Isotope Evidence for Rice Accumulation of Newly Deposited and Soil Legacy Cadmium: A Three-Year Field Study.

Biogeochemical processes of atmospherically deposited cadmium (Cd) in soils and accumulation in rice were investigated through a three-year fully factorial atmospheric exposure experiment using Cd stable isotopes and diffusive gradients in thin films (DGT). Our results showed that approximately 37-79% of Cd in rice grains was contributed by atmospheric deposition through root and foliar uptake during the rice growing season, while the deposited Cd accounted for a small proportion of the soil pools. The highly bioavailable metals in atmospheric deposition significantly increased the soil DGT-measured bioavailable fraction; yet, this fraction rapidly aged following a first-order exponential decay model, leading to similar percentages of the bioavailable fraction in soils exposed for 1-3 years. The enrichment of light Cd isotopes in the atmospheric deposition resulted in a significant shift toward lighter Cd isotopes in rice plants. Using a modified isotopic mass balance model, foliar and root uptake of deposited Cd accounted for 47-51% and 28-36% in leaves, 41-45% and 22-30% in stems, and 45-49% and 26-30% in grains, respectively. The implications of this study are that new atmospheric deposition disproportionately contributes to the uptake of Cd in rice, and managing emissions thus becomes very important versus remediation of impacted soils.

Mapping Phosphorus Availability in Soil at a Large Scale and High Resolution Using Novel Diffusive Gradients in Thin Films Designed for X-ray Fluorescence Microscopy.

A novel binding layer (BL) as part of the diffusive gradients in thin films (DGT) technique was developed for the two-dimensional visualization and quantification of labile phosphorus (P) in soils. This BL was designed for P detection by synchrotron-based X-ray fluorescence microscopy (XFM). It differs from the conventional DGT BL as the hydrogel is eliminated to overcome the issue that the fluorescent X-rays of P are detected mainly from shallow sample depths. Instead, the novel design is based on a polyimide film (Kapton) onto which finely powdered titanium dioxide-based P binding agent (Metsorb) was applied, resulting in superficial P binding only. The BL was successfully used for quantitative visualization of P diffusion from three conventional P fertilizers applied to two soils. On a selection of samples, XFM analysis was confirmed by quantitative laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The XFM method detected significant differences in labile P concentrations and P diffusion zone radii with the P fertilizer incubation, which were explained by soil and fertilizer properties. This development paves the way for fast XFM analysis of P on large DGT BLs to investigate in situ diffusion of labile P from fertilizers and to visualize large-scale P cycling processes at high spatial resolution.

Recycled Iron Phosphates: A New Phosphorus Fertilizer for Paddy Rice.

The potential of recycled iron phosphates (FePs), e.g., vivianites (Fe3(PO4)2·8H2O) and Fe(III)-rich phosphorus (P) adsorbent materials, as phosphorus fertilizer is limited by the strong interaction between Fe and P. In this study, the efficiency of FePs as P fertilizer was explored by applying them as granules or powder in flooded strongly P-fixing soils (acid and calcareous), thereby taking advantage of increased P release induced by reductive dissolution of P-bearing Fe(III) minerals. First, no P diffusion from granular FeP fertilizers into flooded soils was detectable by the diffusive gradient in thin films (DGT) technique and microfocused X-ray fluorescence (µ-XRF) analysis of thin soil sections, in contrast to detectable P diffusion away from granules of soluble triple superphosphate (TSP) fertilizer. On the contrary, powdered FePs demonstrated an excellent increase in extractable P (1 mM CaCl2) in a 120-day incubation experiment in flooded soils. Second, a pot experiment was performed with rice (Oryza sativa) grown in flooded acid and calcareous soils. The fertilizer value of FePs was remarkable when dosed as powder, as it was even up to 3-fold higher than TSP in the acid soil and similar to TSP in the calcareous soil. The beneficial effect of FeP over TSP in the acid soil is attributed to the slow release of P from FePs, which allows to partly overcome P fixation. The promising results of FePs as P fertilizer applied as powders in flooded soils debunk the generally accepted idea that FePs are poor sources of P while demonstrating the importance of the timing of FeP fertilizer application.

Comparison of sediment bioavailable methods to assess the potential risk of metal(loid)s for river ecosystems.

