Flow-through Reactor Experiments Research Articles

Loss of Selenium from Mollisol Paddy Wetlands of Cold Regions: Insights from Flow-through Reactor Experiments and Process-Based Modeling

Mollisols are critical agricultural resources for securing global food supply. Due to its health importance, selenium (Se) fate in the Mollisols attracts growing concerns. Land use change from conventional drylands to paddy wetlands impacts Se bioavailability in the vulnerable Mollisol agroecosystems. The underlying processes and mechanisms however remain elusive. Here, results of flow-through reactor experiments with paddy Mollisols from northern cold-region sites indicate that continuous flooding with surface water for 48 d induced redox zonation that facilitated the loss of Mollisol Se by up to 51%. Further process-based biogeochemical modeling suggests largest degradation rates of dissolved organic matter (DOM) in 30 cm deep Mollisols that contained the highest-level labile DOM and organic-bound Se. Electron shunting from degradation of Se-bearing DOM coupled to reductive dissolution of Se-adsorbed Fe oxides accounts mainly for Se(IV) release into the pore water. Consequent changes in DOM molecular composition make the reservoir of organic-bound Se vulnerable to flooding-induced redox zonation and likely enhance Se loss through destruction of thiolated Se and emission of gaseous Se from the Mollisol layer. This study highlights a neglected scenario where the speciation-driven loss of bioavailable Se from the paddy wetlands can be a significant consequence in the cold-region Mollisol agroecosystems.

Influence of non-equilibrium and nonlinear sorption of 137Cs in soils. Study with stirred flow-through reactor experiments and quantification with a nonlinear equilibrium-kinetic model

This paper addresses the modelling of cesium sorption in non-equilibrium and nonlinear conditions with a two-site model. Compared to the classical Kd approach, the proposed model better reproduced the breakthrough curves observed during continuous-flow stirred tank reactor experiments conducted on two contrasted soils. Fitted parameters suggested contrasted conditions of cesium sorption between 1) equilibrium sites, with low affinity and high sorption capacity comparable to CEC and 2) non-equilibrium sites, with a fast sorption rate (half-time of 0.2–0.3 h), a slow desorption rate (half-time of 3–9 days) and a very low sorption capacity (0.02–0.04% of CEC). Comparison of EK sites densities with sorption capacities derived from the literature suggests that the EK equilibrium and kinetic sites might correspond to ion exchange and surface complexation of soil clay minerals respectively. This work stresses the limits of the Kd model to predict 137Cs sorption in reactive transport conditions and supports an alternative non-equilibrium nonlinear approach.

Does Nitrate Enrichment Accelerate Organic Matter Turnover in Subterranean Estuaries?

Due to the widespread pollution of coastal groundwaters with fertilizers, submarine groundwater discharge (SGD) is often thought to be a large dissolved inorganic nitrogen (DIN) source to the ocean. Whether this N is autochthonous or allochthonous to the subterranean estuary (STE), the availability of large quantities of DIN can nevertheless interact with the cycling of other elements, such as carbon (C). In previous studies, we documented the discharge of large quantities of freshwater and NO3– from the mouth of an STE into the Ria Formosa lagoon (SW Iberian Peninsula). For the period covered in this study (2009–2011), the same STE site was dominated by recirculating seawater due to a prolonged fall in piezometric head in the coupled coastal aquifers. Total SGD rates remained similarly high, peaking at 144 cm day–1 at the lower intertidal during fall. We observed a progressive increase of NO3– availability within the STE associated with the recovery of piezometric head inland. Interestingly, during this period, the highest SGD-derived dissolved organic C and DIN fluxes (112 ± 53 and 10 ± 3 mmol m–2 day–1, respectively) originated in the lower intertidal. NO3– enrichment in the STE influences the benthic reactivity of fluorescent dissolved organic matter (FDOM): when seawater recirculation drives STE dynamics, only small changes in the benthic distribution of recalcitrant humic-like FDOM are observed (from −2.57 ± 1.14 to 1.24 ± 0.19 10–3 R.U. “bulk” sediment h–1) in the absence of DIN. However, when DIN is available, these recalcitrant fractions of FDOM are actively generated (from 1.32 ± 0.15 to 11.56 ± 3.39 10–3 R.U. “bulk” sediment h–1), accompanied by the production of labile protein-like FDOM. The results agree with previous studies conducted with flow-through reactor experiments at the same site and suggest that DIN enrichment in the STE enhances the metabolic turnover of sedimentary organic matter up to the point of discharge to surface waters. DIN pollution of coastal aquifers may therefore promote a contraction of the residence time of particulate organic C within the STE, driving carbon from continental storage into the sea.

