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Mercury (Hg) and methylmercury (MeHg) are easily released from sediments to overlying water and cause secondary contamination. In general, Hg concentrations are low in natural aquatic environments, but Hg toxicity is high. Therefore, it is important to assess the mobility and release risks of Hg and MeHg from surface sediment using in situ high-resolution sampling techniques. The profile distribution of Hg and MeHg was obtained for samples from Weishan sub-lake (WL) and Dushan sub-lake (DL) of Nansi Lake, China, by high-resolution dialysis (HR-Peeper probes) and the diffusive gradients in thin films (DGT) technique at mm-resolution. Furthermore, Hg mobility and release risks in sediments were evaluated by combining BCR (European Community Reference Bureau) extraction and DGT-measured data. The soluble concentrations of Hg in surface sediments in WL and DL were 21.70 and 19.38 ng L−1 and the DGT-labile concentration of Hg were 8.21 and 10.30 ng L−1, respectively. The soluble and labile Hg and MeHg concentrations were higher in the surface sediments (from −40 to 0 mm) than in deep sediments. The distribution of the labile-Hg was controlled by the ferrimanganic (hydr)oxide and total nitrogen rather than organic carbon content. The non-residual components accounted for a greater proportion of the interface, which further confirmed Hg was more active on the surface layer of the sediment. The resupply ability indicated that the release of Hg from sediment was insufficient to maintain the initial concentration in the porewater before consumption. The MeHg fluxes in WL (6.18 ng m−2 day−1) were twice those in DL (2.89 ng m−2 day−1), and the risk assessment code revealed a higher risk in the surface layer (25.21–61.88%) than in the deep layer (0–27.75%). Dissolved Hg and MeHg accumulated on the surface of the sediments and were more active than in the deeper sediments. The DGT-labile state can be used for a better understanding of the bioavailability and mobility of Hg. The diffusion direction of Hg and MeHg was from sediment to the overlying water. The release risks of Hg and MeHg from surface sediments (especially in WL) were found to be worthy of concern.

The diffusive gradients in thin films (DGT) technique has been successfully and widely applied to investigate the labile fractions of inorganic contaminants in soils and sediments, but there have been almost no applications to organic contaminants. Here we developed and tested the approach for the pesticide Atrazine (ATR) in a controlled soil experiment and in situ in an intact lake sediment core. The soil study explored the relationships between soil solution, DGT measured labile ATR and solvent extractable ATR in dosed soils of different organic matter, pH status and incubation times. The results are further interpreted using the DIFS (DGT-induced fluxes in soils and sediments) model. Resupply of ATR to the soil solution was partially sustained by the solid phase in all the soils. This was due to small labile pool size and slow kinetics, with soil pH being an important controlling factor. The in situ sediment study successfully used a DGT probe to examine labile ATR distribution through the core on the subcm scale. It demonstrated-for the first time-an easy to use in situ technique to investigate the effects of redox on resupply kinetics and biogeochemical processes of trace organic contaminants in sediments.

This study applied the techniques of high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) to explore the effects and the behind mechanism for inhibition phosphorus (P) releasing from sediments by nFe3O4 capping. The highest decreasing rates of SRP and labile P (i.e., 49% and 47%, respectively) and the decreased flux of SRP showed that nFe3O4 capping can successfully control sediment internal P release. Adsorption by Fe(III) hydroxides with the oxidation of Fe(II) was one of the reasons for the decrease of P concentrations in nFe3O4 capping sediments. This was supported by the increase of Eh and significant negative correlation between Eh with Fe(II) (soluble and labile Fe(II)) and P (SRP and labile P) and significant positive correlation between Fe(II) and P in sediments by nFe3O4 capping. An outer-sphere complex between positively charged nFe3O4 surface groups and P formation was the other reason to decrease the concentrations of P in the nFe3O4 capping sediments. This was supported by the decrease of pH value in sediments by the capping of nFe3O4. This study shows that nFe3O4, when used as capping agent, can effectively control the sediment internal P release, which is expected to be used as a potential material for repairing lake eutrophication.

Desorption of phosphorus (P) bound to iron-containing minerals (Fe-P) is a crucial component of the eutrophication process in lakes. However, the main process and regulation mechanism of iron (Fe) and sulfur (S) on P release is little known because of a lack of in situ high-resolution data. High-resolution measurement evidence is needed to assess the availability and diffusion kinetic process of P at the water–sediment interface. Soluble reactive phosphate (SRP), ferrous ion (Fe2+), and sulfide (S2−) fluxes through the water–sediment interface in a freshwater lake were detected using the novel double-sided diffusive gradients in thin films (DGT) technique. Different P forms in solid sediment were also measured using the sequential extraction procedure. The diffusion fluxes across the water–sediment interface and dynamic diffusion parameters between solid sediment and solution were calculated using the DGT-induced fluxes in sediments and soils (DIFS) model. There was a clear decrease of the SRPDGT, Fe2+DGT, and S2−DGT fluxes from ~5 cm sediment depth to the water–sediment interface. The significant positive correlation between SRPDGT and Fe2+DGT fluxes in the whole profile demonstrates that Fe-P was a vitally important source of labile P in the solution phase. The significant positive fluxes of SRPDGT and Fe2+DGT indicated upward diffusion from the sediment particle toward the overlying water. This process further indicated the desorption and resupply of SRP and Fe2+ from the solid sediment phase and the synergistic effect between these two parameters. In addition, a gentler decline of R curves fitted with the DIFS model was found as the sediment depths increased, which suggesting the continuous resupply process from solid phase to pore water, especially under anaerobic conditions. The novel DGT technique in combination with DIFS analysis confirmed the considerable remobilization and transport capacity of labile P fractions including loosely adsorbed MgCl2-P and reductive Fe-P. These pools can diffuse from sediment particles to the interstitial and the overlying water, and can be further assimilated by organisms in shallow lacustrine ecosystem.

This study assessed the critical soil characteristics affecting mercury (Hg) bioavailability to the earthworm Eisenia fetida using the diffusive gradient in thin films (DGT) method. The soil samples were collected from a tributary of the Hyeongsan River contaminated with industrial waste and landfill leachates called Gumu Creek. The Hg concentration in the soil had a range of 0.33–170 μg g-1 (average 33 ± 56 μg g-1), and the Hg concentration of earthworms incubated in the soils was 0.83–11 μg g-1 (average 2.9 ± 3.2 μg g-1). When correlation analysis was used to detect the key variables among the soil properties related to Hg accumulation in the soils, earthworms, and resins, the water-holding capacity, which is covaried with the organic matter content, was determined to be a primary factor in increasing Hg accumulation in the soils, earthworms, and resins. However, the experimentally determined earthworm bioaccumulation factor and the DGT accumulation factor were negatively affected by the water-holding capacity. Therefore, the water-holding capacity played a dual role in the Gumu Creek deposits: increasing the soil Hg concentration and decreasing Hg bioavailability and leachability. Further, the DGT–Hg flux was positively correlated with the Hg concentration in earthworms (r = 0.93). Although the earthworm accumulation of Hg is not processed by passive diffusion, this study proves that the DGT method is promising for predicting soil Hg bioavailability to the earthworm E. fetida, and the water-holding capacity simultaneously regulates Hg availability to the DGT and the earthworms.

Soil plays an important role in controlling the biogeochemical cycling of nutrients and contaminants in the environment. Reliable analytical techniques are critical to better understand their trans...