A heavily impacted river basin (Caudal River, NW Spain) by Hg and Cu mining activities, abandoned decades ago, was used to evaluate the environmental quality of their river sediments. The obtained results compared with reference values established by the US EPA and the Canadian Council of Ministers of the Environment for river sediments, have shown that the main elements of environmental concern are arsenic (As), mercury (Hg) and, to a lesser extent, copper (Cu), which reach concentrations up to 1080, 80 and 54 mg kg-1, respectively. To understand the role that river sediments play in terms of risk to ecosystem health, a comparison has been made between the total content of metal(oid)s in the sediments and the bioavailable contents of the same elements in pore water, passive DGT (Diffusive Gradients in Thin films) samplers and the sediment extractant using acetic acid. A good correlation between the As and Cu contents in the DGTs and the pore water was found, resulting in a transfer from the pore water to the DGT of at least 47 % of the Cu and more than 75 % of the As when the concentrations were low, with a deployment time of 4 days. When As and Cu concentrations were higher, their transfer was not so high (above 23.6 % for As and 19.3 % for Cu). The transfer of Hg from the pore water to the DGT was practically nil and does not seem to depend on the content of this metal. The fraction extracted with acetic acid, conventionally accepted as bioavailable, was clearly lower than that captured by DGTs for As and Cu (≤5 % and ≤8.5 % of the total amount, respectively), while it was similar for Hg (0.2 %).

Seasonal Sulfur Redox Cycling in Two Constructed Wetlands with Insight on How They Age.

Long-term metal remediation in wetland treatment systems (WTSs) involves facilitating dissimilatory sulfate reduction to produce sulfide and mineralize metals in deep sediments. We evaluated seasonal sulfur cycling in two constructed wetlands (Maintained WTS constructed in 2007, and the Unmaintained WTS constructed in 2000) on the Savannah River Site in Aiken, South Carolina, USA. Significant interactions in sulfide concentration were observed between sediment depth, season, and wetland (F = 4.64, df = 11, P = 3.28 × 10 - 5). In the Maintained WTS, dissimilatory sulfate reduction dominated the surface sediments during the warm season (0-2 cm depth, t=-2.66, P = 9.70 × 10 - 3), unlike the Unmaintained system. Sulfate concentrations in pore waters increased in the warm season (F = 7.84, df = 1, P = 6.50 × 10 - 3), contrary to expectations. Sulfur limitation in the Unmaintained WTS during the warm season correlated with increased sulfur assimilation in giant bulrush. Lower sulfide concentrations in surface sediments of the Unmaintained WTS illustrated aging effects. The Maintained WTS shows potential for managing erosion, pH reduction, and sulfur limitation observed in the older Unmaintained WTS.

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.

In Situ Insight into the Availability and Desorption Kinetics of Per- and Polyfluoroalkyl Substances in Soils with Diffusive Gradients in Thin Films.

The physicochemical exchange dynamics between the solid and solution phases of per- and polyfluoroalkyl substances (PFAS) in soils needs to be better understood. This study employed an in situ tool, diffusive gradients in thin films (DGT), to understand the distribution and exchange kinetics of five typical PFAS in four soils. Results show a nonlinear relationship between the PFAS masses in DGT and time, implying that PFAS were partially supplied by the solid phase in all of the soils. A dynamic model DGT-induced fluxes in soils/sediments (DIFS) was used to interpret the results and derive the distribution coefficients for the labile fraction (Kdl), response time (tc), and adsorption/desorption rates (k1 and k-1). The larger labile pool size (indicated by Kdl) for the longer chain PFAS implies their higher potential availability. The shorter chain PFAS tend to have a larger tc and relatively smaller k-1, implying that the release of these PFAS in soils might be kinetically limited but not for more hydrophobic compounds, such as perfluorooctanesulfonic acid (PFOS), although soil properties might play an important role. Kdl ultimately controls the PFAS availability in soils, while the PFAS release from soils might be kinetically constrained (which may also hold for biota uptake), particularly for more hydrophilic PFAS.

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.

Evaluation of sediment phosphorus dynamics in cascade reservoir systems: A case study of Weiyuan River, China.

