea floor, represented by over 1 billion complementary DNA (cDNA) sequence reads. Anaerobic metabolism of amino acids, carbohydrates and lipids seem to be the dominant metabolic processes, and profiles of dissimilatory sulfite reductase (dsr) transcripts are consistent with pore-water sulphate concentration profiles. Moreover, transcripts involved in cell division increase as a function of microbial cell concentration, indicating that increases in sub-seafloor microbial abundance are a function of cell division across all three domains of life. These data support calculations and models of sub-seafloor microbial metabolism and represent the first holistic picture of deep biosphere activities.

Modeling Cl− Concentration and δ37Cl Profiles in Porewater Across a 250m-thick Indurated Argillite at the Tournemire URL (France)

Dissolved chloride in argillite porewater has been studied as a natural analogue for radionuclides potentially released from radioactive waste disposal. The Tournemire URL intersects impervious and compacted argillite. A previously obtained chloride concentration profile of intact rock is symmetric with a maximum concentration of 0.6±0.1 g/L, compared to 19 g/L for the original connate seawater. Dissolved chloride shows high δ37Cl values, ranging between +6 and +8‰ vs. SMOC. The modeled profile considers diffusive exchange between connate seawater and meteoric freshwater. Transport parameters were obtained by radial diffusion experiments. Numerical modeling was performed with the coupled reactive-transport code Hytec. Simulations suggest a diffusive-exchange time of 85±10 Ma for Cl, which correlates with a major erosional period. Simulated δ37Cl values between 1.002 and agree with observed porewater δ37Cl. This study strongly suggests that the dissolved chloride profile in the argillites results from diffusive exchange and indicates that unfractured argillites can provide good confinement.

Long-term PAH monitoring results from the Anacostia River active capping demonstration using polydimethylsiloxane (PDMS) fibers

In this paper, the long-term monitoring results for hydrophobic organic compounds, specifically polycyclic aromatic hydrocarbons (PAHs), from a field demonstration of capping contaminated sediments at the Anacostia River in Washington DC are presented and analyzed. In situ pore water concentrations in field-contaminated sediments in the demonstration caps were quantified using a polydimethylsiloxane (PDMS)-based passive sampling device. High resolution vertical pore water concentration profiles were measured using the device and were used to infer fate and transport of polycyclic aromatics hydrocarbons (PAHs) at the site. The derived pore water concentrations were compared with observed bioaccumulation and solid-phase concentration profiles to infer contaminant migration rates and mechanisms. Observed pore water concentrations were found to be a better predictor of bioaccumulation than solid-phase concentrations. Solid-phase concentrations were low in cores which implied containment of contamination; however pore water profiles showed that contaminant migration had occurred in the first few years after cap placement. The discrepancy is the result of the low sorption capacity of the sand. Because of surface re-contamination, low sorption capacity in the demonstration caps and strong tidal pumping effects, steady state contaminant profiles were reached in the caps several years after placement. Despite re-contamination at the surface, steady state concentrations in the capped areas showed decreased contamination levels relative to the control area.

Dissolved oxygen and suspended particles regulate the benthic flux of iron from continental margins

We present ex situ sediment incubation results from the California and Oregon shelves and compare the calculated benthic flux of dissolved Fe with those from in situ incubations and pore water concentration profiles. We also examine the influence of oxygen depletion and sediment re-suspension on benthic Fe exchange. Ex situ incubation of the California and Oregon shelf sites yielded average benthic Fe fluxes of 3.5 and 8.3μmolm−2day−1, respectively, compared to 17 and 55μmolm−2day−1 from the in situ Lander determinations, and 73 and 103μmolm−2day−1 from modeling of pore water concentration profiles. Differences between benthic Fe flux estimates are primarily accounted for by [1] differences in Fe (II) oxidation kinetics, which result from distinct oxygen consumption rates between incubation methods, and the absence of kinetic considerations in the overlying bottom water in pore water flux calculations, and [2] the effects of biological sediment irrigation that are best represented by in situ incubations due to their sampling area and preservation of bottom water conditions. Bottom water oxygen concentrations were higher at the California shelf site than that at the Oregon shelf site, and probably accounted for the greater discrepancy between methods used to determine benthic Fe flux. The comparison of techniques used to determine benthic Fe flux indicates that the concentration of bottom water oxygen exerts a principle control over the fate of dissolved Fe entering the overlying bottom water — supporting the view that the expansion of coastal hypoxia has the potential to enhance the benthic supply of Fe (II) to shelf waters.An episode of surface sediment re-suspension during ex situ incubation led to a rapid removal of 76–89% of dissolved Fe from seawater, followed by a steady return towards initial seawater concentrations during particle settling, indicating that diffusive inputs of dissolved Fe from sediment pore water are rapidly adsorbed and desorbed by particles during periods of benthic re-suspension. The findings suggest that dissolved Fe concentrations in bottom waters may reflect an equilibrium concentration of non-stabilized aqueous Fe and particle-adsorbed Fe phases — where the addition of suspended particles to bottom waters leads to scavenging of dissolved Fe into labile particulate Fe phases. Thus we suggest that suspended particles are a significant buffer of dissolved Fe released from shelf sediments, an important transport mechanism for benthic Fe inputs, and a regulator of dissolved Fe concentrations in seawater.

Nitrogen transformations in a through‐flow wetland revealed using whole‐ecosystem pulsed 15N additions

We used pulsed and continuous additions of 15N together with whole‐ecosystem metabolism measurements to elucidate the mechanisms of nitrogen (N) transformations in a small (1170 m2) through‐flow wetland situated along a stream. From measurements of the wetland inflow and outflow, we observed a consistent decrease in nitrate (by 10% of inflow concentrations), while ammonium increased by an order of magnitude. Outflow ammonium concentrations oscillated in a diel cycle, inverse to the concentration of dissolved oxygen (i.e., greater ammonium export at night). The pulsed 15N additions showed little uptake of nitrate over time in the wetland and rapid daytime uptake of ammonium from the water column (rate constant, kt = 0.11 h−1). A steady‐state 15N‐ammonium addition demonstrated a similar rate of ammonium uptake (kt = 0.067 h−1), no detectable nitrification, and highlighted the spatial pattern of ammonium and nitrate uptake within the wetland. Porewater concentration profiles suggest high rates of net ammonium diffusion from the sediments. Ecosystem metabolism measurements indicate that release was attenuated during the day by autotrophic uptake, resulting in lower ammonium export during the day. Denitrification rates were modeled from dissolved N2 : Ar ratios, but they were not sufficient to account for the observed loss in nitrate. Nitrate was removed near the pond inflow but not actively cycled throughout the pond, while the balance between sediment release and subsequent uptake of ammonium from the water‐column dominated N cycling in this wetland.