The geographical shift of nickel mining to small island countries of the Southeast Asia and Melanesia region has produced a need to assess the environmental risk associated with increased sediment nickel exposure to benthic estuarine/marine biota. Chemical measurements of nickel concentration and potential bioavailability, including the use of diffusive gradients in thin films (DGT), were compared to effects on 10-d reproduction of the epibenthic estuarine/marine amphipod Melita plumulosa in nickel-spiked sediments and field-contaminated sediments with different characteristics. The 10% effect concentrations (EC10s) for amphipod reproduction ranged from 280 to 690 mg/kg total recoverable nickel, from 110 to 380 mg/kg dilute acid-extractable nickel, and from 34 to 87 μg Ni/m2 /h DGT-labile nickel flux. Nickel bioavailability was lower in sediments with greater total organic carbon, clay content, and percentage of fine particles. Measurements of DGT-labile nickel flux at the sediment-water interface integrated exposure to nickel from porewater, overlying water, and ingested sediment exposure pathways and were found to have the strongest relationship with the biological response. At most, there was a 29% reduction in 10-d M. plumulosa reproduction relative to the control when exposed to nickel from field-contaminated sediments collected from nickel laterite mining regions of New Caledonia. The DGT technique can be used as a complementary tool to measure the bioavailability of nickel in estuarine/marine sediments, especially sediments that are in nickel laterite mining regions where there are no or few toxicity data available for determining biological effects on local species. Based on the combined data set of the 3 nickel-spiked sediments a DGT-labile nickel EC10 threshold of 50 (30-69) μg Ni/m2 /h was determined. Environ Toxicol Chem 2021;40:1266-1278. © 2020 SETAC.

Behavior of phosphorus (P) in flooded rice soil is controlled by iron (Fe) redox cycling in root-zone. In this study, we applied a novel approach—the diffusive gradients in thin films (DGT) technique—for investigating the in-situ distribution of labile phosphorus (P) and Fe in close proximity to Asian rice (Oryza sativa L.) roots at submillimeter to millimeter spatial resolutions during the seedling and booting stages. We conducted a seven-year field experiment under rice-wheat rotation with different P fertilizer treatments. The results showed a significant and strong positive relationship of the average DGT-labile P concentration with soil Olsen P (R2 = 0.77, P

Synthetic solutions of Rh and Pt at near neutral pH, as well as spiked natural waters are subjected to an ageing effect, which means that over time the speciation of the PGEs will be changed from their original composition due to aquation and hydrolysis, forming various hydroxy and aqua complexes. Due to slow ligand exchange reactions equilibrium speciation may not be rapidly attained. Ageing may affect the reactivity of the PGE solutions towards chelating resins used in the analysis of PGEs by Diffusive Gradients in Thin films (DGT). The aim of the study was therefore to investigate the performance of the chelating resins (Purolite S914 and S920 with thiourea and isothiourea functional groups, and IONQUEST® MPX-317 with a phosphine oxide thiourea functional group) for their applicability as a binding resin for DGT applications for Pt and Rh in natural waters using 17-day aged spiked solutions. Uptake kinetics experiments revealed that the direct uptake of Pt on the resins from aged solutions was fast and quantitative, whereas only 30% of Rh was directly bound on the resin. Likewise, much lower apparent diffusion coefficients were obtained for Rh in aged spiked river water (70% decrease) which can be explained by the formation of Rh(OH)3(s) which is not taken up by the resin gel. The addition of dissolved organic matter results in an increased solubilisation of Rh(OH)3(s) and an increased DGT labile fraction. The formation of Rh(OH)3(s) is less pronounced in seawater. For Pt, no species are formed which are not DGT labile. Thus, DGT accurately measures labile metal species in solution, discriminating labile from inert metal species.

Lanthanum-modified bentonite (LMB, Phoslock®) is a well-known capping agent for phosphorus immobilization in sediments. Herein, LMB was used to immobilize As in sediments. Batch capacity experiments for arsenate and arsenite adsorption were carried out to obtain adsorption isotherms and kinetics using the Langmuir and Freundlich model calculations. High-resolution (HR) diffusive gradients in thin films (DGT) were applied to monitor the changes of weakly bound As fraction near sediment-water interface (SWI). The interaction of As(III) and As(V) with LMB was influenced by pH and initial mineral composition. As(V) was more obviously adsorbed than As(III) at pH 4 to 9, with mean adsorption of 3.89 mg g-1 and 0.04 mg g-1, respectively, while at pH > 9 As(III) was preferentially adsorbed. After LMB amendment for 2 months, the maximum As removal efficiency in the pore and overlying water reached 84.5% and 99.3%, respectively. The capping agent remained stable in the top sediments, while the maximum DGT labile As content decreased to 0.89 and 0.51 μg L-1 in dosage-and time-treatments. The As concentration inflection point moved down to a deeper layer. As species changed from labile exchangeable-As to Fe-oxide-bound and residual As. The proportion of mobile As finally decreased to 10.5% of the total As in the upper 20-mm layer sediment. The increase of Kd (the distribution coefficient at SWI) and k1 (adsorption rate constant) and the decrease of Tc (response time of (de)sorption) in the DGT-induced fluxes model (DIFS) indicated the time-dependent impediment of As release from the sediment due to LMB immobilization.

The in situ passive sampling technique, diffusive gradients in thin films (DGT), confronts many of the challenges associated with current sampling methods used for emerging contaminants (ECs) in aquatic systems. This study compared DGT and grab sampling for their suitability to screen and monitor ECs at the catchment scale in the River Thames system (U.K.) and explored their sources and environmental fate. The ubiquitous presence of endocrine disrupting chemicals, parabens, and their metabolites is of concern. This study is the first to report organophosphate esters (OPEs) in the study area. TEP (summer 13-160 and winter 18-46, ng/L) and TCPP (summer 242-4282 and winter 215-854, ng/L) were the main OPEs. For chemicals which were relatively stable in the rivers, DGT and grab sampling were in good agreement. For chemicals which showed high variation in water bodies, DGT provided a better integral of loadings and exposure than grab sampling. DGT was not as sensitive as grab sampling under the procedures employed here, but there are several options to improve it to give comparable/better performance. DGT samples require shorter preparation time for analysis in the laboratory than grab samples. Overall, DGT can be a powerful tool to characterize ECs throughout a large dynamic water system.

Selenium (Se) is an essential micronutrient for humans but is toxic when consumed in excess through the food chain, such as vegetables. Therefore, it is imperative to understand the relationship be...

Cadmium (Cd) uptake by plants or benthic organisms largely depends on its bioavailability in sediments, so it is necessary to understand Cd bioavailability for determining its ecological risks in riverine sediments. Pore water is easily disturbed during sample collection, indicating that there was a shortage of traditional methods for investigating Cd bioavailability. Here, sediment cores were collected from rivers, after which sequential extraction and diffusive gradients in thin films (DGT) method were employed to determine Cd potential bioavailability in the sediments and pore water. We found that Cd concentrations measured by DGT were lower than that in pore water profiles, and Cd distribution in various fractions changed remarkably. Pearson correlation analysis showed significant positive correlations between Cd concentrations measured by DGT and total Cd concentrations (r2 = 0.76), exchangeable and weak acid soluble fraction (r2 = 0.68), ferromanganese fraction (r2 = 0.72) and bound organic matter or oxidizable fraction (r2 = 0.54). However, the correlation was relatively low between Cd concentrations measured by DGT and that in pore water profiles (r2 = 0.26). These results demonstrated that DGT method could provide more accurate information of Cd bioavailability in sediment profiles than traditional methods.

Determination of the median effective concentration (EC50) of Cu on Mytilus galloprovincialis larvae by diffusive gradient in thin films (DGT) has been shown to effectively reduce the need to consider dissolved organic carbon (DOC) concentration and quality. A standard toxicity test protocol was used to validate previously modeled protective effects, afforded to highly sensitive marine larvae by ligand competition, in 5 diverse site waters. The results demonstrate significant narrowing of M. galloprovincialis toxicological endpoints, where EC50s ranged from 3.74 to 6.67 μg/L as CDGT Cu versus 8.76 to 26.8 μg/L as dissolved Cu (CuDISS ) over a DOC range of 0.74 to 3.11 mg/L; Strongylocentrotus purpuratus EC50s were 10.5 to 19.3 μg/L as CDGT Cu versus 22.7 to 67.1 μg/L as CuDISS over the same DOC range. The quality of DOC was characterized by fluorescence excitation and emission matrices. The results indicate that the heterogeneity of competing Cu binding ligands, in common marine waters, minimizes the need for class determinations toward explaining the degree of protection. Using conservative assumptions, an M. galloprovincialis CDGT Cu EC50 of 3.7 µg/L and corresponding criterion maximum concentration CDGT Cu of 1.8 µg/L, for universal application by regulatory compliance-monitoring programs, are proposed as a superior approach toward both integration of dynamic water quality over effective exposure periods and quantification of biologically relevant trace Cu speciation. Environ Toxicol Chem 2020;39:873-881. © 2020 SETAC.