Impact of Suspended Solids and Organic Matter on Chlorine and UV Disinfection Efficiency of Greywater

Reusing greywater (GW) can lower domestic water consumption. However, the GW must be treated and disinfected for securing user health. This research studied at the laboratory scale, and in flow-through setups, which are generally used in full-scale GW treatment the disinfection efficiency of the two commonly used technologies (a) chlorination and (b) low-pressure UV irradiation. The disinfection methods were studied under a commonly found range of total suspended solids (TSS; 3.9–233 mg/L) and 5-d biochemical oxygen demand (BOD5) concentrations (0–107 mg/L) as a representative/proxy of bioavailable organic matter. The negative effect of TSS began even at low concentrations (<20 mg/L) and increased consistently with increasing TSS concentrations across all the concentrations tested. On the other hand, the negative effect of BOD5 on FC inactivation was observed only when its concentration was higher than 50 mg/L. Multiple linear regression models were developed following the laboratory results, establishing a correlation between FC inactivation by either chlorination or UV irradiation and initial FC, TSS, and BOD5 concentrations. The models were validated against the results from the flow-through reactors and explained the majority of the variability in the measured FC inactivation. Conversion factors between the laboratory scales and the flow-through reactor experiments were established. These enable the prediction of the required residual chlorine concentration or the UV dose needed for an on-site flow-through reactor. This approach is valuable from both operational and research perspectives.

In Situ Formation of Silver Nanoparticles (Ag-NPs) onto Textile Fibers

Silver nanoparticles (Ag-NPs) adhered/inserted on textile fibers have an effective antimicrobial role. However, their release due to low adherence and their fate in the natural settings have been questioned in terms of toxicity level. In order to overcome this recurrent problem of adherence, the in situ formation of Ag-NPs in five textile fibers (cotton (untreated and chemically bleached), sheep’s wool, polyamide, and polyester) was assessed. Herein, the fibers were first immersed in a silver ion solution (1 g/L of AgNO3) for ion saturation at room T for 24 h followed by draining fibers and their reimmersion this time in a strong chemical reducing solution (0.25 g/L of NaBH4) at room T for 24 h. This latter step leads to the in situ formation of Ag-NPs where size (5 nm < size < 50 nm), surface covering concentration, and aggregation degree depend on the textile fiber kind as deduced from FESEM images. This simple lab chemical method allows instantaneous in situ formation of Ag-NPs onto fibers without the requirement of additional thermal treatment. Moreover, for natural fibers, the formation of Ag-NPs inside of them is also expected as confirmed from FESEM images in cotton cross sections. In complement, all textile fibers containing Ag-NPs (sheep’s wool 10 mg/g > untreated cotton 2.3 mg/g > bleached cotton 1 mg/g > polyamide 0.62 mg/g > polyester 0.28 mg/g) were submitted to interact with strong oxidants in an aqueous media (7.5% v/v of H2O2, 0.5 and 0.05 M of HNO3 and ultrapure water as the control) using flow-through reactor experiments. Here, breakthrough curves reveal that the oxidative dissolution rate (given in mol/g min) of adhered Ag-NPs (ionic release) depends strongly on fiber nature, and nature and concentration of oxidant solution. In summary, this fundamental study suggests that Ag-NPs may be successfully adhered/inserted in natural fibers (wool and cotton) in a safety-design perspective with performant biocide properties as confirmed by using Bacillus subtilis.

