Diffusive Equilibration In Thin Films Research Articles

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.

2D distribution of Pseudomonas fluorescens activities at the soil-root interface of sunflower grown on vineyard soils: Effects on copper uptake

Pseudomonas fluorescens is a siderophore producing bacteria that is expected to alter the mobility and bioavailability of Cu in vineyard soils due to its ability to produce pyoverdine under iron deficiency. In this study, we monitored the effect of this bacterial species, particularly the production of siderophore, on the mobility and bioavailability of copper (Cu) and other elements using a spatialized approach. Two vineyard soils cultivated with sunflower, one non-carbonated (N-Carb) and one carbonated (Carb), were bioaugmented with P. fluorescens or not. 2D mapping using diffusive equilibration in thin films (DET) and diffusive gradient in thin films (DGT) was performed on day 15 after germination. At the end of the experiment, elements concentrations were measured in the plants and in the soil extracts (CaCl2 0.01 M). The results showed that the mobility of Cu and other elements (Fe, Al, Mn, Zn, N and P) was enhanced in both soils when bioaugmented. The chemistry of DET and DGT provided insights into the processes behind mobility, such as the presence and distribution of free metallophore spots (2–3.5 μM), interpreted as pyoverdine, which played a non-negligible role in Cu, Fe, Al mobilization and to a lesser extent in that of Mn, whereas pH played a limited role. DGT imaging showed that, depending on the speciation of metals in the soil solution, the increase in mobility measured by DET did not always increase bioavailability. Nevertheless, the concentration of copper in the aerial part of sunflower cultivated on the bioaugmented carbonated soil increased by 30% and copper content by 200%. These results identify bioaugmentation with P. fluorescens as a potential way to increase Cu phytoextraction, especially in carbonated soil, mainly because of its effect on plant growth but also on Cu bioavailability at the soil-plant interface.

Early Diagenesis in the Hypoxic and Acidified Zone of the Northern Gulf of Mexico: Is Organic Matter Recycling in Sediments Disconnected From the Water Column?

Hypoxia and associated acidification are growing concerns for ecosystems and biogeochemical cycles in the coastal zone. The northern Gulf of Mexico (nGoM) has experienced large seasonal hypoxia for decades linked to the eutrophication of the continental shelf fueled by the Mississippi River nutrient discharge. Sediments play a key role in maintaining hypoxic and acidified bottom waters, but this role is still not completely understood. In the summer 2017, when the surface area of the hypoxic zone in the nGoM was the largest ever recorded, we investigated four stations on the continental shelf differentially influenced by river inputs of the Mississippi-Atchafalaya River System and seasonal hypoxia. We investigated diagenetic processes under normoxic, hypoxic, and nearly anoxic bottom waters by coupling amperometric, potentiometric, and voltammetric microprofiling with high-resolution diffusive equilibrium in thin-films (DET) profiles and porewater analyses. In addition, we used a time-series of bottom-water dissolved oxygen from May to November 2017, which indicated intense O2 consumption in bottom waters related to organic carbon recycling. At the sediment-water interface (SWI), we found that oxygen consumption linked to organic matter recycling was large with diffusive oxygen uptake (DOU) of 8 and 14 mmol m–2 d–1, except when the oxygen concentration was near anoxia (5 mmol m–2 d–1). Except at the station located near the Mississippi river outlet, the downcore pore water sulfate concentration decrease was limited, with little increase in alkalinity, dissolved inorganic carbon (DIC), ammonium, and phosphate suggesting that low oxygen conditions did not promote anoxic diagenesis as anticipated. We attributed the low anoxic diagenesis intensity to a limitation in organic substrate supply, possibly linked to the reduction of bioturbation during the hypoxic spring and summer.