Reservoirs tend to accumulate phosphorus (P) originating from agriculture, industry, and other upstream sources in sediment, with this stored P later released. However, the spatiotemporal dynamics of sediment P release in reservoirs remains unclear. This study investigated the spatiotemporal dynamics in P of the sediment and water of three cascade reservoirs in the Weiyuan River (Tuojiang tributary). The results showed elevated P in sediment [total P (TP): 1208.93 mg kg-1] and water (TP: 0.23 mg L-1) during the low-water season (LWS), which could be attributed to notably higher organic matter content (9.65%), finer particle size (20.95 µm), and extended hydraulic retention time (HRT: 13.13 days) downstream of the cascade reservoirs. Further study employing static in-situ diffusive gradient in thin films (DGT) and dynamic ex-situ adsorption kinetic experiments confirmed that the downstream release of P from sediments [diffusion flux (Fd): 1.67 mg m-2 d-1, equilibrium P concentrations (EPC0): 0.22 ± 0.10 mg L-1] greatly exceeded those upstream (-0.66 ± 0.17 mg m-2 d-1, 0.07 ± 0.001 mg L-1), Fe (II) was a critical factor in regulating sedimentary P release. The combined effects of high P in overlying water and sediment significantly stimulated downstream phytoplankton growth, particularly among cyanobacteria (26.48%) and green algae (8.33%). Further regulatory steps are needed to regulate LWS algal blooms downstream of cascade reservoirs.

Short-term arsenic mobilization, labilization, and microbiological aspects after gasoline and diesel addition in tropical soils.

The effect of the presence of gasoline and diesel on the speciation and mobility of inorganic arsenic species in tropical topsoils was investigated. Topsoil samples (n = 25) were contaminated with gasoline and diesel (500 mg kg-1) in laboratory and were incubated under unsaturated conditions and regular aeration for 21 days. Speciation analysis and chemical fractionation were performed in the pore water from control, gasoline, and diesel-contaminated soil samples. Arsenic concentrations were compared to microbiological parameters (microbial metabolic quotient and soil basal breathing) and the presence of ArsM-harboring bacteria. The spike of gasoline and diesel to the topsoils increased pore water As3+ (H3AsO3) concentration. Arsenic mobilization was lower compared to previously reported data for other sources of organic matter (biochar, litter, and a mixture of sphagnum peat moss and composted poultry manure). However, gasoline or diesel addition mobilized As fractions that were adsorbed to the solid phase, in approximately 60% of the soils. Methylation presented an important role in the As3+ regulation in control soils, which was no longer observed after gasoline or diesel addition. The quantification of the labile fractions sampled by the diffusive gradients in thin films technique showed that the increased As concentration in the gasoline or diesel-contaminated soils mostly included inert species. Dissolved organic carbon content seems to be an important control mechanism of the labile As concentration. The increase in As mobility seems to pose a more concerning scenario due to As leaching than to plant uptake.

Evaluating the release risk of potentially toxic elements from sediments in the New Zhuzhao River Estuary of Nansi Lake, using high-resolution technology and sequential extraction.

Potentially toxic elements (PTEs) re-release from sediment is an essential process in the sediment-water interface (SWI), especially for the influent river estuary as an important accumulation site. In this study, the diffusive gradient in thin films (DGT), high-resolution dialysis (HR-peeper) technique, and BCR sequential extraction were employed to evaluate the release risk of PTEs (As, Cu, Pb, Zn, Cd) in the New Zhuzhao River Estuary of Nansi Lake. Results showed that Cd existed primarily in the non-residual fraction (accounting for 59.87%), and the residual fractions of As, Cu, Pb, and Zn accounted for a greater proportion (12.65 to 33.07%). The mobility of Cd was the highest with a risk assessment code of 33.53% reaching the medium risk category. The resupply capacity calculated by CDGT/CDis showed that As was the largest, with an average value of 0.43, indicating the strongest release capacity of As from the sediment to pore water. Furthermore, the diffusive fluxes using DGT and HR-peeper showed that As possesses a much higher potential to release upward overlying water than other elements.

In Situ Understanding of the Effect of Manure on the Availability of Sulfonamide Antibiotics in Soils Using DGT.

In this study, the effects of manure on the availability of sulfonamide antibiotics (SAs) in soils were explored in situ by the Diffusive gradients in thin films (DGT) technique. Five antibiotics, including sulfadiazine (SDZ), sulfamethoxazole (SMX), sulfamethazine (SMZ), sulfachloropyridazine (SCP), and sulfadimethoxine (SDM), were selected as target compounds. Results showed that the manure application to soil could reduce the antibiotic availability indicated by DGT. DGT measurement (CDGT) showed good correlations with the soil solution concentrations (Cd). Manure application can suppress the fluxes of SAs from the soil to the soil solution. Using the DGT-induced soil/sediment flux model (DIFS), the labile pool size (Kdl), the rate constants (k1, k-1) of adsorption and desorption and response time (Tc) of SAs in soils were obtained. The addition of manure increased extractable fraction, labile pool size (Kdl) and k1 but decreased k-1. Together with the nonlinear relationship between DGT fluxes and the reciprocal of diffusive layer thickness (Δg), these findings suggested that the release of SAs from soil particles into the soil solution is thermodynamically and kinetically limited, and the manure application could enhance this limitation. This study offers insight into antibiotic availability in soils caused by manure application.