Influences of phosphorus concentration and porewater advection on phosphorus dynamics in carbonate sands around the Weizhou Island, northern South China Sea

A series of flow-through reactor experiments were undertaken to assess the potential effect of porewater advection and dissolved inorganic phosphorus (DIP) concentration on benthic DIP dynamics in permeable sediments collected from the Weizhou Island, northern South China Sea. The flux of DIP ranged from −0.13 to 0.05 mmol m−2 h−1, and the reversal from DIP efflux to influx occurred when the DIP concentration reached a threshold. DIP release from the sediment into the seawater peaked at intermediate advection rate, which perhaps provide optimum conditions for DIP release related to CaCO3 dissolution. Phosphorus limitation in seawater could be relieved by DIP release from the sediment, and CaCO3-bound P in carbonate sands may play a major role in benthic DIP release and decrease in the molar nitrogen/phosphorus ratio in seawater around the Weizhou Island.

Carbon and nutrient dynamics of permeable carbonate and silicate sands adjacent to coral reefs around Weizhou Island in the northern South China Sea

Permeable sandy sediment acts as an active biogeochemical reactor, but its role in the circulation of elements in coastal areas is not yet clear. Here, repacked flow-through reactor experiments were conducted at 5 stations adjacent to coral reefs around Weizhou Island in the northern South China Sea in May 2018 to investigate the carbon and nutrient dynamics in permeable carbonate and silicate sands. The potential rates of organic metabolism ranged from 1.82 to 12.08 mmol m−2 h−1, which impacted carbon and nutrient dynamics in permeable sands. CaCO3 calcification and dissolution indicated by the flux of total alkalinity (−0.43–0.59 mmol m−2 h−1) were controlled by the saturation state of the inflow seawater. Most dissolved inorganic nutrients were taken up by the permeable sediments, but a small amount of dissolved organic nitrogen and phosphorus was released from the sediments. The uptake rates of dissolved inorganic phosphorus and dissolved silicate were higher in the carbonate sands than in the silicate sands, while the mineralogical characteristics did not seem to play a relevant role in the fluxes of dissolved inorganic carbon and nitrogen. Our results show that the uptake of nutrients in permeable sediments resulted in a decreased ratio of nitrogen to phosphorus in seawater, which may benefit reef ecosystems. However, we still need a better understanding of the role of permeable sediments in elemental cycling under natural conditions and of their interactions with environmental factors, such as the input of terrigenous organic matter.

Bacterial fermentation and respiration processes are uncoupled in anoxic permeable sediments.

Permeable (sandy) sediments cover half of the continental margin and are major regulators of oceanic carbon cycling. The microbial communities within these highly dynamic sediments frequently shift between oxic and anoxic states, and hence are less stratified than those in cohesive (muddy) sediments. A major question is, therefore, how these communities maintain metabolism during oxic-anoxic transitions. Here, we show that molecular hydrogen (H2) accumulates in silicate sand sediments due to decoupling of bacterial fermentation and respiration processes following anoxia. In situ measurements show that H2 is 250-fold supersaturated in the water column overlying these sediments and has an isotopic composition consistent with fermentative production. Genome-resolved shotgun metagenomic profiling suggests that the sands harbour diverse and specialized microbial communities with a high abundance of [NiFe]-hydrogenase genes. Hydrogenase profiles predict that H2 is primarily produced by facultatively fermentative bacteria, including the dominant gammaproteobacterial family Woeseiaceae, and can be consumed by aerobic respiratory bacteria. Flow-through reactor and slurry experiments consistently demonstrate that H2 is rapidly produced by fermentation following anoxia, immediately consumed by aerobic respiration following reaeration and consumed by sulfate reduction only during prolonged anoxia. Hydrogenotrophic sulfur, nitrate and nitrite reducers were also detected, although contrary to previous hypotheses there was limited capacity for microalgal fermentation. In combination, these experiments confirm that fermentation dominates anoxic carbon mineralization in these permeable sediments and, in contrast to the case in cohesive sediments, is largely uncoupled from anaerobic respiration. Frequent changes in oxygen availability in these sediments may have selected for metabolically flexible bacteria while excluding strict anaerobes.

