Diffusive Gradients In Thin Films Research Articles

Development and application of diffusive gradients in thin films for in situ sampling of the organic UV filter 4-methylbenzylidene camphor (4-MBC) in waters.

4-Methylbenzylidene camphor (4-MBC), a typical organic UV filter (OUVF) in personal care products, is considered to be a potential endocrine disruptor due to its estrogenic activity and bioaccumulation. Although 4-MBC residues have been extensively identified in aquatic waters, little is known about their occurrence, levels, and potential risk in coastal waters. This study developed a reliable sampling approach, based on diffusive gradients in thin films (DGT) with XAD-2 as the binding agent, for monitoring 4-MBC in coastal waters. The diffusion coefficients of 4-MBC in freshwater and artificial seawater were 3.65 × 10-6 cm2/s and 3.83 × 10-6 cm2/s, respectively. XAD-2 binding gel showed rapid adsorption to 4-MBC. The accumulated masses of 4-MBC in XAD-2 DGT increased linearly with deployed time for 7days in freshwater and seawater, which agreed well with theoretical predictions. The sampling performance was independent of ionic strength (0.0001-0.5M), pH (4.0-8.5), and dissolved organic matter (0-20mg/L). Field deployment in the river estuary and bathing beach showed that DGT-measured 4-MBC concentrations were consistent in comparison with grab sampling. Environmental risk assessment showed that 4-MBC may pose a medium risk to aquatic organisms based on computed risk quotient (RQ) values. Sewage discharge is the main source of 4-MBC risk, while the residue in recreation beaches contributes more significantly in summer. The established DGT sampling is suitable for seasonal monitoring, source identification, and risk assessment of 4-MBC in coastal waters.

Application of high-resolution techniques in the assessment of the mobility of Cr, Mo, and W at the sediment-water interface of Nansi Lake, China.

There are few studies on the simultaneous behavior of chromium (Cr), molybdenum (Mo), and tungsten (W) belonging to group VIB of the periodic table. Herein, based on high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) technology, the vertical distribution characteristics of DGT-labile and soluble Cr, Mo, and W in two lakes of Nansi Lake (Weishan Lake and Dushan Lake) were analyzed. In addition, the net diffusion fluxes and R-value (CDGT/Csol) were used to evaluate the mobility and release risk of metals at the sediment-water interface. The results showed that the DGT-labile concentrations of the three metal elements (Cr, Mo, and W) in Weishan Lake were higher than those in Dushan Lake, both in overlying water and sediment. This is mainly due to the dredging of the Dushan Lake area, which can permanently remove the polluted sediment in the lake. Meanwhile, the exogenous input is relatively high near the tourist area of Weishan Island. The net diffusion fluxes indicate that the W has a potential release risk of diffusion to the overlying water in Dushan Lake. The release of Cr, Mo, and W is thought to be related to the reductive dissolution of Fe/Mn (hydr)oxides based on Pearson correlation coefficients. The R-values of Cr and W indicate that Cr and W belong to the partial continuity case. The R-value of Mo was lower than the minimum value, meaning that Mo belongs to the single diffusion type and it is difficult for Mo sediments to supply pore water.

Assessment of 226Ra and U colloidal transport in a mining environment

The colloidal transport of trace (Fe, Al, Ba, Pb, Sr, U) and ultra-trace (226Ra) elements was studied in a mining environment. An original approach combining 0.45 μm filtered water sampling, the Diffusive Gradient in Thin films (DGT) technique, mineralogical characterization, and geochemical modelling was developed and tested at 17 sampling points. DGT was used for the truly dissolved fraction of the elements of interest, while the 0.45 μm filtration includes both colloidal and truly dissolved fractions (together referred to as total dissolved fraction). Results indicated a colloidal fraction for Al (up to 50%), Ba (up to 86%), and Fe (up to 99%) explained by the presence of submicrometric grains of kaolinite, barite, and ferrihydrite, respectively. Furthermore, the total dissolved 226Ra concentration in the water samples reached up to 10–25 Bq/L (1.2–3.0 10−12 mol/L) at 3 sampling points, while the truly dissolved aqueous 226Ra concentrations were in the mBq/L range. Such high total dissolved concentrations are explained by retention on colloidal barite, accounting for 95% of the total dissolved 226Ra concentration. The distribution of 226Ra between the truly dissolved and colloidal fractions was accurately reproduced using a (Rax,Ba1-x)SO4 solid solution, with values of the Guggenheim parameter a0 close to ideality. 226Ra sorption on ferrihydrite and kaolinite, other minerals well known for their retention properties, could not explain the measured colloidal fractions despite their predominance. This illustrates the key role of barite in such environments. The measured concentrations of total dissolved U were very low at all the sampling points (<4.5 10−10 mol/L) and the colloidal fraction of U accounted for less than 65%. U sorption on ferrihydrite could account for the colloidal fraction. This original approach can be applied to other trace and ultra-trace elements to complement when necessary classical environmental surveys usually performed by filtration on 0.45 μm.