Made available in DSpace on 2020-12-10T19:50:02Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-02-23 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Novel Diffusive Gradients in Thin Films (DGT) binding agents, Musa cavendishi banana peel (BP) and Moringa Oleifera seeds (MOS) immobilised in agarose gel, have been developed and validated for the determination of Cd, Cu, Pb and Zn in waters. The agarose-BP and agarose-MOS gel disks were characterised by Scanning Electron Microscopy, Energy Dispersive X-ray Spectrometry and Porosimetry by nitrogen adsorption. Elution of analytes from the binding agents was successfully performed with 2 mol L-1 HCl. The accumulation of Cd, Cu, Pb and Zn in DGT devices based on agarose-BP and agarose-MOS (DGT-BP and DGT-MOS) agreed well with the theoretical curves predicted by the DGT equation in synthetic solutions (500 mu g L-1 for each analyte). The uptake of DGT-BP and DGT-MOS for Cd, Cu, Pb and Zn was found to be independent of ionic strength of solutions up to 0.005 mol L-1 and for the entire studied pH range (from 3.5 to 8.0). Validation of DGT-BP and DGT-MOS methods was carried out by deploying the devices in spiked river water (the Corumbatai and the Piracicaba river). The recoveries obtained for the natural water matrices ranged between 40% and 150%. DGT-labile concentrations in situ for DGT-BP and DGT-MOS (performed in acid mine drainage) were also consistent with the values measured by conventional DGT-Chelex, albeit DGT-BP had a better binding capacity in acid drainage water. The predictions performed by chemical speciation modelling vMINTEQ were in general agreement for Pb using DGT-MOS (CDGT-MOS/C-dissolved 50% and Pb+2 (MINTEQ) species 41.9%) and for Cu using DGT-BP (CDGT-BP/C-dissolved 55% and Cu-MINTEQ(+2) species 62%). The proposed DGT-BP and DGT-MOS reaffirm the use of residual biomass as binding phase in the DGT technique, featuring low costs in production and 'green' technology approaches. Univ Estadual Paulista Unesp, Inst Geociencias & Ciencias Exatas, Rio Claro, Brazil Univ Estadual Paulista Unesp, Ctr Estudos Ambientais, Rio Claro, Brazil Univ Estadual Paulista Unesp, Inst Geociencias & Ciencias Exatas, Rio Claro, Brazil Univ Estadual Paulista Unesp, Ctr Estudos Ambientais, Rio Claro, Brazil FAPESP: FAPESP -2018/17069-7 FAPESP: FAPESP -2016/14227-5 CNPq: CNPq -304849/2016-2 CNPq: CNPq -403666/2016-3

Diffusive gradients in thin films (DGT) have gained wide attention for in situ measurement of reactive phosphorus species (PO4) in natural water, sediments and potentially soils. In this study, a novel Mg(OH)2 binding gel was formed using magnesium hydroxide obtained by in situ hydration of calcined magnesium oxide. Laboratory scale experiments showed that the novel Mg(OH)2 gel had a homogeneous dispersion of fine particles of Mg(OH)2 with a particle size of 2-5 μm. With 10 mL of 2.0 mol L-1 NaOH as the eluting agent, the optimal elution efficiency of PO4 on the Mg(OH)2 gel was 72 ± 5%. There were linear relationships between the accumulated PO4 mass and the applied PO4 concentration (0.1 to 20 mg P per L), time (0 to 24 h) and temperature (22 to 40 °C). The capacity of the Mg(OH)2 binding layer was determined to be 99.5 μg P per disc. Tests in synthetic seawater, Chaohu Lake and Yihai Pond confirmed that Mg(OH)2-DGT was able to accurately measure phosphorus up to 10 days. This was indicated by the good agreements between the concentrations measured by DGT (CDGT) technology and by an ex situ chemical method in solution (Csoln), with a CDGT/Csoln ratio between 0.91 and 1.09.

A major gap in understanding nanomaterials behaviour in the environment is a lack of reliable tools to measure their available concentrations. In this research we use diffusive gradients in thin films (DGT) for measuring concentrations of zinc oxide nanoparticles (ZNO NPs) in soils. Available nanoparticle concentrations were assessed by difference, using paired DGT devices with and without 1000 MWCO dialysis membranes to exclude NPs. We used ZnO because its toxic effects are accelerated through dissolution to Zn2+. Our test soils had different pH and organic matter (OM) contents, which both affect the dissolution rate of ZnO NPs. Woburn (pH ≈ 6.9, OM ≈ 1.8%) and Lufa (pH ≈ 5.9, OM ≈ 4.2%) soils were spiked to a single concentration of 500 mg of ZnO NPs per 1 kg of soil and the available concentrations of ZnO NPs and dissolved zinc were evaluated in 3, 7, 14, 21, 28, 60, 90, 120, 150 and 180 day intervals using DGT. The results showed that the dissolution of ZnO NPs, as well as the available concentrations of both dissolved and nanoparticulate Zn, was much higher in Lufa soil than in Woburn. This work demonstrates that DGT can be used as a simple yet reliable technique for determining concentrations of ZnO NPs in soils and probing its dissolution kinetics.

International audience; The performance of the newly developed DGT technique for the platinum group elements (PGEs) rhodium (Rh), platinum (Pt) and palladium (Pd) was evaluated in two tributaries of the Scheldt River, the Marque River close to the city of Lille (France), and the Zenne River which flows through the city of Brussels (Belgium). In the Marque River, an interlaboratory comparison was performed between the two laboratories where the DGT techniques dedicated to PGEs were developed (AMGC, VUB & LASIRE, U-Lille). PGEs were also analysed in an effluent of a Brussels hospital and monthly grab sampling was performed at the wastewater treatments plants (WWTPs) of Brussels. The concentrations of the 3 elements are higher in the Zenne River than in the Marque River and much higher Pt concentrations are found in the hospital effluent. Good agreement for Pt was observed between the three selected chelating resins and a relatively good agreement was observed between the two laboratories using the same chelating resin, whereas lower results were observed with the anion-exchange resin. Larger discrepancies between the two laboratories were observed for Pd and no comparison could be made for Rh due to the low natural concentrations. The results show that in small urban rivers with high impact of urbanization, WWTPs are an important source of Pt, resulting from the use of anticancer drugs in hospitals and households. The limited retention of PGEs in WWTPs results in increased concentrations in urban rivers downstream.For Pd and Rh, similar trends were found with other traffic related elements such as Cu, Zn and Pb, showing the highest concentrations in waters collecting runoff from a highway. The data show that these elements, together with Gd, can be useful to trace specific pollution sources and their dispersion.

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV). It can be concluded that, in general, the median ratios of DGT/ICP and DGT/ASV(CSV) were lower than 1, except for Ni (median ratio close to 1) and Zn (higher than 1). This indicates the importance of speciation and time-integrated concentrations measured using passive sampling techniques, which is in line with the WFD suggestions for improving the chemical assessment of waterbodies. It is the variability in metal content in waters rather than environmental conditions to which the variability of the ratios can be attributed. The ratios were not significantly affected by the temperature, salinity, pH, oxygen, DOC or SPM, giving a great confidence for all the techniques used. Within a regulatory context such as the EU Water Framework Directive this is a great advantage, since the simplicity of not needing to use corrections to minimize the effects of environmental variables could help in implementing DGTs within monitoring networks.