Arsenite and chromate sequestration onto ferrihydrite, siderite and goethite nanostructured minerals: Isotherms from flow-through reactor experiments and XAS measurements.

Sorption isotherms remain a major tool to describe and predict the mobility of pollutants in natural and anthropogenic environments, but they are typically determined by independent batch experiments. In the present study, the sequestration of As(III), Cr(VI) and competitive As(III)-Cr(VI) on/in 6L-ferrihydrite, siderite and goethite nanostructured minerals was reinvestigated using stirred flow-through reactor experiments. Herein, sorption isotherms were particularly determined from breakthrough curves for inert and reactive tracers monitored simultaneously in a single percolation experiment. In complement, X-ray absorption spectroscopy (XAS) was used to identify As sorption sites on 6L-ferrihydrite and goethite. As expected, the minerals have high potential to remove As and Cr from water (siderite = ferrihydrite (about 60 mg/g) > goethite (20 mg/g)). As and Cr sorption isotherms were modelled with a Langmuir model, and with a sigmoidal Hill model in the case of the competitive sorption. XAS measurements have revealed that As(III) was partially oxidized (up to 22%) in the competitive system with chromate oxyanion Cr(VI). As(III) sorbed on ferrihydrite and goethite adopted edge-sharing and corner sharing complex geometries. Nowadays, a new class of adsorbing phases is being developed for wastewater treatment, including engineered nanostructured materials and nanocomposites. The use of flow through reactor experiments as a high throughput method, combined with XAS, should be considered as efficient screening methods to test their sorbing properties on various contaminants.

Selenate reduction rates and kinetics across depth in littoral sediment of the Salton Sea, California

To predict selenium cycling in sediments, it is crucial to identify and quantify the processes leading to selenium sequestration in sediments. More specifically, it is essential to obtain environmentally-relevant kinetic parameters for selenium reduction and information on how they spatially vary in sediments. The Salton Sea (California, USA) is an ideal model system to examine selenium processes in sediments due to its semi-enclosed conditions and increasing selenium concentration over the last century. Selenium enters the Salton Sea mainly as selenate and might be sequestered in the sediment through microbial reduction. To determine the potential selenium sequestration of Salton Sea littoral sediments and which sediment properties are controlling selenate reduction kinetics, we determined the centimeter-scale vertical distribution of potential selenate reduction rates and apparent kinetic parameters (maximum selenate reduction rates, Vmax, and selenate half-saturation concentration, Km) using flow-through reactor (FTR) experiments. We compared sediments from two littoral sites (South and North) and four depth intervals (0–2, 2–4, 4–6 and 6–8 cm). Furthermore, we characterized the selenium fractions in the sediment recovered from the FTR experiments to identify the processes leading to the sequestration of selenium. Our results reveal higher potential for selenium reduction and sequestration in the topmost sediment (0–2 cm) suggesting that microorganisms inhabiting surface sediment are well adapted to reduce selenate entering the Salton Sea. As apparent Km values (103–2144 µM) exceed the average selenium concentration in the overlying water (6–25 nM), in situ selenate reduction is limited by the low availability of selenate and the resident selenate-reducing microorganisms operate well below their Vmax (11 and 43 nmol cm−3 h−1). Selenium speciation after FTR experiments confirms the primary sequestration of reduced biomass-associated and elemental selenium (68–99% of total selenium) in the sediment. Further, the absence of correlation between the tested sediment physical (porosity, bulk density, clay content), chemical (Corg, Ntot, total selenium content) and biological characteristics (abundance of culturable selenate-reducers) with the kinetic parameters of selenate reduction indicates that these sediment characteristics cannot be used as predictors of apparent Vmax or Km. Conclusively, microbial selenate reduction is an important, if not the primary process, leading to the sequestration of reduced selenium in the Salton Sea sediments and making the surficial Salton Sea sediments an important selenium sink.