Predicting the Kinetics of Resupply of Organic Pollutants from Sediments Using Diffusive Gradients in Thin Film Samplers and their Bioavailability to Aquatic Invertebrates.

The present study used diffusive gradients in thin film (DGT) samplers deployed in situ at a wastewater-impacted site (Clarkboro Ferry) for 20 days to develop a predictive model between time-weighted mean concentrations of seven selected antipsychotic compounds in water and those in resident benthic invertebrates, specifically crayfish (Faxonius virilis). The model was further combined with a model of desorption of antipsychotic compounds to predict kinetics at the sediment-water interface. Antipsychotic compounds were mostly detected in adult crayfish and internal concentrations were similar among targeted compounds, except for lesser concentrations of duloxetine. The model, based on the mass balance of organic chemicals, to predict uptake by organisms exhibited good agreement with measured values (R2 = 0.53-0.88), except for venlafaxine (R2 = 0.35). At the sediment-water interface, positive fluxes were observed for antipsychotic compounds and the results from DGT-induced fluxes in sediments (DIFS) coupled with equilibrium hydroxyl-β-cyclodextrin extraction further indicated partial resupply of antipsychotic compounds from sediments to the aqueous phase, despite the labile pool being relatively limited. The results of the present study affirm that DGT techniques can be used as a predictive tool for contamination in benthic invertebrates and can simulate the ability of contaminant resupply from sediments. Environ Toxicol Chem 2023;42:1696-1708. © 2023 SETAC.

Copper Contamination Affects the Biogeochemical Cycling of Nitrogen in Freshwater Sediment Mesocosms

Trace elements can have a wide variety of effects on microbial populations and their function in the aquatic environment. However, specific impacts on chemical and biological processes are often difficult to unravel, due to the wide variety of chemical species involved and interactions between different elemental cycles. A replicated mesocosm experiment was used to test the effect of increasing copper concentrations, i.e., from 6 mg kg−1 to 30 and 120 mg kg−1, on nitrogen cycling in a freshwater sediment under laboratory conditions. Nitrous oxide emissions from the treated sediments were measured over three consecutive 24 h periods. This was followed by measurements of iron, manganese, copper and mineral nitrogen species (nitrate and ammonium) mobilisation in the sediments using the diffusive gradients in thin films (DGT) and diffusive equilibria in thin films (DET) techniques and sequential extractions. Increasing copper concentrations are shown to have resulted in significantly reduced nitrate formation near the sediment–water interface and increased nitrous oxide emissions from the sediment overall. The concomitant mobilisation and sequestration of iron with ammonium in the sediment with the highest Cu treatment strongly imply links between the biogeochemical cycles of the two elements. Modest Cu contamination was shown to affect the nitrogen cycle in the tested freshwater sediment, which suggests that even relatively small loads of the metal in fresh watercourses can exert an influence on nutrient loads and greenhouse gas emissions from these environments.