Denitrification by benthic foraminifera and their contribution to N-loss from a fjord environment

Abstract. Oxygen and nitrate availabilities impact the marine nitrogen cycle at a range of spatial and temporal scales. Here, we demonstrate the impact of denitrifying foraminifera on the nitrogen cycle at two oxygen and nitrate contrasting stations in a fjord environment (Gullmar Fjord, Sweden). Denitrification by benthic foraminifera was determined through the combination of specific density counting per microhabitat and specific nitrate respiration rates obtained through incubation experiments using N2O microsensors. Benthic nitrate removal was calculated from submillimeter chemical gradients extracted from 2D porewater images of the porewater nitrate concentration. These were acquired by combining the DET technique (diffusive equilibrium in thin film) with chemical colorimetry and hyperspectral imagery. Sediments with high nitrate concentrations in the porewater and oxygenated overlying water were dominated by the non-indigenous species (NIS) Nonionella sp. T1. Denitrification by this species could account for 50 %–100 % of the nitrate loss estimated from the nitrate gradients. In contrast sediments below hypoxic bottom waters had low inventories of porewater nitrate, and denitrifying foraminifera were rare. Their contribution to benthic nitrate removal was negligible (&lt; 5 %). Our study showed that benthic foraminifera can be a major contributor to nitrogen mitigation in oxic coastal ecosystems and should be included in ecological and diagenetic models aiming to understand biogeochemical cycles coupled to nitrogen.

Transport and speciation of uranium in groundwater-surface water systems impacted by legacy milling operations

Growing worldwide concern over uranium contamination of groundwater resources has placed an emphasis on understanding uranium transport dynamics and potential toxicity in groundwater-surface water systems. In this study, we utilized novel in-situ sampling methods to establish the location and magnitude of contaminated groundwater entry into a receiving surface water environment, and to investigate the speciation and potential bioavailability of uranium in groundwater and surface water. Streambed temperature mapping successfully identified the location of groundwater entry to the Little Wind River, downgradient from the former Riverton uranium mill site, Wyoming, USA. Diffusive equilibrium in thin-film (DET) samplers further constrained the groundwater plume and established sediment pore water solute concentrations and patterns. In this system, evidence is presented for attenuation of uranium-rich groundwater in the shallow sediments where surface water and groundwater interaction occurs. Surface water grab and DET sampling successfully detected an increase in river uranium concentrations where the groundwater plume enters the Little Wind River; however, concentrations remained below environmental guideline levels. Uranium speciation was investigated using diffusive gradients in thin-film (DGT) samplers and geochemical speciation modelling. Together, these investigations indicate uranium may have limited bioavailability to organisms in the Little Wind River and, possibly, in other similar sites in the western U.S.A. This could be due to ion competition effects or the presence of non- or partially labile uranium complexes. Development of methods to establish the location of contaminated (uranium) groundwater entry to surface water environments, and the potential effects on ecosystems, is crucial to develop both site-specific and general conceptual models of uranium behavior and potential toxicity in affected ground and surface water environments.

In situ, high-resolution measurement of labile phosphate in sediment porewater using the DET technique coupled with optimized imaging densitometry

Obtaining two-dimensional distributions of reactive phosphorus in sediment porewater is very important for understanding fine-scale phosphorus mobilization and sequestration processes in sediments. In this study, the diffusive equilibrium in thin films (DET) measurement based on computer imaging densitometry (CID) was studied in detail with optimal conditions described. This study focuses on evaluating the two-dimensional colorimetric DET method coupled with CID (DET-CID method) for porewater labile phosphate measurements. The result shows that the red channel filter is the optimum channel for sensitivity to process the image. Additionally, staining time and temperature have great influence on the method, and 20 min staining time and ≥25 °C staining temperature were recommended. The minimum detection limit of labile phosphate of this method was 0.300 mg P/L, and the maximum detection limit could reach 50.00 mg P/L. The DET-CID technique can be used to measure labile phosphate in a wide range of acidic and alkaline water bodies (pH = 2–10 and water hardness from 0 to 2000 mg/L as CaCO3). The linear regression analysis shows that this technique presents very similar results compared with other two existing methods (R2 = 0.999). Our results would give insights into the precisely measurements of labile phosphate in field applications.