Influence of labile dissolved organic matter on nitrate reduction in a seepage face.

Seepage faces, the outer rim of subterranean estuaries, are an important reaction node for SGD-borne nitrate (NO3-) on a global scale. Labile dissolved organic matter (DOM) has been suggested to be a key factor constraining the NO3- removal rate in aquifer systems. To determine whether and to what extent the availability of labile DOM affects benthic NO3- reduction in seepage faces, a series of flow-through reactor (FTR) experiments with sandy sediment collected from a seepage face was conducted under oxic conditions. Experimental results revealed that the addition of labile DOM (glucose) to porewater did not trigger a significant enhancement in NO3- reduction rate. In contrast, the aerobic respiration was boosted from ca. 50 to 90μmoldm-3 sediment h-1 by glucose amendments, accounting for approximately 70% consumption of the labile DOM pool. This rapid consumption may increase the NO3- reducing capability within the sediment, but only indirectly. Together with fluorescent DOM (FDOM) analyses, it can be inferred that NO3- reducers tend to choose sediment organic matter the prime electron donor under the experimental conditions. As a result, enrichment of DOM in seepage faces, depending on composition, might only stimulate aerobic respiration and nitrification, thus promoting the increase of ensuing NO3- fluxes to adjacent coastal waters.

Flow-through reactor experiments on basalt-(sea)water-CO2 reactions at 90 °C and neutral pH. What happens to the basalt pore space under post-injection conditions?

Recent publications on the successful mineralisation of carbon dioxide in basalts in Iceland and Washington State, USA, have shown that mineral storage can be a serious alternative to more mainstream geologic carbon storage efforts to lock away permanently carbon dioxide. In this study we look at the pore solution chemistry and mineralogy of basaltic glass and crystalline basalt under post-injection conditions, i.e. after rise of the pH via matrix dissolution and the first phase of carbonate formation. Experimental findings indicate that further precipitation of carbonates under more alkaline conditions is highly dependent on the availability of divalent cations. If the pore water is deficient in divalent cations, smectites and/or zeolites will dominate the secondary mineralogy of the pore space, depending on the basalt matrix. At low carbonate alkalinity no additional secondary carbonates are expected to form meaning the remaining pore space is lost to secondary silicates, irrespective of the basalt matrix. At high carbonate alkalinity, some of this limited storage volume may additionally be occupied by dawsonite −if the Na concentration in the percolating groundwater (brine) is high. Using synthetic seawater as a proxy for the groundwater composition and thus furnishing considerable amounts of divalent cations to the carbonated solution, results in massive precipitation of calcite, magnesite, and other Ca/Mg-carbonates under already moderate carbonate alkalinity. More efficient use of the basaltic storage volume can thus be attained by promoting formation of secondary carbonates compared to the inevitable formation of secondary silicate phases at higher pH. This can be done by ensuring that the pore water does not become depleted in divalent cations, even after carbonate formation. Using seawater as carbonating fluid or injection of CO2 into the basaltic oceanic crust, where saline fluids percolate, can reach this goal. However, such an approach needs sophisticated reactive transport modelling to adjust CO2 injection rates in order to avoid too rapid carbonate deposition and clogging of the pore space too close to the injection well.

Kinetics of inorganic nitrogen turnover in a sandy seepage face on a subterranean estuary