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

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

Hydrogeochemistry of groundwater surrounding a pyrite mine in southern China: Assessment of the diffusive gradients in thin films technique for in situ monitoring

Acid mine drainage (AMD) resulting from pyrite mining causes hydrogeochemical evolution of groundwater and, in particular, the consequent release of potentially toxic elements (PTEs), posing health risks to populations dependent on groundwater. In this study, hydrogeochemical characteristics and evolutionary mechanisms were systematically illustrated via multivariate statistical methods and hydrogeochemical methods based on groundwater samples (n = 40) collected in a pyrite mining area in southern China. The diffusive gradients in thin films (DGT) technique was applied to evaluate the accuracy of metal content detection in groundwater at low concentrations. Based on principal component analysis (PCA), the groundwater dataset was classified into four types: brackish water dominated by sulfate, brackish water dominated by Ca-HCO3, low-mineralized water with the presence of PTEs, and freshwater in its natural state. The main controlling factors of hydrogeochemistry are evaporative crystallization and water–rock interactions. Fe, Mn, Pb, and Cd were detected in groundwater in the study area at levels exceeding World Health Organization (WHO) parameter values, and the highly toxic trace metal Tl was detected at levels up to 20 μg/L. The assessment of the applicability of the DGT technique to groundwater systems showed that reliable DGT detection results could be obtained under neutral or alkaline conditions at low Mn and Cd levels. This study highlights the evolution of the groundwater hydrogeochemistry under the combined influences of human activities such as mining and remediation management. In particular, the release of PTEs can affect human health, while the adoption of in situ DGT technology can provide strong support for studying these issues.

Back Accumulation of Diffusive Gradients in Thin-Films Devices with a Stack of Resin Discs To Assess Availability of Metal Cations to Biota in Natural Waters.

Determining species, concentrations, and physicochemical parameters in natural waters is key to improve our understanding of the functioning of these ecosystems. Diffusive Gradients in Thin-films (DGT) devices with different thicknesses of the resin or of the diffusive disc can be used to collect independent information on relevant parameters. In particular, DGT devices with a stack of two resin discs offer a simple way to determine dissociation rate constants of metal complexes from the accumulation of the target metal in the back resin disc. In this work, simple approximate expressions for the determination of the dissociation rate constant are reported and applied to a model Ni nitrilotriacetic complex as well as to Zn complexes in the Mediterranean Osor stream. Once the physicochemical parameters are known, one can plot the labile fraction of the metal complexes in terms of the thickness of the diffusion domain. These plots reveal a strong dependence on the nature of complexes as well as on the characteristics of the diffusion domain, and they are of high interest as predictors of availability to biota whose uptake is limited by diffusion.

Resupply, diffusion, and bioavailability of Hg in paddy soil-water environment with flood-drain-reflood and straw amendment

Mercury (Hg) poses a significant risk in paddy fields, particularly when it is converted to methylmercury (MeHg) and accumulates in rice. However, the bioavailability and resupply kinetics of Hg in the paddy soil-water environment are not well understood. In this study, the diffusive gradients in thin films (DGT) and the ‘DGT-induced fluxes in sediments’ model (DIFS) were first adopted to investigate the Hg resupply kinetics, diffusion fluxes and bioavailability in a paddy environment subjected to flood-drain-reflood treatment and straw amendment. Our results show that although the straw amendment limited the bioavailability of Hg (38.2%–47.9% lower than control) in porewater by decreasing its resupply capacity, especially with smaller straw particles, the net production of MeHg in paddy fields was significantly increased after straw amendment (73.5%–77.9% higher than control). The results of microbial sequencing indicate that enhanced methylators (e.g., family Geobacter) and non-Hg methylators (e.g., Methanosarcinaceae) played a crucial role in MeHg production following straw amendment. Moreover, Hg-containing paddy soils generally tend to release Hg into the overlying water, while drain-reflood treatment changes the direction of Hg diffusion fluxes in the paddy soil-water interface. The drainage-reflooded treatment decreases the Hg reactive and resupply capacity of the paddy soil, thereby hindering the release of Hg from soil into overlying water during the early stages of reflooding. Overall, this study provides novel insights into the behavior of Hg in paddy soil-water surface microlayers.