A new colorimetric DET technique for determining mm-resolution sulfide porewater distributions and allowing improved interpretation of iron(II) co-distributions.

Measurement of sulfide in pore waters is critical for understanding biogeochemical processes, especially within coastal sediments. Here we report the development of a new colorimetric DET (diffusive equilibration in thin films) technique for determining mm-resolution, two-dimensional sulfide distributions in sediment pore waters. This colorimetric sulfide DET method was based on the standard spectrophotometric methylene blue assay, but modified to allow quantitation of sulfide by computer imaging densitometry. The method detection and effective upper measurement limits of the optimised technique were 3.7 and 1000μmolL-1, respectively. The optimised sulfide DET method was combined with the colorimetric iron(II) DET method to obtain co-distributions in coastal seagrass (Zostera muelleri) colonised sediment under light and dark conditions. In the dark, seagrass sediments were more reduced than in the light, with large areas being dominated by high porewater sulfide concentrations. These co-distributions were compared with those obtained using the previously described DET-DGT (diffusive gradients in thin films) method for measuring iron(II) and sulfide co-distributions. There was less overlap of iron(II) and sulfide distributions using the sulfide DET as the two DET methods are influenced most by the later hours of deployment, whereas the sulfide-DGT measurement integrates concentrations over the whole deployment period. Overlap was most apparent in very dynamic sediment zones, such as burrow wall sediments.

In situ biochar capping is feasible to control ammonia nitrogen release from sediments evaluated by DGT

Evaluation of in situ capping with biochar (BC) to control ammonia nitrogen (NH4+-N) release from the sediments of Baiyangdian Lake, the largest freshwater lake in northern China, was performed after 10 months of field and mesocosm experiments. The concentration of NH4+-N in pore water and its resupply from native sediments and capped sediments were determined using the technique of diffusive equilibrium in thin films (DET) and the technique of diffusive gradients in thin films with CMI-7000 cation ion exchange membrane (CMI-DGT) binding layer. The results showed a low concentration of NH4+-N in pore water and a low resupply from the sediment or capping materials after BC capping. The concentration of bioavailable NH4+-N measured by DGT of the top 4 cm layer in BC capping layer was only 12.8%−29.2% of the native sediments. Flux DET-NH4+-N, could be reduced from 12.74 to 3.44 mg·m−2·d−1 and Flux DGT-NH4+-N was further reduced from 13.38 to 1.59 mg·m−2·d−1. The calculated concentration gradient at the sediment-water interface following the capping treatment was lower than the control. These results implied that BC capping reduced the release of NH4+-N from the sediments. The low resupply from the sediments was further demonstrated by the smaller ratio of CDGT to CDET (R) in the BC capping layer, which their average values were 0.48, 0.59, 0.68 in the BC capping layer, BC/soil layer and native sediments, respectively. The physical, chemical and microbiological effects were attributed to inhibit the NH4+-N release from sediments by the BC capping.

Diffusive gradients in thin films: devices, materials and applications

A large number of ex situ sampling techniques have been used traditionally to investigate the impact and fate of pollutants in soil, sediment and waters. However, the distribution and form of chemical species present are often altered prior analysis, due to the alterations during sampling and transfer to the laboratory. Alternatively, a robust in situ passive sampling technique , diffusive gradients in thin films (DGT), has been developed for the measurement of labile concentrations, species and distribution of various solutes in soil, sediment and waters. Here we review the recent developments in DGT device configurations and components, e.g., binding agents, diffusive phases and filter membranes. We highlight new configurations for effectively reducing the measurement errors and the disturbance of environmental media. We discuss DGT applications for the analysis of soil, sediment and water, such as evaluation of bioavailability and toxicity, measurement of nutrients and organic substances, and assessment of relationships between multiple solutes. We also present the coupling of DGT with other in situ measurement techniques such as dialysis samplers (Peeper), diffusive equilibrium in thin films (DET) and planar optodes (PO).