The effects of chironomid larval (Propsilocerus akamusi) bioturbation on sediment phosphorus (P) mobility were studied over the course of 34 days using the indoor larval cultivation method on in situ sediment cores. High-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) techniques were used to record fine-scale changes of soluble and DGT-labile P and iron (Fe) concentrations in the sediment. The larval-driven irrigation of the overlying water into their burrows significantly increased the oxygen penetration depth (OPD) and redox state (Eh) in sediments. In addition, the soluble and DGT-labile P and Fe decreased with the increase of OPD and Eh in larval-bioturbated sediments. The greatest decrease in the mean concentration of SRP, soluble Fe, and DGT-labile P in the Propsilocerus group was observed on Day 15 of the experiment, with a decrease by over half of the mean concentration of the control group. Furthermore, two-dimensional measurements of DGT-labile P concentration showed notable reductions of DGT-labile P around larval burrows. The DGT-induced fluxes in sediments (DIFS) model also exhibited a much longer response time (420 s) and a much higher rate of P adsorption (0.002 s−1) in the bioturbation sediments than those in the control sediments (116 s and 0.009 s−1, respectively). A significant correlation was shown for DGT-labile P and DGT-labile Fe. We conclude that Fe(II) oxidation and its enhanced adsorption were the major mechanisms responsible for the decrease of soluble and DGT-labile P in sediments.

In this study, we evaluated the application of the diffusive gradient in the thin films (DGT) technique to predict the bioavailability of methamphetamine (METH) and its metabolite, amphetamine (AMP...

A generally accepted method to predict selenium (Se) bioavailability of long-term contaminated soils has not yet been established, even if risk assessments in selenosis areas are crucial. In this study, a set of methods were tested to assess the bioavailability of Se to field maize. Fifty maize (Zea mays L.) samples and corresponding soils were collected from a selenosis area (Ziyang, China). The diffusive gradients in thin-films (DGT) technique and the traditional chemical extraction methods, including seven single-step extraction procedures and a five-step sequential extraction were used to predict the bioaccumulation of Se in plant. The result verified the presence of 50% of total Se in the form of residual Se fraction, followed by organic-bound and Fe-Mn oxide-bound Se fractions in soil. In addition, Se6+, Se4+, and Se2− were all detected in the solution extracted by H2O, KCl, phosphate-buffered solution (PBS), NaHCO3, ethylenediaminetetraacetic acid-2Na (EDTA-2Na) and ammonium bicarbonate–diethylenetriaminepentaacetic acid (AB-DTPA), but Se6+ was not extracted by NaOH. The Se extracted by single-step extraction methods was weakly correlated with the Se uptake by plants with relatively high Se concentration (>3 mg·kg−1). The abilities of the tested methods to predict Se bioavailability in naturally Se-enriched soils declined in the following order: DGT > soil solution > PBS > KCl > H2O > NaHCO3 > EDTA > DTPA > NaOH. The ratio of CDGT to soil solution Se (Csoln) totaled 0.13, indicating an extremely low Se supply from the soil solid phase to the soil solution. Se measured by DGT was mainly derived from the soluble and exchangeable Se fractions that can accurately reflect the plant-absorbed Se pool. Therefore, the DGT technique is highly applicable in the simultaneous prediction of Se bioavailability in naturally Se-enriched soils.

A good understanding of lead (Pb) mobilization in eutrophic lakes is a key to the accurate assessment of Pb pollution. In this work, dissolved and labile Pb was determined by both high resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) in sediment-water profiles of the hyper-eutrophic Meiliang Bay of Lake Taihu on a monthly basis during one year. The drinking water standards for dissolved Pb of the World Health Organization (10μg/L) and those of China were exceeded in the overlying water (20.79-118.5μg/L). Out of which, a total of five months even exceeded the fisheries water quality limitation (50μg/L) in China. The algal blooms created an anaerobic environment in the surface sediments in July. The reductive conditions led to the dissolution of Fe/Mn and this caused the release of Pb, followed by organic matter complexation. This was supported by the coincident changes of dissolved Pb with dissolved organic matter (DOM) in sediments under anaerobic incubation. Algae residue decomposition in October caused another distinct release of Pb, but this process should be considerably suppressed by increased sulfide precipitation and pyrite adsorption of Pb ion. These results indicated that Pb mobilization in sediments can be significantly enhanced by algal blooms in eutrophic lakes, indicating that further attention should be paid to Pb pollution in waters with harmful algal blooms.

Robust environmental assessments and contaminant monitoring in Antarctic near-shore marine environments need new techniques to overcome challenges presented by a highly dynamic environment. This study outlines an approach for contaminant monitoring and risk assessment in Antarctic marine conditions using diffusive gradients in thin-films (DGT) coupled to regionally specific ecotoxicology data and environmental quality standards. This is demonstrated in a field study where DGT samplers were deployed in the near-shore marine environment of East Antarctica around the operational Casey station and the abandoned Wilkes station to measure the time-averaged biologically available fraction of metal contaminants. The incorporation of DGT-labile concentrations to reference toxicity mixture models for three Antarctic organisms predicted low toxic effects (5% effect to the growth or development of each organism). The comparison of metal concentrations to the Australian and New Zealand default water quality guideline values (WQGVs) showed no marine site exceeding the WQGVs for 95% species protection. However, all sites exceeded the 99% WQGVs due to copper concentrations that are likely of geogenic origin (i.e., not from anthropogenic sources). This study provides evidence supporting the use of the DGT technique to monitor contaminants and assess their environmental risk in the near-shore marine environment of Antarctica.

In-situ sampling of 2-chlorophenol (CP), 2,4-dichlorophenol (DCP), and 2,4,6-trichlorophenol (TCP) in industrial wastewater was carried out by the diffusive gradients in thin films (DGT) device based on mesoporous carbon (MC). The diffusion coefficients of CP ((1.33 ± 0.05) × 10−6 cm2 s−1), DCP((1.35 ± 0.04) × 10−6 cm2 s−1) and TCP((1.09 ± 0.07) × 10−6 cm2 s−1)) in nylon membrane at 25 °C were independent of pH 3–9 and ionic strength as pNaCl from 0.155 to 3, and were less than their values in water, demonstrating that the nylon membrane with good tolerance and constant diffusion coefficients was suitable as the DGT diffusion layer for controlling the diffusion of CPs. MC-DGT accurately measured the concentrations of CP, DCP and TCP in synthetic solution (CDGT/CSOLN = 0.956–1.04) over the deployment of 120 h. The experimental data also agreed well with the theoretical data calculated on the DGT equation. The performance of MC-DGT for sampling CPs was independent of pH (3–8) and ionic strength as pNaCl (1.3–3) due to the change of the interaction between MC and CPs under relatively high pH and ionic strength. Deployments in laboratory and field trials demonstrated that the MC-DGT was a reliable simple, robust and accurate tool for the in-situ sampling of CP, DCP and TCP in the industrial wastewater.

Accurate measurement of tetrabromobisphenol A (TBBPA) is very important because of its widespread environmental pollution. Diffusive gradients in thin films technique (DGT), an in-situ passive sampling method, is regarded as a reliable and robust measurement technique. A new DGT technique based on mesoporous imprinted polymer was combined with high-pressure liquid chromatography (HPLC) method for sampling, preconcentration and monitoring low concentration TBBPA in natural waters. The diffusion coefficient of TBBPA through the diffusive gel was measured by diffusion cell test and simulated using mathematical expression. The effects of different ambient conditions were tested under laboratory conditions and the performance of DGT sampler was validated in natural waters. The diffusion coefficient of TBBPA in the diffusive gel was measured as 2.18 × 10−6 cm2 s−1 and simulated as in the range 1.41–3.48 × 10−6 cm2 s−1 by Amsden model. Comparison of experimental and theoretical data, the validity of the experimental method can be verified by the mathematical model. The binding agent with mesoporous imprinted polymer showed selective affinity to TBBPA and its adsorption rate met the requirement of DGT device. The DGT method detection limit was at the level of ng L−1 for 7 days deployment. DGT sampler was suitable for application in aquatic environment with a range of pH (4.5–7.6), ionic strength (1 × 10−4 - 0.5 mol L−1), and dissolved organic matter (DOM) concentration (0–10 mg C L−1). The coupling method of DGT and HPLC was a promising technique for in situ sampling, preconcentration and monitoring low concentration TBBPA in most typical natural waters.