Control of phosphorus release from sediment by hydrous zirconium oxide combined with calcite, bentonite and zeolite

This study investigated the effectiveness and mechanism for the control of internal phosphorus (P) liberation from sediment by hydrous zirconium oxide (HZrO2) combined with calcite, bentonite and zeolite. The results suggested that coexisting calcite, calcium-modified bentonite (CaBT) and calcium-modified zeolite (CaZ) all had the ability to promote the adsorption of phosphate (PO43−) onto HZrO2. The mechanisms of PO43− elimination by HZrO2/calcite mixture involved the adsorption of PO43− on calcite, the precipitation of PO43− with Ca2+, and the inner-sphere complexation of PO43− with HZrO2. The amendment of sediment with HZrO2/calcite, HZrO2/CaBT or HZrO2/CaZ mixture can effectively prevent the sedimentary P release, and the immobilization of mobile P in the sediment and the uptake of dissolved reactive P (DRP) from the interstitial water by the amendment material played a key role in the control of P release from sediment by the combined amendment. Capping sediment with HZrO2/calcite, HZrO2/CaBT or HZrO2/CaZ mixture also can effectively intercept sediment P release, and the formation of P static layer attributed to the uptake of interstitial water DRP and DGT (diffusive gradient in thin-films)-unstable P in the upper sediment by the capping material was a key to the inhibition of sedimentary P migration into the overlying water by the combined capping. The great majority of P immobilized by the HZrO2/calcite, HZrO2/CaBT or HZrO2/CaZ combined covering layer is stable P and it has a low re-releasing risk under dissolved oxygen-deficit and pH 5–9 condition. The stability of P bound by the combined covering layer was larger than that by the single HZrO2 covering layer. The results of this research show that the combined use of HZrO2 and calcite, HZrO2 and CaBT, or HZrO2 and CaZ as a capping material has great potential in the reduction of sediment P loading.

Oxidative compensation mechanism of Fe-S synergetic inhibition of Cd activity in paddy field during flooding and drainage

It is known that the transformation of Fe and S forms in soil affects the migration and activity of Cd, but the coordinated regulation of Cd activity by Fe and S under different redox conditions is still unclear. Here, Diffusive gradients in thin films (DGT), an in-situ monitoring technique, is used to explore the difference of the regulation of Cd activity in paddy fields with ferrihydrite (FH) and ferrihydrite coprecipitated by sulfate (FH-S) under the flooding and drainage conditions. The addition of FH-S and FH significantly reduced the activity of Cd (Dissolved, Exchanged, and CDGT-Cd). Compared with pure FH, the adsorption extent of Cd in FH was enhanced by increasing concentrations of SO42− (i.e., S/Fe ratio), which is attributed to the decrease in the crystallinity of FH by sulfate. During soil flooding, the addition of FH-S promoted the production of metal sulfide (CdS and FeS/FeS2). The activity of Cd increased after drainage, while the FH-S treatment groups delayed the release of Cd. After 30 days of drainage, the concentration of Cd in FH-S treatment groups decreased by 28.9–44.1 % compared with the control group. The fresh FeS/FeS2 is not the main adsorbent for fixing Cd, and due to the existence of oxidation compensation mechanism, the preferential oxidation of FeS/FeS2 delays the release of Cd in the drainage stage. Our study shed new light on the mechanism of Fe-S synergistic regulation of Cd and remediation of Cd-contaminated soils.

Inhibition of sediment erosion and phosphorus release by remediation strategy of contaminated sediment backfilling

The management of sediment-water interfaces, especially bed stability, is essential for controlling accumulated contaminants in the sediment. In this study, the relationship between sediment erosion and phosphorus (P) release under the remediation strategy of contaminated sediment backfilling (CSBT) was explored through a flume experiment, i.e. the dredged sediment was calcined into ceramsite after dewatering and detoxification and then backfilled to the dredged area for sediment capping, thus avoiding the introduction of foreign materials via in-situ remediation and the large-scale land occupation associated with ex-situ remediation. Acoustic Doppler velocimeter (ADV) and optical backscatter sensor (OBS) were used to measure the vertical distributions of flow velocity and sediment concentration in the overlying water, respectively, and diffusive gradients in thin films (DGT) was used to measure the P distribution in the sediment. The results revealed that improving bed stability from CSBT can considerably improve the robustness of sediment-water interface and reduce sediment erosion by more than 70%. The corresponding P release from the contaminated sediment could be inhibited with an inhibition efficiency as high as 80%. CSBT is a potent strategy for managing contaminated sediment. This study provides a theoretical reference for controlling sediment pollution, further supporting river and lake ecological management and environmental restoration.