Evaluation and Application of a Novel Diffusive Gradients in Thin-Films Technique for In Situ Monitoring of Glucocorticoids in Natural Waters.

The potential environmental risks of glucocorticoids (GCs) have attracted attention in the past few decades. In this study, a novel diffusive gradients in thin-films (DGT) device and analytical technique based on the second generation of polar enhanced phase (PEP-2), PEP-2-DGT, were developed for sampling and quantifying natural and synthetic GCs in aquatic systems. The capacity of PEP-2 gels for accumulating all target compounds was >600 µg per disc, sufficient for long-term passive sampling of selected GCs, even in wastewaters. Systematic tests were carried out to verify the application of DGT in natural waters and wastewaters. The performance of PEP-2-DGT devices was independent (CDGT/Csoln was in the acceptable range of 0.9-1.1) of a wide range of environmental conditions: ionic strength (0.001-0.5 mol L-1), dissolved organic matter (0-20 mg L-1), and pH (3.06-9.02). It was tested for various diffusive layer thicknesses (0.565-2.065 mm) and different deployment times (10-168 h). Diffusion coefficients (D) of selected GCs through an agarose-based diffusive gel were determined for the first time (3.80-4.85 × 10-6 cm-2 s -1 at 25 °C). Linear correlations between D and log Kow were established for three groups of target GCs (R2 = 0.96-0.99). This could enable prediction of D values for other GCs with similar structures in the future, which will help for rapid screening and emergency monitoring. Concentrations and distribution patterns of analytes obtained by PEP-2-DGT devices in five rivers after 7- and 14-day deployments were in accordance with those measured from grab samples, with total GC concentrations ranging from 7 to 27 ng L-1 at all sampling sites, confirming the reliability and robustness of the DGT devices for monitoring GCs in natural waters. The development of the new DGT technique will help improve understanding of the behavior and fate of these compounds in the aquatic environments.

Assessment of dissolved mercury by diffusive gradients in thin films devices in abandoned ponds impacted by small scale gold mining.

In order to fulfil the Minamata Convention on Mercury, it is necessary to monitor the Hg contamination in freshwater ecosystems nearby artisanal and small scale gold mining (ASGM) areas. Since most of these ASGM communities are located in remote areas, a convenient method for sampling, preserving and transporting samples is needed. In this study we evaluated the feasibility of the diffusive gradient in thin-films (DGT) technique to detect and quantify the labile fraction of Hg and other metals (Pb, Cu, Zn, Cd, Ni, Mn and Cr) in a hard-to-reach gold mining district in the state of Chocó, Colombia. We deployed DGT at sampling sites along the Atrato river and abandoned mining ponds (AMPs) which were deserted in different periods since 1997 to 2019 (6-15 years). In average, the labile THg concentrations in AMPs (148.9 ± 43.2 ng L-1) were a 50% higher than in the river water (99.9 ± 37.4 ng L-1). In the ponds, no significant differences were found in labile Hg with respect abandonment period. Labile Ni (0.9-493.1), Mn (1.33-11.48), Cu (0.030-2.233), and Zn (0.67-10.29) (in µg L-1) were found in higher amounts than for the rest of metals. Labile concentrations of metals are related with their downstream proximity to gold mining activities, being higher in devices deployed close to ASGM sites. Moreover, this study demonstrates the feasibility of the DGT technique to sample, transport, storage, and preserve labile Hg from hard-to-reach ASGM areas.

Assessing the environmental risk and mobility of cobalt in sediment near nonferrous metal mines with risk assessment indexes and the diffusive gradients in thin films (DGT) technique.