Subterranean estuary seepage faces are recognized as important reactive interfaces that regulate solute transport to coastal ecosystems via Submarine Groundwater Discharge (SGD). Here we describe benthic processes and rates driving the biogeochemical regulation of SGD-borne inorganic N loading into the Ria Formosa lagoon (Iberian peninsula) through a sandy seepage face. Maximum potential NO3− reduction rates, obtained by kinetic modeling of advection-controlled flow-through reactor experiments, ranged from 2.33 ± 1.06 to 14.17 ± 0.22 nmol cm−3 “bulk” sediment (bs) h−1. Maximum potential nitrification ranged from 0 to 7.5 ± 1.3 nmol cm−3 bs h−1 while potential ammonium assimilation was valued at 2.0 ± 0.3 nmol cm−3 bs h−1. These NO3− reduction rates are in good agreement with previous estimates obtained by diagenetic modeling of in-situ porewater NO3− vertical profiles at the same location. Potential NO3− reduction rates were very sensitive to temperature (Q10 = 3.5 ± 0.2). Porewater velocity seems to control net NO3− reduction rates, probably by determining solute distribution but also its supply to the microbial community by shaping the diffusive boundary layer around sediment particles. Nevertheless, NO3− reduction rates seem ultimately limited by organic matter availability at high velocities. Half-saturation constants of NO3− for NO3− reduction were low, suggesting that the NO3− reducing microbial community had high affinity for NO3−. In addition, our experiments provide evidence for the occurrence of alternative NO3− reduction pathways, including Dissimilatory Nitrate Reduction to Ammonium (DNRA) and apparent aerobic NO3− reduction within the shallow subsurface sediment layer (2–12 cm depth).

Metabolism in anoxic permeable sediments is dominated by eukaryotic dark fermentation.

Permeable sediments are common across continental shelves and are critical contributors to marine biogeochemical cycling. Organic matter in permeable sediments is dominated by microalgae, which as eukaryotes have different anaerobic metabolic pathways to prokaryotes such as bacteria and archaea. Here we present analyses of flow-through reactor experiments showing that dissolved inorganic carbon is produced predominantly as a result of anaerobic eukaryotic metabolic activity. In our experiments, anaerobic production of dissolved inorganic carbon was consistently accompanied by large dissolved H2 production rates, suggesting the presence of fermentation. The production of both dissolved inorganic carbon and H2 persisted following administration of broad spectrum bactericidal antibiotics, but ceased following treatment with metronidazole. Metronidazole inhibits the ferredoxin/hydrogenase pathway of fermentative eukaryotic H2 production, suggesting that pathway as the source of H2 and dissolved inorganic carbon production. Metabolomic analysis showed large increases in lipid production at the onset of anoxia, consistent with documented pathways of anoxic dark fermentation in microalgae. Cell counts revealed a predominance of microalgae in the sediments. H2 production was observed in dark anoxic cultures of diatoms (Fragilariopsis sp.) and a chlorophyte (Pyramimonas) isolated from the study site, substantiating the hypothesis that microalgae undertake fermentation. We conclude that microalgal dark fermentation could be an important energy-conserving pathway in permeable sediments.

Identifiability of sorption parameters in stirred flow-through reactor experiments and their identification with a Bayesian approach

This paper addresses the methodological conditions –particularly experimental design and statistical inference– ensuring the identifiability of sorption parameters from breakthrough curves measured during stirred flow-through reactor experiments also known as continuous flow stirred-tank reactor (CSTR) experiments. The equilibrium-kinetic (EK) sorption model was selected as nonequilibrium parameterization embedding the Kd approach. Parameter identifiability was studied formally on the equations governing outlet concentrations. It was also studied numerically on 6 simulated CSTR experiments on a soil with known equilibrium-kinetic sorption parameters. EK sorption parameters can not be identified from a single breakthrough curve of a CSTR experiment, because Kd,1 and k− were diagnosed collinear. For pairs of CSTR experiments, Bayesian inference allowed to select the correct models of sorption and error among sorption alternatives. Bayesian inference was conducted with SAMCAT software (Sensitivity Analysis and Markov Chain simulations Applied to Transfer models) which launched the simulations through the embedded simulation engine GNU-MCSim, and automated their configuration and post-processing. Experimental designs consisting in varying flow rates between experiments reaching equilibrium at contamination stage were found optimal, because they simultaneously gave accurate sorption parameters and predictions. Bayesian results were comparable to maximum likehood method but they avoided convergence problems, the marginal likelihood allowed to compare all models, and credible interval gave directly the uncertainty of sorption parameters θ. Although these findings are limited to the specific conditions studied here, in particular the considered sorption model, the chosen parameter values and error structure, they help in the conception and analysis of future CSTR experiments with radionuclides whose kinetic behaviour is suspected.