Ecotoxicological risk of antibiotics and their mixtures to aquatic biota with the DGT technique in sediments

Antibiotics are emerging contaminants and widely used in human healthcare, livestock, and aquaculture. The toxicity posed by antibiotics and their mixtures in sediments depends on their bioavailability. Now, the bioavailability of organic materials can be determined accurately by the diffusive gradients in thin films (DGT) technique. This technique was used for the first time ever in this study to evaluate in detail the integral toxicity of antibiotics in sediments to aquatic biota. Zhelin Bay was selected as a case study, because it is the largest mariculture area in eastern Guangdong, South China. Two antibiotics, chlortetracycline (CTC) (A) and sulfachlorpyridazine (SCP), were detected at average concentrations of 2.83 and 1.14 ng/ml, respectively. The other fifteen antibiotics were undetectable. The single risk assessment based on the risk quotient (RQ) of CTC and SCP shows that a relatively low risk has occurred. After this careful assessment of probabilistic ecotoxicological risks, the combined toxicity of antibiotic mixtures (CTC and SCP) clearly indicates that the toxicity probability of surface sediments to aquatic organisms was relatively low (0.23%).

A new approach to using Diffusive Gradient in Thin-films (DGT) labile concentration for Water Framework Directive chemical status assessment: adaptation of Environmental Quality Standard to DGT for cadmium, nickel and lead

Integrative passive samplers, such as DGT (Diffusive Gradients in Thin-films), are identified in European Technical Guidance Documents as promising tools to improve the quality of the assessment, in the context of the WFD (EU Water Framework Directive). However, DGT results cannot yet be used directly in a regulatory framework to assess the chemical status of water bodies, as DGT labile concentrations cannot be directly compared to the metal AA-EQSmarine water (Annual Average Environmental Quality Standard) established by the WFD, which are defined in the dissolved concentration. Therefore, prior to using DGT results in a regulatory context, for cadmium, nickel and lead, an adaptation of existing AA-EQSmarine water for DGTs should be pursued, ensuring at least the same level of protection. In this sense, in the framework of the MONITOOL project, a robust database of dissolved and labile metal concentrations in transitional and coastal waters, for adapting the existing AA-EQSmarine water for DGT technique, was obtained. Building on these results, this study proposes a methodology and provides values and equations for using DGT results for the chemical status assessment of marine waters, by adapting the EQSmarine water to adapted EQSDGT or predicting dissolved concentrations from DGT results. Based on available dataset, a first simulation of “chemical status” assessment per MONITOOL sampling site using DGT measured labile concentrations was carried out and the results were compared to an assessment based on dissolved concentration to check their compliance. These results demonstrate that the use of DGT passive samplers is appropriate for the metal concentrations level encountered in the marine environment. Further work is recommended to test the effectiveness of the methodology proposed in this study under WFD conditions on more sites and to establish common strategy guidelines for the use of DGT passive samplers in monitoring.

Adaptation of the o-DGT for the sampling of 12 hormones: calibration, performance evaluation, and recommendation.

This work highlights the methodology for the development of diffusive gradients in thin films (o-DGT) through its adaptation for 12 natural and synthetic hormones belonging to three different families (estrogens, progestins, and androgens). A reliable strategy must be applied during o-DGT lab adaptation to avoid issues related to the analysis (i.e., presence of matrix effects in grab or passive samples) but also to the o-DGT configuration (i.e., undesirable sorption or desorption, lack of performance with insufficient elution or unreliable diffusion coefficient). To avoid analytical issues due to the presence of salts in grab samples, CaCl2 exposure solutions must be used on a lab-scale development to monitor the hormone concentration. The selected o-DGT was composed of an Oasis®HLB binding gel and a diffusive gel in agarose because they provided better performance than polyacrylamide gels (i.e., higher elution factors and more repeatable diffusion coefficients). The elution factors of the binding gel were then from 0.79 ± 0.13 to 1.04 ± 0.13 (RSD < 15%) and the diffusion coefficients at 25°C were from 4.07 ± 0.24 to 5.49 ± 0.28 × 10-6cm2s-1 (RSD < 9%). A laboratory exposure to a synthetic solution was performed to check the consistency with the DGT quantification model validating the calibration parameters for all hormones (except 17α-ethinylestradiol with a bias of 40%). Therefore, the o-DGT configuration is suitable for sampling hormones in the natural environment with LOQDGT ranging from 0.3 to 6.6ngL-1.