Chromium bioavailability in aquatic systems impacted by tannery wastewaters. Part 1: Understanding chromium accumulation by indigenous chironomids

The tanning industry uses large quantities of Cr whose contribution to the contaminant burden of aquatic organisms is not yet fully understood. The present study investigated Cr bioaccumulation by indigenous chironomids in a freshwater ecosystem impacted by tannery effluents. Total Cr content in sediments and in chironomids was determined on several occasions. Chromium distribution among sediments and pore waters, and Cr speciation in overlying and pore waters were studied in detail to understand possible factors controlling Cr bioavailability to chironomids. Total chromium concentration ranged from 69 to over 3000 μg g−1 dry weight in sediments and from negligible to over 300 μg g−1 dry weight in chironomids (values corrected for sediment gut content). Filterable (<0.45 μm) Cr concentration in overlying waters and pore waters from the surface sediment layers (upper 2 cm) ranged from 3 to 120 μg L−1, with Cr(VI) representing 0.5–28% of the total filterable Cr. Chromium profiles in pore waters as determined by diffusive equilibration in thin films (DET) and diffusive gradient in thin films (DGT) were comparable. DGT-labile Cr accounted for <2% of the total Cr measured by DET. Although Cr concentrations in sedimentary and aqueous matrices were not directly proportional to Cr levels measured in chironomids, the available findings suggested that Cr inputs from tanneries were bioavailable to resident chironomids. These observations are of particular importance considering that Cr(III), putatively of limited bioavailability and ecotoxicological concern, is the predominant redox form of Cr in bed sediments impacted by tannery discharges. The companion paper provides further insight into Cr bioavailability and effects in tannery impacted ecosystems using a combination of in situ and laboratory approaches.

Diffusive Gradients in Thin Films Reveals Differences in Antimony and Arsenic Mobility in a Contaminated Wetland Sediment during an Oxic-Anoxic Transition.

Antimony (Sb) and arsenic (As) are priority environmental contaminants that often co-occur at mining-impacted sites. Despite their chemical similarities, Sb mobility in waterlogged sediments is poorly understood in comparison to As, particularly across the sediment-water interface (SWI) where changes can occur at the millimeter scale. Combined diffusive gradients in thin films (DGT) and diffusive equilibration in thin films (DET) techniques provided a high resolution, in situ comparison between Sb, As, and iron (Fe) speciation and mobility across the SWI in contaminated freshwater wetland sediment mesocosms under an oxic-anoxic-oxic transition. The shift to anoxic conditions released Fe(II), As(III), and As(V) from the sediment to the water column, consistent with As release being coupled to the reductive dissolution of iron(III) (hydr)oxides. Conversely, Sb(III) and Sb(V) effluxed to the water column under oxic conditions and fluxed into the sediment under anoxic conditions. Porewater DGT-DET depth profiles showed apparent decoupling between Fe(II) and Sb release, as Sb was primarily mobilized across the SWI under oxic conditions. Solid-phase X-ray absorption spectroscopy (XAS) revealed the presence of an Sb(III)-S phase in the sediment that increased in proportion with depth and the transition from oxic to anoxic conditions. The results of this study showed that Sb mobilization was decoupled from the Fe cycle and was, therefore, more likely linked to sulfur and/or organic carbon (e.g., most likely authigenic antimony sulfide formation or Sb(III) complexation by reduced organic sulfur functional groups).