The Jialing River is the tributary of the Yangtze River with the largest drainage area. In recent years, the Jialing River has suffered a series of environmental problems, such as discharge of industrial effluent and sand mining activities, which have severely threatened the aquatic ecosystem of the river. In the present study, we employed risk assessment indexes, sequential extraction and the diffusive gradients in thin films (DGT) technique to assess environmental risks and study the remobilization of cobalt (Co) in sediments. The potential ecological risk index and risk assessment code results demonstrated that Co may pose a low environmental and ecological risk to the local aquatic environment. However, BCR sequential extraction showed that the sum of the F1, F2 and F3 fractions of Co still accounted for over 50% of the Co in the study areas, indicating that sediments may be a source of Co release. The DGT results showed an increasing trend for DGT-labile Co in deep sediments (-8 cm to -12 cm), and the calculated flux values ranged from 0.08 to 15.54 ng cm2·day-1, indicating that Co tends to transfer across the sediment-water interface at all sampling sites. Correlation analysis showed that F1-Co, F2-Co and F3-Co are the fractions readily captured by DGT and can be used for predicting Co remobilization in sediment. Sand mining activities contribute substantially to the release of Co from the F1 and F3 fractions as a result of strong stirring of sediments and introduction of oxygen into the sediments. The reductive dissolution of iron (Fe) and manganese (Mn) hydroxides or oxides causes the release of Co and Fe/Mn in the sediment, which leads to Co release from the reducible fraction. The above work suggests that sand mining in the Jialing River should be reasonably regulated to prohibit illegal sand mining activities.

Validation and application of diffusive gradient in thin-film (DGT) equipped novel cyclodextrin polymer gels for monitoring endocrine disrupting chemicals (EDCs) and environmental risk assessment in the Taihu lake basin.

Taihu Lake is the most important drinking water source of the major cities in the Yangtze River Delta. The pollution of endocrine disruptors (EDCs)in Taihu Lake has been increasing recently, the accurate determination is an important guide for predicting its health risks and developing appropriate controls. Monitoring organic pollutants in water using the diffusive gradient in thin film technique (DGT) has attracted much attention due to more accuracy and convenience than the grab sampling methods. In this study, a novel cyclodextrin polymer (CDP) synthesized by the simple and green method in water was taken as an adsorbent for the binding gel. Four endocrine-disrupting chemicals (EDCs), bisphenol A (BPA), 17α-ethinylestradiol (EE2), 17ß-estradiol (E2), and estriol (E3), were taken as models to determine the diffusion coefficients (4.68 × 10-6, 3.38 × 10-6, 3.34 × 10-6 and 4.31 × 10-6 cm2/s) and to test the performance of DGT, such as adsorption capacity and deployment time (1-5 day). The assembled CDP-DGT was adopted to determine four EDCs in a simulated water environment (3-9 of pH, 0.001-0.5 M of ionic strength (IS), and dissolved organic matter (DOM) of 0-20 mg/L). The ability of CDP-DGT sampling was verified in the Jiuxiang River and was carried out for a large-scale field application of in situ sampling EDCs in Taihu Lake basin. The results show that the total EDCs concentration range and the estradiol equivalent concentrations (EEQ) in Taihu Lake and its main rivers are 2.78 ng/L to 11.08 ng/L and 2.62 ng/L to 10.91 ng/L, respectively. The risk quotients (RQs) of all sampling sites in the region were greater than 1, indicating that EDCs pose a serious threat to aquatic organisms in the area. Therefore, the monitoring of EDCs in the Taihu Lake basin should be further strengthened.

The impact of river sand mining on remobilization of lead and cadmium in sediments - A case study of the Jialing River.