Use of carminic acid immobilized in agarose gel as a binding phase for DGT: A new approach for determinations of rare earth elements

Recently, rare-earth elements (REEs) have attracted great interest due to their importance in several fields, such as the high-technology and medicine industries. Due to the recent intensification of the use of REEs in the world and the resulting potential impact on the environment, new analytical approaches for their determination, fractionation and speciation are needed. Diffusive gradients in thin films are a passive technique already used for sampling labile REEs, providing in situ analyte concentration, fractionation and, consequently, remarkable information on REE geochemistry. However, data based on DGT measurements until now have been based exclusively on the use of a single binding phase (Chelex-100, immobilized in APA gel). The present work proposes a new method for the determination of rare earth elements using an inductively coupled plasma‒mass spectrometry technique and a diffusive gradients in thin films (DGT) technique for application in aquatic environments. New binding gels were tested for DGT using carminic acid as the binding agent. It was concluded that acid dispersion directly in agarose gel presented the best performance, offering a simpler, faster, and greener method for measuring labile REEs compared to the existing DGT binding phase. Deployment curves obtained by immersion tests in the laboratory show that 13 REEs had linearity in their retention by the developed binding agent (retention x time), confirming the main premise of the DGT technique obeying the first Fick's diffusion law. For the first time, the diffusion coefficients were obtained in agarose gels (diffusion medium) and carminic acid immobilized in agarose as the binding phase for La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb and Lu, which were 3.94 × 10−6, 3.87 × 10−6, 3.90 × 10−6, 3.79 × 10−6, 3.71 × 10−6, 4.13 × 10−6, 3.75 × 10−6, 3.94 × 10−6, 3.45 × 10−6, 3.97 × 10−6, 3.25 × 10−6, 4.06 × 10−6, and 3.50 × 10−6 cm2 s−1, respectively. Furthermore, the proposed DGT devices were tested in solutions with different pH values (3.5, 5.0, 6.5 and 8) and ionic strengths (I = 0.005 mol L−1, 0.01 mol L−1, 0.05 mol L−1 and 0.1 mol L−1 – NaNO3). The results of these studies showed an average variation in the analyte retention for all elements at a maximum of approximately 20% in the pH tests. This variation is considerably lower than those previously reported when using Chelex resin as a binding agent, particularly for lower pH values. For the ionic strength, the maximum average variation was approximately 20% for all elements (except for I = 0.005 mol L−1). These results indicate the possibility of a wide range of the proposed approach to be used for in situ deployment without the use of correction based on apparent diffusion coefficients (as required for using the conventional approach). In laboratory deployments using acid mine drainage water samples (treated and untreated), it was shown that the proposed approach presents excellent accuracy compared with data obtained from Chelex resin as a binding agent.

Chemical imaging reveals environmental risk of minor tungsten and lead shotgun pellet constituents during weathering in soil

Tungsten (W)-based shots are considered more environmentally safe than lead (Pb)-based shots, but knowledge about the W-shot fate in the soil environment is still limited, especially in terms of minor constituents such as iron, copper, and nickel (Ni). Contaminant behaviour in soil strongly depends on pH; in turn, the corrosion of metal composites may affect the pH locally. The aim of this study was to compare Pb- and W-shot weathering dynamics in soil (silt loam, pH 6.3) and reveal the interplay of shot weathering-induced pH-changes on the mobility of elements using in situ chemical imaging (Diffusive gradients in thin films for labile elements, planar optodes for soil pH) and batch incubation experiments over time (16 months). Despite our expectation to find acidification due to W oxidation, we observed a pH increase by 0.2 units in extracted soil solutions and by 0.6 units in the soil around W-shots as Ni dissolved from the binder phase of the shot. After 10 weeks, release of labile Ni was 3-times higher compared to W despite the low Ni content in the shot (7 %, m/m). Pb-shot oxidation increased soil solution pH by 0.5 units which likely supported mobility of Pb-shot-derived antimony (Sb). Steep gradients of labile W and Pb and soil solution concentrations <0.8 μmol L−1 indicated that transfer from shot to soil was low. Contrastingly, labile Ni and Sb were found up to ~4 mm from the shot surface and in higher soil solution concentrations as suggested by the shot constitution, indicating higher mobility of minor as compared to major shot constituents. After 16 months, 36 % of total Ni were dissolved in the soil solution highlighting the environmental relevance of minor shot constituents in Pb-shot alternatives after short term weathering in soil.