Comparing in situ colorimetric DET and DGT techniques with ex situ core slicing and centrifugation for measuring ferrous iron and dissolved sulfide in coastal sediment pore waters

In productive coastal sediments the separation between different biogeochemical zones (e.g. oxic, iron(III)-reducing and sulfate-reducing) may be on the scale of millimetres. Conventional measurement techniques simply cannot resolve changes in pore water solute concentrations over such small distances. The diffusive equilibration in thin films (DET) and the diffusive gradients in thin films (DGT) techniques allow in situ determination of pore water solute concentration profiles with one-dimensional profiles and/or two-dimensional distributions on the millimetre scale. Here we compare measurements of pore water iron(II) and sulfide using conventional core sampling (slicing and centrifugation) and colorimetric DET-DGT techniques. DET-DGT samplers were deployed within replicate sediment cores from three different sites, which were processed by slicing and centrifugation following retrieval of the samplers, so that the measurements were approximately co-located. Iron(II) concentrations were determined by DET at all three sites (0.3–262 μmol L−1), while dissolved sulfide was consistently measured by DGT at one site only (0.003–112 μmol L−1). Pore water concentrations of iron(II) and sulfide determined conventionally following pore water extraction (iron(II); 0.4–88 μmol L−1 and sulfide; 0.05–36 μmol L−1), were systematically lower than the colorimetric DET and DGT measurements in the same sample. This underestimation was most likely due to the mixing of sediment from different biogeochemical zones during pore water extraction, which resulted in the precipitation of iron(II) and sulfide. This study shows that conventional pore water extraction methods can be unreliable for the determination of redox-active solutes due to artefacts associated with pore water mixing.

Opening Opportunities for High-Resolution Isotope Analysis - Quantification of δ15NNO3 and δ18ONO3 in Diffusive Equilibrium in Thin-Film Passive Samplers.

The fate of nitrate transported across groundwater-surface water interfaces has been intensively studied in recent decades. The interfaces between aquifers and rivers or lakes have been identified as biogeochemical hotspots with steep redox gradients. However, a detailed understanding of the spatial heterogeneity and potential temporal variability of these hotspots, and the consequences for nitrogen processing, is still hindered by a paucity of adequate measurement techniques. A novel methodology is presented here, using Diffusive Equilibrium in Thin-film (DET) gels as high-spatial-resolution passive-samplers of δ15NNO3 and δ18ONO3 to investigate nitrogen cycling. Fractionation of δ15NNO3 and δ18ONO3 during diffusion of nitrate through the DET gel was determined using varying equilibrium times and nitrate concentrations. This demonstrated that nitrate isotopes of δ15NNO3 and δ18ONO3 do not fractionate when sampled with a DET gel. δ15NNO3 values from the DET gels ranged between 2.3 ± 0.2 and 2.7 ± 0.3‰ for a NO3- stock solution value of 2.7 ± 0.4‰, and δ18ONO3 values ranged between 18.3 ± 1.0 and 21.5 ± 0.8‰ for a NO3- stock solution of 19.7 ± 0.9‰. Nitrate recovery and isotope values were independent of equilibrium time and nitrate concentration. Additionally, an in situ study showed that nitrate concentration and isotopes provide unique, high-resolution data that enable improved understanding of nitrogen cycling in freshwater sediments.

Simultaneous Nitrite/Nitrate Imagery at Millimeter Scale through the Water–Sediment Interface

The present study describes new procedures to obtain at millimeter resolution the spatial distribution of nitrite and nitrate in porewaters, combining diffusive equilibrium in thin films (DET), colorimetry and hyperspectral imagery. Nitrite distribution can be easily achieved by adapting the well-known colorimetric method from Griess (1879) and using a common flatbed scanner with a limit of detection about 1.7 μmol L(-1). Nitrate distribution can be obtained after reduction into nitrite by a vanadium chloride reagent. However, the concentration of vanadium chloride used in this protocol brings coloration with a wide spectral signature that creates interference only deconvolvable by imaging treatment from an entire visible spectrum for each pixel (spectral analysis). This can be achieved by hyperspectral imaging. The protocol retained in the present study allows obtaining a nitrite/nitrate image with micromolar limit of detection. The methods were applied in sediments from the Loire Estuary after different treatments and allowed to precisely describe two-dimensional millimeter features. The present technique adds to the combination of gel-colorimetry and hyperspectral imagery a very promising new application of wide interest for environmental issues in the context of early diagenesis and benthic fluxes.

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.