Oxygen transport and reactivity within a sandy seepage face in a mesotidal lagoon (Ria Formosa, Southwestern Iberia)

Sandy sediments are now recognized as sites of high carbon turnover enhanced by porewater flow. However, it is unclear how coupling between porewater advection and benthic metabolism might permit O2-saturated areas and suboxic environments to coexist in close proximity. Field sampling campaigns, flow-through reactor (FTR) experiments and diagenetic modeling were used to study benthic O2 dynamics in surface sediments of a permeable intertidal seepage face (Ria Formosa; Southwestern Iberia). Field results demonstrated that the pressure gradient imposed by tidal oscillation at the seepage face permits seawater infiltration at high tide, and hence resupplies the benthos in O2 and organic matter (OM). Significant aerobic respiration rates (12.1–26.8 nmol cm−3 “bulk sediment” (bs) h−1) were derived from vertical O2 gradients taken from the top 28 cm of the sediment during active seepage. FTR experiments showed a vertical zonation of respiration rates following benthic OM availability (from 8.63 ± 1.88 nmol cm−3 bs h−1 at 12–32 cm depth to 53.55 ± 7.93 nmol cm−3 bs h−1 at 0–2 cm depth). Advection enhances O2 consumption rates, but respiration is ultimately limited by OM availability at high seepage rates. Diagenetic modeling of O2 distribution in the porewater suggests that even within a well-oxygenated beach aquifer, local respiration is sufficiently high to lower the porewater O2 concentration near the sediment surface during active seepage. Our results indicate that high seepage rates, OM and O2 loading promoted by tidally-driven seawater infiltration control the O2 consumption at the sediment surface, thus favoring the occurrence of suboxic biogeochemical processes near the sediment surface.

Effects of recirculation of seawater enriched in inorganic nitrogen on dissolved organic carbon processing in sandy seepage face sediments

Human activities are now the main source of bioavailable Nitrogen to Earth's ecosystems. Disruption of the N cycle can promote changes to the biogeochemical cycling of other elements in particular to the oxygen and carbon cycles. Nevertheless, information on how increasing Dissolved Inorganic Nitrogen (DIN) availability might affect the benthic processing of organic matter in coastal sandy sediments is currently unavailable. Here, we present a series of flow-through reactor experiments conducted with undisturbed sediment cores collected at an intertidal seepage face (Ria Formosa lagoon, SW Iberian Peninsula) in order to evaluate the effect of increasing DIN availability on benthic dissolved organic C (DOC) reactivity. Our results show that the metabolic activity of the benthic community can be a significant source of DOM to the porewater. Furthermore, in the absence of DIN, increasing porewater flow rates accelerated benthic DOM production and increased the recalcitrant nature of DOC transported across the sediment-water interface. In contrast, the co-occurrence of high DIN concentrations and high seepage velocities increased the microbial breakdown of organic material. Our results suggest that the availability of DIN in permeable seepage faces increases the net production of labile DOC, by enhancing the ability of the benthic microbial community to process refractory organic matter. Hence, we suggest that increasing DIN availability in coastal permeable sediments accelerates benthic organic C processing, promoting the release of more labile DOC to receiving water bodies.

Kinetics of selenate sorption in soil as influenced by biotic and abiotic conditions: a stirred flow-through reactor study