Insights into the release of triclosan from microplastics in aquatic environment assessed with diffusive gradient in thin-films

Organic chemicals associated with microplastics (MPs) can be released and thus pose potential risks during weathering processes. However, the thermodynamics and kinetics of their release processes still need to be better understood. Herein, the adsorption and desorption kinetics of triclosan on polystyrene (PS) and polyvinyl chloride (PVC) were investigated by using both batch experiments and diffusive gradients in thin-films (DGT) technique. The pseudo-second-order model fitted the data best, implying that both intraparticle diffusion and external liquid film diffusion influence the adsorption and desorption processes. DGT continuously accumulated triclosan from MP suspensions but slower than theoretical values, indicating some restrictions to desorption. The DGT-induced fluxes in Soils/Sediment (DIFS) model, employed to interpret DGT data, gave distribution coefficients for labile species (Kdl) of 5000 mL g−1 (PS) and 1000 mL g−1 (PVC) and the corresponding response times (Tc) were 10 s and 1000 s, respectively. Higher Kdl but smaller Tc for PS than PVC showed that more triclosan adsorbed on PS could be rapidly released, while there were some kinetic limitations for triclosan on PVC. A novel finding was that pH and ionic strength individually and interactively affected the supply of triclosan to DGT. This is the first study to quantify interactions of organics with MPs by using DGT, aiding our understanding of MPs' adsorption/desorption behavior in the aquatic environment.

Characterization of iron, sulfur, and phosphorus diagenesis in muddy sediments of the South Yellow Sea using the diffusive gradients in thin films (DGT) technique

Characterization of iron, sulfur, and phosphorus diagenesis in muddy sediments of the South Yellow Sea using the diffusive gradients in thin films (DGT) technique

Investigation on metal geochemical cycling in an anthropogenically impacted tidal river in Belgium

The geochemical behavior of metals in water and sediment was investigated in the tidal section of the Zenne River in Belgium. Twelve-hour sampling campaigns were performed in October 2013 and March 2021 at the mouth of the Zenne River, under dry and rainy weather conditions respectively. Water samples were collected every hour while the passive samplers of Diffusive Gradients in Thin-films (DGT) were deployed continuously during a tidal cycle. In addition, bottom sediments were sampled at the tidal station and water samples were taken upstream and downstream of that station to identify the metal sources. The highest concentrations of Fe, Mn, Pb, Cr, Ni and Zn appear at low tide, indicating the Zenner River as a main source. However, for Co, Cd and Cu, other sources including upstream transport may explain their behavior during a tidal cycle. Fe, Pb and Cr are essentially transported in the particulate phase (<10 % dissolved) while the other metals in the dissolved phase (20 to 90 %). Rainfall and wind gust events also play an important role in trace metal distribution, increasing sediment resuspension and metal desorption. A good agreement was found between the time-averaged dissolved and DGT-labile metal concentrations with the exception of Cu and Fe, which form strong organic Cu complexes and Fe colloids respectively. The sediments of the tidal Zenne are contaminated by trace metals, thus acting as a secondary pollution source to the river. The reductive dissolution of Mn and Fe oxyhydroxides and the release of associated trace metals are the main mobilization mechanisms. Knowledge of the upstream and downstream levels in the water column, the benthic fluxes, which are based on turbulent diffusion, and the partitioning between dissolved and particulate phases allow to explain the metal concentration variations during the tidal cycle.