Solid-phase speciation and porewater chemistry measured by the diffusive gradients in thin films (DGT) technique were used to understand the diagenesis of sulfur (S), iron (Fe), and phosphorus (P) in sediments of Jiaozhou Bay (China), which has been impacted by multiple anthropogenic perturbations. Despite water eutrophication, sediments of the bay are low in organic carbon and sulfide, but high in unsulfidized Fe(II). Dissimilatory iron reduction (DIR) prevails in sediments of the bay, and there is no evidence for responses of S and Fe diagenesis to the water eutrophication, which is largely attributable to unique depositional and diagenetic regimes in association with multiple anthropogenic perturbations. Good coupling of porewater Fe2+ and P in the porewaters suggests that P mobilization is driven mainly by DIR. Low Fe2+/P ratios in porewaters imply that oxidative regeneration of Fe oxides within the upper sediments is incapable of efficiently scavenging upward diffusing P.

Biochar has emerged as a useful tool to reduce the bioavailability of heavy metals in contaminated soils. However, limited research has been directed towards determining the effects of pyrolysis conditions and feedstock types of biochar on the bioavailability of heavy metals in biochar-treated soils. This work evaluated the efficacy of plant- and manure-derived hydrochar and pyrochar for alleviating Cd bioavailability in soils using conventional chemical extraction, diffusive gradients in thin films (DGT) and plant uptake. For each feedstock type, hydrochar showed lower maximum adsorption capacity than pyrochar. As determined by diethylenetriamine pentaacetic acid, BCR extraction and DGT measurement, pyrochar significantly decreased the theoretical bioavailability of Cd. Moreover, a slight decrease in the ability of soil to resupply Cd to the solution was detected. Also, pyrochar induced a substantial reduction in Cd uptake in ryegrass. Corresponding to the high sorption capacity, swine solid-derived 450 °C pyrochar was the most effective in alleviating Cd bioavailability in soils, indicating its great potential for remediating Cd-contaminated soils. Additionally, the bioavailable Cd amount determined by DGT had the best correlation with the Cd content in ryegrass, showing that DGT technology could better represent the effects of biochars on Cd phytoavailability in the studied soil.

Understanding bioavailable metal behaviour in situ is critical for pollution evaluation and contaminant management in mangrove wetland. Here, the diffusive gradients in thin films technique (DGT) was used for characterizing the (bio)available portions of Cr, Zn, Pb, Cu, Fe and Mn in two mangrove wetlands affected by industrial waste discharges (Jiulong Estuary) and domestic discharges (Zhangjiang Estuary), in Fujian Province, China. In addition, fluorescence excitation emission matrices-parallel factor analysis (EEM-PARAFAC) was applied for characterizing the occurrence and behaviour of dissolved organic matter (DOM) in soil solution, as well as their feasibility for assessing behaviours of metals. The results demonstrated that the combination of DGT and EEM, which are well suitable for studying DOM impacted metal behaviors in mangrove sediments. Discharge of difference wastewater into the mangrove wetlands of Jiulong and Zhangjiang Estuaries, gave rise to the DGT-labile metal concentration of Zn > Cu > Cr > Pb and Zn > Cr > Pb > Cu, respectively. A variety of humic-like fluorescent components was characterized here, providing valuable insights into the chemical composition of DOM in rhizosphere and bulk sediment. Terrestrial humic-like compounds indicated a different binding affinity for heavy metals in mangrove sediments. These findings are useful for the future understanding of the metal speciation and molecular binding mechanisms in such mangrove wetlands.

As one of the largest man-made reservoir, the Three Gorges Reservoir (TGR) brings great uncertainty and challenges regarding trace metal (e.g., Cu) remobilization in the sediment. Therefore, in this study, sediment cores were collected from the mainstream of the Yangtze River and its three tributaries in the TGR, with a focus on evaluating the Cu remobilization risk and release dynamics using conventional methods, diffusive gradients in thin films (DGT), and the DGT-induced fluxes in sediments (DIFS) model. The results showed that although total Cu concentrations were slightly higher than background values, Cu was mainly observed in the unreactive residual fraction. Additionally, assessment of sediment quality guidelines and the risk assessment code indicated low Cu contamination risk for all sampling sites. However, the results of DGT measurements at the sediment-water interface showed efflux of Cu from sediment to the overlying water at most sites, except for the upstream of the Meixi River and the mainstream of the Yangtze River. Interestingly, diffusion fluxes at the three tributaries displayed an increase trend from the upper to lower reaches. The DIFS model simulation further implied that the highest resupply capacity and desorption rate occurred in the Zhuyi River and the upstream of the Meixi River. In fact, the accumulation of Cu from the upper to the lower reaches of the Zhuyi River significantly elevated the Cu resupply capacity. Thus, more attention should be paid to Cu mobilization in the TGR, especially in the Zhuyi River and the upstream of the Meixi River.

Nitrochlorobenzene compounds (NCBs) are of key interest in environmental monitoring due to their high toxicity. To better understand the presence and fate of NCBs in aquatic environments, an in-situ sampling technique of diffusive gradients in thin films (DGT) based on hydrophilic-lipophilic-balanced (HLB) resin, combined with gas chromatography, was developed to measure four typical NCBs, e.g. meta-chloronitrobenzene (MNCB), para-chloronitrobenzene (PNCB), ortho-chloronitrobenzene (ONCB), and 2,4-dinitrochlorobenzene (CDNB). The diffusion coefficients of MNCB, PNCB, ONCB, and CDNB in agarose-based gel were firstly determined in diffusion cell experiments and ranged from 7.19 × 10−6 to 7.49 × 10−6 cm/s. The capacities of HLB-DGT for MNCB, PNCB, ONCB, and CDNB were higher than 114.65, 117.52, 117.72, and 37.58 μg/cm2, respectively. The HLB-DGT performance on NCBs determination was demonstrated to be independent of natural fluctuations in pH (3–9), ionic strength (0.001–0.5 M), and dissolved organic matter concentrations (0–20 mg/L) and of deployment time (0–120 h). In the field application, the DGT-based method to measure NCBs not only proved to be accurate and effective, but also performed better than the grab sampling method under the variable conditions. This study demonstrates that the newly developed in-situ method based on DGT can provide an attractive alternative for the routine monitoring of NCBs in aquatic environments.

Water, sediment, and biota from two streams on the Savannah River Site were sampled to study mercury (Hg) biogeochemistry. Total and methyl- Hg (MHg) concentrations were measured for all samples, speciation models were used to explore Hg speciation in the water, and Diffusive gradients in thin films (DGT) were applied to indicate the vertical profiles of labile Hg (DGT-Hg). Trophic position (δ15N) was estimated for biota and used to establish MHg biomagnification model. The speciation model indicated Hg methylation in the water occurred on settling particles and the most bioavailable Hg species to bacteria were complexes of inorganic Hg and labile organic ligands. Correspondingly, dissolved organic carbon concentrations were positively related to MHg concentrations in the water. In the sediment, the sharp increase of DGT-Hg around the sediment water interface underscores the importance of this interface, which determines the differences in the accumulation and generation of labile Hg among different waterbodies. The positive correlation between sediment MHg and sulfate concentrations suggested possible methylation reaction by dissimilatory sulfate reducing bacteria in the sediment. The food web magnification factors of MHg were 9.6 (95% CI: 4.0-23.4) and 4.4 (95% CI: 2.5-7.7) for the two streams established with trophic data of biofilm, invertebrates, and fish. Meanwhile, DGT-Hg concentrations in the water were positively correlated to biofilm Hg concentrations, which can be combined with the MHg biomagnification model to generate a modified biomagnification model that estimate MHg bioaccumulation with only labile Hg concentrations in the water. With this approach, Hg accumulation in abiotic and biotic environmental compartments was connected and the different bioaccumulation patterns of Hg in different waterbodies were explained with both geochemical and biological factors.