A Holistic Approach to Understanding the Desorption of Phosphorus in Soils.

The mobility and resupply of inorganic phosphorus (P) from the solid phase were studied in 32 soils from the UK. The combined use of diffusive gradients in thin films (DGT), diffusive equilibration in thin films (DET) and the "DGT-induced fluxes in sediments" model (DIFS) were adapted to explore the basic principles of solid-to-solution P desorption kinetics in previously unattainable detail. On average across soil types, the response time (Tc) was 3.6 h, the desorption rate constant (k-1) was 0.0046 h(-1), and the desorption rate was 4.71 nmol l(-1) s(-1). While the relative DGT-induced inorganic P flux responses in the first hour is mainly a function of soil water retention and % Corg, at longer times it is a function of the P resupply from the soil solid phase. Desorption rates and resupply from solid phase were fundamentally influenced by P status as reflected by their high correlation with P concentration in FeO strips, Olsen, NaOH-EDTA and water extracts. Soil pH and particle size distribution showed no significant correlation with the evaluated mobility and resupply parameters. The DGT and DET techniques, along with the DIFS model, were considered accurate and practical tools for studying parameters related to soil P desorption kinetics.

Transformation of external sulphate and its effect on phosphorus mobilization in Lake Moshui, Wuhan, China

Average concentrations of sulphate in lakes continue to increase sharply. The response of phosphorus to sulphate input is of great importance due to the relationship between eutrophication and ecological health. A four-week experiment was conducted under simulated conditions using samples from a heavily polluted lake, Lake Moshui, in Wuhan, China, to examine the influence of external sulphate on phosphorus release and the transformation of sulphate. The results showed that the diffusion of sulphate into the sediments promoted the proliferation of sulphate-reducing bacteria (SRB) and the reduction of sulphate. Acetic acid was consumed due to sulphate reduction. The soluble reactive phosphorus (SRP) and soluble Fe measured with diffusive equilibration in thin-films (DET) probes increased significantly after the input of sulphate. The content of SRP was consistent with the variation in both the SRB number and the S0 content in the sediments. The maximum SRP concentration of 100.43mgL−1 was recorded 3cm below the sediment–water interface on the 29thd, which was more than twice the value of the control. There was a positive correlation between concentrations of Fe and SRP in the overlying water and the pore water of the sediments.

Phosphorus losses from agricultural land to natural waters are reduced by immobilization in iron-rich sediments of drainage ditches

Redox reactions involving iron (Fe) strongly affect the mobility of phosphorus (P) and its migration from agricultural land to freshwater. We studied the transfer of P from groundwater to open drainage ditches in an area where, due to Fe(II) rich groundwater, the sediments of these ditches contain accumulated Fe oxyhydroxides. The average P concentrations in the groundwater feeding two out of three studied drainage ditches exceeded environmental limits for freshwaters by factors 11 and 16, but after passing through the Fe-rich sediments, the P concentrations in the ditch water were below these limits. In order to identify the processes which govern Fe and P mobility in these systems, we used diffusive equilibration in thin films (DET) to measure the vertical concentration profiles of P and Fe in the sediment pore water and in the ditchwater. The Fe concentrations in the sediment pore water ranged between 10 and 200 mg L−1 and exceeded those in the inflowing groundwater by approximately one order of magnitude, due to reductive dissolution of Fe oxyhydroxides in the sediment. The dissolved P concentrations only marginally increased between groundwater and sediment pore water. In the poorly mixed ditchwater, the dissolved Fe concentrations decreased towards the water surface due to oxidative precipitation of fresh Fe oxyhydroxides, and the P concentrations decreased more sharply than those of Fe. These observations support the view that the dynamics of Fe and P are governed by reduction reactions in the sediment and by oxidation reactions in the ditchwater. In the sediment, reductive dissolution of P-containing Fe oxyhydroxides causes more efficient solubilization of Fe than of P, likely because P is buffered by adsorption on residual Fe oxyhydroxides. Conversely, in the ditchwater, oxidative precipitation causes more efficient immobilization of P than of Fe, due to ferric phosphate formation. The combination of these processes yields a natural and highly efficient sink for P. It is concluded that, in Fe-rich systems, the fate of P at the sediment–water interface is determined by reduction and oxidation of Fe.