This study (i) quantified the kinetics of selenate sorption and (ii) measured the influence of biotic processes in soil selenate stabilisation. Stirred flow-through reactor experiments were conducted on samples of a silty clay soil (pH = 8, Eh = 240–300 mV) from Bure (France) in both non-sterile and sterile conditions. Parameters of the proposed two-site sorption model (EK), adapted from van Genuchten and Wagenet (1989), were estimated by nonlinear regression. Fast selenate sorption on type-1 sites was moderate, with an equilibrium constant of 25.5 and 39.1 L/kg for non-sterile and sterile conditions. Rate-limited sorption on type-2 sites increased with time, and was predominant for longer periods of time in non-sterile conditions. At equilibrium, it would represent over 96% of the sorbed inventory, with mean sorption times of 17 h and 191 h for non-sterile and sterile conditions. Our results showed for Bure soil that (i) selenate sorption in flowing and mildly-oxidising conditions was strongly kinetically controlled, especially in non-sterile conditions, (ii) selenate desorption was much slower than sorption, which suggests its pseudo-irreversible stabilisation, and (iii) microbial activity increased the contribution of rate-limited sorption on type-2 sites, for which it increased sorption rate by a factor 7 but also facilitated its reversibility. This work stresses the limits of the Kd approach to represent selenate sorption in flowing conditions and supports an alternative formulation like the EK model, but also points out that biotic conditions are significant sources of variability for sorption parameters.

Enhancement of denitrification in permeable carbonate sediment due to intra-granular porosity: A multi-scale modelling analysis

It has recently been hypothesized that bulk denitrification rates in carbonate sands may be enhanced by reactions occurring in the intra-granular pores, cracks and crevices. We tested this hypothesis using a series of flow and reactive transport models spanning from the pore-scale (∼mm) to the continuum scales (∼10cm bedforms). Pore-scale simulations solved the coupled Navier–Stokes and Brinkman equations and represented flow-through reactor experiments previously performed on coral reef sands. The results revealed that intra-granular transport and reactions can explain over-all denitrification enhancement. A sensitivity study with a single grain diffusive transport model showed that in the majority of cases, the resultant increase in denitrification was not coupled to nitrification within a single grain. Only for large grain diameters of 2 and 4mm was coupled nitrification–denitrification important. In most cases, coupled nitrification–denitrification instead arose as conditions became more reducing along a flow path, as is the case in quartz sands without intragranular pores. An intra-granular reaction rate based on a single grain model was incorporated into a continuum-scale Darcy flow and reactive transport model for a rippled sand bed, where porewater flow is driven by the turbulent current over the ripple. The results of the Darcy-scale model suggest that intra-granular pores increase the amount of slow-flowing areas within which coupled nitrification–denitrification can occur. We conclude that the complex advective flow field does not strongly inhibit denitrification enhancement by carbonate sand grains, as it does in silica sands. Thus, intra-granular reactions may enhance bulk denitrification in carbonate sediment with porous grains under natural advective conditions.

Nano-FeS Inhibits UO2 Reoxidation under Varied Oxic Conditions

Bioreductive in situ treatment of U-contaminated groundwater can convert soluble U(VI) species to immobile reduced U(IV) solid phases such as UO2(s) to contain U movement. Once active bioremediation is halted, UO2 may be subsequently reoxidized if oxidants such as oxygen enter the reducing zone. However, iron sulfide minerals that form during bioreduction may serve as electron sources or oxygen scavengers and inhibit UO2 reoxidation upon oxygen intrusion. In this study, flow-through reactor experiments examined the abiotic kinetics of UO2 oxidative dissolution in the presence of oxygen and nanoparticulate FeS as a function of pH, dissolved oxygen (DO) concentration, and FeS content. The UO2 dissolution rates in the presence of FeS were over 1 order of magnitude lower than those in the absence of FeS under otherwise comparable oxic conditions. FeS effectively scavenged DO and preferentially reacted with oxygen, contributing to a largely unreacted UO2 solid phase during an "inhibition period" as determined by X-ray absorption spectroscopy (XAS). The removal of DO by FeS was significant but incomplete during the inhibition period, resulting in surface-oxidation-limited dissolution and greater UO2 dissolution rate with increasing influent DO concentration and decreasing FeS content. Although the rate was independent of solution pH in the range of 6.1-8.1, the length of the inhibition period was shortened by substantial FeS dissolution at slightly acidic pH. The reducing capacity of FeS was greatest at basic pH where surface-mediated FeS oxidation dominated.