© 2019 SETAC Anthropogenic contamination in the Antarctic near-shore marine environment is a challenge for environmental managers because of its isolation, high costs associated with monitoring and remediation activities, and the current lack of Antarctic-specific ecotoxicological data. The present study investigated the application of diffusive gradients in thin films (DGT) with a Chelex-100 binding resin for metal contaminant assessment in Antarctic marine conditions. Diffusion coefficients for cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn), determined at 1 °C, ranged between 2.1 and 2.6×10–6 cm2/s and were up to 32% lower than those derived by theoretical calculations. Competition of metals on the DGT binding resin was observed at subsaturation concentrations, reducing the effective capacity for metal uptake by approximately 60%. The lability of the dissolved (0.45 µm filterable) Cd, Cu, Pb, and Zn metal fraction to DGT was generally >90% and unaffected by the presence of the Antarctic marine microalga Phaeocystis antarctica. Both DGT and dissolved metal concentrations gave equivalent mixture toxicity predictions in independent action and concentration addition models to P. antarctica and Cryothecomonas armigera; that is, predictions using DGT-labile concentrations also showed antagonism to P. antarctica, which agrees with previously determined mixture interactivity. The benefits of DGT over traditional sampling techniques (i.e., discrete water sampling) include lower method detection limits (MDLs), in situ assessment, and time-averaged concentrations which capture pulses of contamination typical of the Antarctic near-shore marine environment. The present study provides MDLs and recommended minimum deployment times to guide field deployments in Antarctica. Environ Toxicol Chem 2019;38:1323–1333. © 2019 SETAC.

Phosphorus (P) pollution is a significant environmental problem in lakes, especially in lakes highly impacted by human activities, e.g., Honghu Lake. Years of farming activities have led to a complex occurrence of P in the sediment which has not been studied in detail. Iron redox cycling is a key mechanism controlling P adsorption–desorption behavior, and its study is an effective means of assessing P dynamics, which could provide basic theoretical data for the control of internal phosphorus in such lakes. The high-resolution ZrO-Chelex DGT (ZrO-Chelex diffusive gradients in thin films) and HR-Peeper (high-resolution dialysis sampler) techniques were used to assess labile P, labile Fe, and soluble reactive P (SRP) in five sediment samples from four functional areas of Honghu Lake. The temperature, pH, and dissolved oxygen levels of water samples were measured in situ using a portable water quality analyzer, and the dissolved organic carbon (DOC) concentration was analyzed with a TOC analyzer after 0.45 μm membrane filtration. Total Fe concentrations were determined using the phenanthroline colorimetric approach. Sediment porosity was calculated based on weight loss after drying for 6 h at 105 °C. One-dimensional changes in labile P and Fe in different functional areas of the lake were quite heterogeneous, and there was a significant linear correlation between labile P and Fe near the sediment–water interface (SWI). Sediment samples HH-2 and HH-5 exhibited positive P diffusion flux (F) and tended to be a P source, while sites HH-1, HH-3, and HH-4 tended to take in P from overlying water. The ratio (R) of labile P to SRP was used as an indicator of potential soluble reactive P release from sediments into the surrounding water and initially increased at four sampling sites, then decreased deeper in the sediment except at site HH-4. The results indicated that the tendency of P released from sediments or uptake from overlying water was distinct in different functional areas and that iron redox cycling was a key mechanism controlling P dynamics in the sediments of Honghu Lake. Thus, the iron–phosphorus relationship can provide an accurate assessment of P release processes in a surface water environment.

In general, the diffusive gradients in thin films (DGT) technique is an effective tool for evaluating metal bioavailability; however, its applicability is subject to the type of metal and organism involved. In this study, the accumulated masses of Hg in DGT probes and in the earthworm species Eisenia fetida were monitored for 10 days, to test if the DGT technique can be used as a predicting method for the bioavailability of soil Hg to earthworms. In the Hg exposure tests using soils prepared with different peat moss concentrations of 5, 10, 15, and 20% and varying pH values of 4.6, 5.6, and 6.2, the experimentally determined DGT-soil accumulation factor (DSAF) and biota-soil accumulation factor (BSAF) both increased as the peat moss content decreased and the pH increased. According to a one compartment model, this was a result of the increased Hg uptake rate constant (k1) and the relatively stable Hg elimination constant (k2) under lower peat moss and higher pH conditions. It is interesting to note that the Hg uptake rates by DGT and earthworms were considerably higher for fresh soils than for aged soils, while porewater (and acid-extractable) Hg concentrations were rather similar between the two types of soils. Across diverse soil properties, steady-state Hg in earthworm tissue showed a strong positive correlation with DGT-measured Hg flux ([earthworm Hg] = 354(DGT−Hg flux)−34, r2 = 0.88), while meager correlations were found between Hg concentration in earthworms and that in porewater (and acid-extractable). The overall results indicate that DGT-measured Hg flux is a better tool than conventional methods for predicting Hg bioavailability for earthworms inhabiting diverse types of soil.

Because of its high adsorption capacity, biochar has been used to stabilize heavy metals when remediating contaminated soils; to date, however, it has seldom been used to remediate contaminated sediment. In this study, a biochar was used as a stabilization agent to remediate Cu-and Pb-contaminated sediments, collected from three locations in or close to Beijing. The sediments were mixed with a palm sawdust gasified biochar at a range of weight ratios (2.5%, 5%, and 10%) and incubated for 10, 30, or 60 days. The performance of the different treatments and the heavy metal fractions in the sediments were assessed using four extraction methods, including diffusive gradients in thin films, the porewater concentration, a sequential extraction, and the toxicity characteristic leaching procedure. The results showed that biochar could enhance the stability of heavy metals in contaminated sediments. The degree of stability increased as both the dose of biochar and the incubation time increased. The sediment pH and the morphology of the metal crystals adsorbed onto the biochar changed as the contact time increased. Our results showed that adsorption, metal crystallization, and the pH were the main controls on the stabilization of metals in contaminated sediment by biochar.

Due to the limited aeration capacity of current aeration techniques at the sediment-water interface (SWI), we developed a specialized aeration material aimed at the SWI, known as oxygen nano-bubble-modified minerals (ONBMMs). Furthermore, we simulated its aeration efficiency at the SWI and the control effects of internal phosphorous (P) release under anaerobic conditions during 20 days. High resolution diffusive gradients in thin films (DGT) and Planar luminescent optode (PO) technologies were used to measure the temporal variation of reactive P, reactive Fe (II) and dissolved oxygen (DO) of the SWI. These results show that ONBMMs can effectively increase the content of DO at the SWI and decrease the release flux of internal P from sediments. The use of ONBMMs reduced 97.9% of the soluble reactive P concentration of the overlaying water and reduced the release flux of DGT-P from sediments by 78.9%. Inhibition of reductive dissolution of FeP from sediments was the primary principle that effectively inhibited the input of internal P by ONBMMs. Therefore, ONBMMs are potentially promising technology for the treatment of internal P pollution in eutrophic lakes.