In situ chemical transformations of silver nanoparticles along the water-sediment continuum.

In order to accurately assess the potential environmental risk posed by silver nanoparticles (Ag-NPs), their transformation and fate must be investigated in natural systems. This has proven to be very challenging due to the difficulties encountered in retrieving/analyzing NPs dispersed in complex and heterogeneous environmental matrices at relevant (i.e., low) concentrations. In this study, we overcame this challenge by immobilizing functionalized Ag-NPs onto plasma polymerized solid substrates to form "nano in situ deployment devices" (nIDDs). This method allowed us to retrieve and analyze the Ag-NPs after 48 h of direct exposure in freshwater-sediment and saltwater-sediment environments. The type and extent of Ag-NPs transformation was expected to vary along the water-sediment continuum as sediments typically contain steep gradients in solute concentrations and redox potential. To trace the distribution of redox sensitive elements (e.g., Fe, Mn), Diffusive Equilibration in Thin-films (DET) devices were inserted into the sediments alongside the nIDDs. Chemical transformation of the immobilized Ag-NPs across the water-sediment continuum was investigated after retrieval by synchrotron radiation X-ray Absorption Spectroscopy. Linear combination fitting of Ag K-edge X-ray absorption spectra indicated that the chemical transformations of Ag-NPs in both freshwater and saltwater sediments were strongly affected by the redox conditions over the investigated range. Silver bound to reduced sulfur was the principal product of Ag-NP transformations but different extents of transformation were observed for Ag-NPs exposed to different depths in the sediment. These field results add important insights about the transformation of Ag-NPs in heterogeneous environments.

Diffusive equilibrium in thin films provides evidence of suppression of hyporheic exchange and large‐scale nitrate transformation in a groundwater‐fed river

AbstractThe hyporheic zone of riverbed sediments has the potential to attenuate nitrate from upwelling, polluted groundwater. However, the coarse‐scale (5–10 cm) measurement of nitrogen biogeochemistry in the hyporheic zone can often mask fine‐scale (&lt;1 cm) biogeochemical patterns, especially in near‐surface sediments, leading to incomplete or inaccurate representation of the capacity of the hyporheic zone to transform upwelling NO3−. In this study, we utilised diffusive equilibrium in thin‐films samplers to capture high resolution (cm‐scale) vertical concentration profiles of NO3−, SO42−, Fe and Mn in the upper 15 cm of armoured and permeable riverbed sediments. The goal was to test whether nitrate attenuation was occurring in a sub‐reach characterised by strong vertical (upwelling) water fluxes. The vertical concentration profiles obtained from diffusive equilibrium in thin‐films samplers indicate considerable cm‐scale variability in NO3− (4.4 ± 2.9 mg N/L), SO42− (9.9 ± 3.1 mg/l) and dissolved Fe (1.6 ± 2.1 mg/l) and Mn (0.2 ± 0.2 mg/l). However, the overall trend suggests the absence of substantial net chemical transformations and surface‐subsurface water mixing in the shallow sediments of our sub‐reach under baseflow conditions. The significance of this is that upwelling NO3−‐rich groundwater does not appear to be attenuated in the riverbed sediments at &lt;15 cm depth as might occur where hyporheic exchange flows deliver organic matter to the sediments for metabolic processes. It would appear that the chemical patterns observed in the shallow sediments of our sub‐reach are not controlled exclusively by redox processes and/or hyporheic exchange flows. Deeper‐seated groundwater fluxes and hydro‐stratigraphy may be additional important drivers of chemical patterns in the shallow sediments of our study sub‐reach. © 2015 The Authors. Hydrological Processes Published by John Wiley &amp; Sons Ltd.