Flow velocity is known to alter passive sampling accuracy. We investigated the POCIS (Polar Organic Chemical Integrative Sampler) with PRC (Performance Reference Compounds) approach and Diffusive Gradients in Thin Films samplers (o-DGT) to limit the effect of flow on the quantification accuracy of ten model pharmaceuticals compounds (0.16

Antimony (Sb) mobilization in sediments and its impact on water quality remained to be studied. In this study, high-resolution dialysis (HR-Peeper) and diffusive gradients in thin films (DGT) technique were used to measure soluble Sb and labile Sb in sediment-overlying water profiles for a full year in a eutrophic region of Lake Taihu. Results showed that the highest mean concentrations of soluble Sb in overlying water (11.27 and 6.99 μg/L) appeared in December 2016 and January 2017, due to oxidation of Sb(III) to Sb(V) by Mn and Fe oxides, all of which exceeded the surface or drinking water limits set by China, United States and European Union. From April to November 2016, the concentrations of soluble Sb remained low with small monthly fluctuations and mean values ranging from 1.79 to 2.93 μg/L. This was attributed to the predominance of insoluble Sb(III) in sediments under anoxic conditions. The concentration of soluble Sb was slightly higher in summer than in autumn, due to the complexation of Sb(III) with DOM, as shown under anaerobic incubation. The mobility of inorganic Sb in sediments was mostly determined by the transition between Sb(III) and Sb(V), with Sb pollution in bottom water during winter being of concern.

The activity of e-waste recycling often causes the combined pollution of tetrabromobisphenol A (TBBPA) and cadmium (Cd) in soils. In this study, the effects of their co-existence on each other's fate, further reflecting the bioavailability, were analyzed in the presence of two ecologically different earthworm species, endogeic Metaphire guillelmi and epigeic Eisenia fetida. Mineralization of 14C-TBBPA combined with 10 mg Cd kg−1 was suppressed by the presence of M. guillelmi, whereas a facilitating effect was produced by the combination of 1 mg Cd kg−1 in the soil-E. fetida system after a 14-day exposure. The uptake of 14C-TBBPA by M. guillelmi (17% of initial amount) and by E. fetida (10%) dominantly contributed to significant (P 0.05) influence the accumulation and metabolism of TBBPA in the earthworms. Both earthworms accumulated only ~7% of Cd in soil, however, the bioavailable Cd determined by the diffusive gradients in thin films technique declined by ~46% in the presence of M. guillelmi, and a much smaller decrease was determined in the presence of E. fetida. Amendment of TBBPA at environmental levels did not alter the accumulation and subcellular distribution of Cd in both earthworms unless that at high doses. The results highlighted the importance of considering the difference of the earthworm species and the interaction of pollutants in soil-risk assessments of such combined contamination. Capsule M. guillelmi displayed greater effect on the fate of TBBPA and Cd co-existed in soils than E. fetida, while the accumulation, metabolism, or distribution of the two pollutants in earthworms did not significantly alter due to interactions between the two pollutants.

Iron (Fe) and manganese (Mn) reactions have been regarded as the primary factors responsible for the mobilization of phosphorus (P) in lake sediments, although their individual roles are hard to distinguish. In this study, in situ mobilization of P, Fe and Mn in sediments was assessed by high resolution spatio-temporal sampling of their labile forms using diffusive gradient in thin films (DGT) and suction device (Rhizon) techniques. It was found that the monthly concentration distributions showed greater agreement and better correlation coefficients between labile P and labile Fe, than those between labile P and labile Mn, implying that Fe plays a key role in controlling P release in sediments. Furthermore, better correlations were observed between hourly changes in concentrations of soluble reactive phosphorus (SRP) and soluble Fe(II), than those between SRP and soluble Mn. Changes were observed under simulated anaerobic incubation conditions, suggesting that P release was caused by the reductive dissolution of Fe oxides. This was supported by the lack of influences on P release from reductive dissolution of Mn oxides in the sediment-water interface and top sediment layers under the anaerobic incubations. In simulated algal bloom experiments, positive correlations and consistent changes were observed between SRP and soluble Fe(II) concentrations, but not between SRP and soluble Mn concentrations. This further demonstrated the Fe-dependent and Mn-independent release of P in sediments. Therefore, Fe redox reactions have a high impact on P mobilization in sediments, while Mn redox reactions appear to have negligible influences.

In-situ study on arsenic speciation and the release kinetics in marine sediments was scarce. In this study, the distributions of labile As and their speciation in coastal sediments of Daya Bay were obtained by separate diffusive gradients in thin films (DGT) probes. Results showed that the DGT-labile As(V) was the main speciation in surface sediments (from −20 to 0 mm) with a concentration range of 0.07–3.05 μg·L−1, while the labile As(III) was the main speciation in deep layers of sediments (from −100 to −20 mm). In coastal areas, mariculture farms was the most dominated contributor to As(V) contamination in surface sediments. Both the apparent diffusion flux estimation and the DGT induced flux in sediments (DIFS) simulation indicated that As(V) contamination in surface sediments of mariculture, harbor and petrochemical areas suffered the potential risk of As(V) release into the overlying water from sediments. DIFS modeling also found that the sediments of mariculture farms were the main sediment As pools. Linear regression analysis indicated that the mobility of As mainly attributed to the As(V) in sediments.

The pollution of antibiotics, including tetracyclines (TCs), in aquatic environments has become an issue of concern in recent years. Herein, an in situ sampling of TCs in pig breeding wastewater that utilizes the technique of diffusive gradients in thin films (DGT), based on commercial nanosized ZnO (nanoZnO) particles as the potential effective binding agent and a polyethersulfone (PES) membrane as the diffusion layer, was developed. The diffusion coefficients of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) in a PES membrane at 25 °C were (1.37 ± 0.06) × 10−6 cm2 s−1, (1.29 ± 0.05) × 10−6 cm2 s−1 and (1.94 ± 0.07) × 10−6 cm2 s−1, respectively. The results showed that the adsorption capacities of a gel disc containing 2.5 g L−1 of nanoZnO particles were as high as 3.93 ± 0.20 mg disc−1 for TC, 3.21 ± 0.20 mg disc−1 for OTC and 4.62 ± 0.22 mg disc−1 for CTC. Both a solution pH in the range of 5–9 and an ionic strength (as pNaCl) in the range of 1–3 had an insignificant influence on the TCs uptake by nanoZnO−DGT samplers. There was no significant influence of fulvic acid or tannic acid on the TC uptake by nanoZnO−DGT samplers at the tested mass ratios. For all spiked freshwater samples, there was no notable interference of matrices on the performance of the nanoZnO−DGT samplers, suggesting that the nanoZnO−DGT samplers yielded satisfactory results for the uptake of TCs at concentrations existing in the spiked freshwater samples. Field deployment of the nanoZnO−DGT samplers in pig breeding wastewater also exhibited excellent precision and accuracy, indicating that the nanoZnO−DGT samplers could be used as a promising method for the in situ sampling of TC antibiotics in aquatic environments.

The toxicity and bioavailability of Cr depends on its speciation in the aquatic environment. Here, we developed a new method for simultaneously obtaining in-situ data on labile Cr(III) and Cr(VI) using diffusive gradients in thin films (DGT) and high-performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). A Zr-oxide DGT was applied to accumulate both labile Cr(III) and Cr(VI). The elution of Cr species was carried out with 50 mM EDTA-2Na at pH 9.5 for 1.5 h. Agilent Bio WAX anion-exchange chromatography was used to separate Cr species in the slightly alkaline mobile phase containing 40 mM NH4NO3 at pH 7.4. An ICP-MS was used to quantitatively measure Cr within 4.5 min. Method detection limits were 0.05 μg/L for Cr(III) and 0.02 μg/L for Cr(VI). Labile Cr(III) and Cr(VI) was accurately quantified in synthetic solutions for pH in the range of 5–8 and ionic strength ranging from 10 to 100 mmol L−1. The method allows quantification of labile Cr(III) and Cr(VI) in natural water and was consistent with results of when a separate measurement method based on DGT was used. This study was an attempt at simultaneous in-situ quantification of labile Cr(III) and Cr(VI), and will facilitate in-situ labile Cr speciation analysis in the environment.

To better understand the biogeochemical processes of iron, sulfur, and phosphorus and their coupled relationships, we used the in situ high-resolution diffusive gradients in thin films (DGT) technique to characterize labile Fe, S, and P in the sediment porewater of a mangrove coast in the Jiulong River Estuary, China. The distributions of DGT-labile Fe and S indicated that microbial sulfate reduction (MSR) and microbial iron reduction (MIR) exhibited an intense competitive relationship and temperature-dependent behavior. Thus, in addition to the expected MSR, MIR is an important or even predominant biogeochemical process for organic matter (OM) mineralization in this Fe-rich mangrove coast. Labile Fe, S, and P distributions and variations demonstrate that Fe redox cycling plays a crucial role in regulating P behavior and P cycling. An additional new finding is that the flux of labile S in the intertidal zone increases during flood tides and decreases during ebb tides, indicating that the formation and reoxidation of sulfide in surface layers are regulated by tide-induced redox changes. The net P flux associated with recirculated seawater was estimated to range from −0.306 ± 0.001 to 0.343 ± 0.013 mmol m−2 d−1 in the winter survey, suggesting that sediment porewater tends to be a P source in the subtidal zone and a P sink in the intertidal zone for the overlying seawater in winter. The continuous accumulation of labile P in surface sediment could be intensively released into the overlying seawater through prevailing MIR process in the subsequent riverine flood season, which may promote eutrophication of the adjacent Xiamen Bay.

As the sole drinking water source for Beijing City, Cd has been previously assessed as the major contaminant in Miyun Reservoir (MYR) riparian soils. However, the potential release risk of Cd in such soils, and the labile-Cd release–resupply process from the soil solid phase to solution after water impoundment remain poorly understood. We established a geochemical baseline concentration (GBC) of Cd in MYR riparian soils, combined with the diffusive gradient in thin films (DGT) technique and DGT-induced fluxes in soil (DIFS) model, to reveal a dynamic release–resupply process and influencing factors of labile Cd in riparian soils. The results showed that Cd GBC in riparian soils was 0.12 mg/kg, which was higher than the Cd background value (BV) for Beijing. Using Cd GBC as BV to assess the Cd contaminant level, the geo-accumulation index showed that Cd in riparian soils was at the uncontaminated level. In addition, Cd in the soils belonged to the non-residual fraction using the Community Bureau of Reference method. Cd mobility coefficients (F1/CTotal-Cd) of soils at low elevation had relatively high values, implying that Cd may be released during the initial impoundment of the MYR. Moreover, correlation analysis was used to found the major influencing factors between DGT-labile Cd and several parameters. The results showed that the DGT-labile Cd was positively correlated to the reducible and oxidizable fraction, CDGT-Fe, and total organic carbon, illustrating that the release of Cd from soils was controlled by Fe oxides and organic matter. The resupply ability (R values) and DIFS model parameters revealed that Cd in MYR soils belonged to the partially sustained case, and the slow desorption rate suggested that the release risk of Cd was low in the MYR riparian soils.

Aluminum-salt inactivating agents are extensively applied to the restoration of lakes polluted by internal phosphorus (hereinafter referred to as "P"). However, there is a lack of micromechanism information regarding the sediment P cycle and its interactions with aluminum salts, which has restricted the engineering applications of aluminum salts. In this study, a sediment core incubation system was used to simulate the influence of aerobic and anaerobic conditions on the effectiveness and stability of aluminum-modified clay (AMC). This study also investigated the millimeter-scale dynamics of P across the sediment-water interface (SWI) using the HR-Peeper and DGT techniques. According to the results, sediment P release mainly occurred under anaerobic conditions. When the incubation system was in an anaerobic state, AMC effectively reduced the internal-P loading. In pore water, there was a positive correlation between soluble Fe and SRP, suggesting that the reductive dissolution of Fe-P constituted the main mechanism of sediment P release. After with dosing AMC, the concentrations of SRP and labile P in the capping layer both dropped abruptly to low levels and the content of Al-P in surface sediments rose, suggesting that AMC had strongly adsorbed phosphates, formed inert Al-P and blocked the phosphate exchange between pore water and overlying water. This study elaborated on the micromechanism of the control of sediment internal P input by AMC and revealed that Al-P precipitation constituted the main mechanism of the inhibition of sediment P release by aluminum-salt inactivating agents. The research findings have a great significance for guiding field applications of aluminum-salt inactivating agents.

There is generally a significant heterogeneity in the vertical distribution of mobile phosphorus (P) in sediments, but the previous studies concerning the effect of zirconium-modified zeolite (ZrMZ) addition on the mobilization of P in sediments neglected this feature. In this study, microcosm experiments were conducted to investigate the effect of ZrMZ addition on the mobilization of P in river surface sediments at different depths. A high-resolution diffusive gradients in thin films technology (DGT) was used to measure the concentration of labile P in the overlying water-sediment profiles at a submillimeter vertical resolution. Results showed that the ZrMZ amendment not only could reduce the concentration of soluble reactive P (SRP) in the overlying water, but also could decrease the concentrations of SRP in the pore water at different depths. Furthermore, the ZrMZ amendment resulted in the reduction of both the releasing flux of SRP from sediments to the overlying water and the diffusion flux of SRP from the pore water to the overlying water. After the addition of ZrMZ into the top sediment, the static layer with low DGT-liable P (DGT-P) concentration was observed in the upper sediment. The addition of ZrMZ into the upper sediment resulted in the reduction of mobile P (Pm) in the upper and lower sediments via the transformation of Pm to more stable NaOH-extractable P (NaOH-rP) and residual P (Res-P). In addition, the contents of bioavailable P (BAP) including water-soluble P (WSP), readily desorbable P (RDP) and iron oxide paper extractable P (FeO-P) in the upper sediment were greatly reduced by the ZrMZ addition. Results of this study show that the immobilization of pore water SRP, DGT-P, sediment Pm and sediment BAP by ZrMZ played a very important role in the control of P release from sediments to the overlying water by the ZrMZ amendment.

Cadmium (Cd) is highly toxic to living organisms and the contamination of Cd in paddy soil in China has received much attention. In the present study, by conducting pot experiment, the influence of S fertilizer (S0) on rice growth, iron plaque formation, Cd accumulation in rice plants and bacterial community in rice rhizosphere soil was investigated. The biomass of rice plants was significantly increased by S0 addition (19.5–73.6%). The addition of S0 increased the formation of iron plaque by 24.3–45.8%, meanwhile the amount of Cd sequestered on iron plaque increased. In soil treated with 5 mg/kg Cd, addition of 0.2 g/kg S0 decreased the diffusive gradients in thin films (DGT) extractable Cd by 60.0%. The application of S0 significantly decreased the concentration of Cd in rice grain by 12.1% (0.1 g/kg) and 36.6% (0.2 g/kg) respectively. The addition of S0 significantly increased the ratio of Acidobacteria, Bacteroidetes in rice rhizosphere soil. Meanwhile, the ratio of Planctomycetes and Chloroflexi decreased. The results indicated that promoting Fe- and S-reducing and residue decomposition bacterial in the rhizosphere by S0 may be one biological reason for reducing Cd risk in the soil-rice system.

The determination of the concentration of an environmental pollutant is not sufficient to assess the related health risk because this pollutant may not be bioavailable. Therefore, methods to determine pollutant bioavailability are more relevant to assess toxicity than measuring the total concentration. For instance, the diffusive gradient in thin films (DGT) is an in situ dynamic technique used to measure the concentration of labile compounds in the environment. Here we review the latest developments achieved in speciation and bioavailability of metals and metalloids using this technique. We detail the technique, common binding agents and diffusive gels. We give laboratory procedures to prepare the gels, and we explain calculations using the DGT-induced fluxes in soils (DIFS) modeling. DIFS models can predict the resupply capacities from soils to porewater, and the uptake of trace elements by plants. Procedures for in situ field deployments, including issues of biofilm growth, are also discussed.