Due to the fast pace of urbanization worldwide, industrial sand mining activities have imposed great pressure on the environment, and consequently, these activities have led to serious environmental problems in aquatic ecosystems. However, the current understanding of the effect of sand mining on heavy metal remobilization in river sediments remains incomplete. The present study employed sediment quality guidelines (SQGs) and the sequential extraction (SE) and diffusive gradients in thin films (DGT) techniques to comprehensively investigate the effect of sand mining on the remobilization process of heavy metals in the aquatic system of the Jialing River. The SQGs results indicated that stations (S1 to S4) with sand mining disturbance exhibited Pb and Cd accumulation in surface sediments. Both Ctotal-Pb (61.78-122.04 mg·kg-1) and Ctotal-Cd (0.85-3.96 mg·kg-1) were higher than CSQGI (60 mg·kg-1 for Pb and 0.5 mg·kg-1 for Cd) and TEC (35.8 mg·kg-1 for Pb and 0.99 mg·kg-1 for Cd) limitation in most of sand mining stations. Pb and Cd were mainly bounded in the acid-soluble/exchangeable fraction (F1) and oxidizable fraction (F3) of the surface sediments. At the four stations with sand mining disturbance, about 5-10 folds of DGT-labile Pb and Cd were released in deep sediments (-9 to -12 cm), and Pb and Cd exhibited a transport trend from the sediments into the overlying water, while the above phenomenon was not observed at the two stations without sand mining activities. Correlation analysis revealed that DGT-labile Pb and Cd were suitably correlated with the F1 and F3 fractions, indicating that the acid-soluble/exchangeable and oxidizable fractions were the main sources leading to Pb and Cd remobilization in the sediments. A potential mechanism explanation may be that (1) intense sediment stirring could result in remobilization of the weakly bound fraction, which is related to the contribution of the F1 fraction, and (2) Cd/Pb experienced a corelease process with sulfur due to O2 introduction (elevation of the dissolved oxygen level) attributed to sediment evacuation, which is related to the contribution of the F3 fraction. The above results suggested that sand mining in the Jialing River should be paid high attention to prevent heavy metal pollution in aquatic ecosystem.

New insight for the diffusion-resupply kinetics of Cr(VI) in contaminated soil using DGT/DIFS.

Chromium (Cr) is a widespread pollutant with high toxicity and mobility. However, the diffusion-resupply kinetics of Cr(VI) between the solid phase and solution in the soils remain unclear. Here, we quantified the contributions of the soil solution and solid phase to the diffusion-resupply process of Cr(VI) in the contaminated soils using the diffusive gradients in thin-films (DGT) and DGT-induced fluxes in soils model. Based on the solution extraction result, Cr(VI) was the main available Cr species in the contaminated soils. Comparing the two diffusion-resupply stages of the kinetic process, the potential hazards due to the resupply from the solid phase can reach 10.71-50.66 %, although the soil solution accounted for the largest proportion of the effective concentration of Cr(VI) (49.34-89.29 %), which was ignored in the traditional equilibrium method. The kinetic parameters can be used to interpret the dynamic process. The resupply ability of the solid phase was closely related to the response time (Tc). The longer Tc was consistent with the low desorption constant, indicating a kinetic limitation. The magnitude of the resupply from the solid phase was related to labile pool size of Cr(VI) and soil organic carbon content. This study established a new quantification method for assessing diffusion-resupply kinetics of Cr(VI) in the soil， indicating the underestimation of Cr(VI) risk based on the use of traditional equilibrium methods. Our data provided a scientific basis for ecological risk assessment, pollution prevention, surface- and groundwater control, and environmental governance in areas with Cr contaminated soil.

Metal Removal by a Free Surface Constructed Wetland and Prediction of Metal Bioavailability and Toxicity with Diffusive Gradients in Thin Films (DGT) and Biotic Ligand Model (BLM).

The H-02 constructed wetland is a free water surface wetland to remove copper (Cu) and zinc (Zn) from the industrial wastewater. In this study, we evaluated the performance of the wetland from 2018 to 2019 and coupled the diffusive gradients in thin films (DGTs) and biotic ligand model (BLM) to explore metal speciation and bioavailability in wetland waters. Surface water samples were collected and piston DGTs were deployed in different sites of the wetland. The H-02 wetland functioned well during the sampling period with high removal efficiencies (Cu: 73.8 ± 1.2% and Zn: 75.2 ± 16.0%). In our study, with the assumption that the combination of BLM predicted inorganic metals species, BLM Cu(II) and BLM Zn(II), were the bioavailable and toxic species, DGT-Cu did not correlate to BLM Cu(II) (P = 0.47), but DGT-Zn positively correlated to BLM Zn(II) (R2 = 0.35, P < 0.001). Compared to the modeling results of BLM, DGT-indicated labile and/or bioavailable Cu included not only free Cu ions and inorganic Cu complexes but also a high percentage of Cu-labile organic matter complexes. DGT-indicated Zn included free Zn ion, inorganic Zn, and only a low percentage of Zn-labile organic matter complexes. Our findings illustrated the appropriate use of passive sampling techniques and geological modeling when biomonitoring could be substituted. The close monitoring of metal concentrations, speciation, and bioavailability helps us understand metal biogeochemistry and metal removal processes and ensure the long-term sustainability of the constructed wetland.

Assessing the Impact of Atrazine on the Availability of Arsenic in Soils Using DGT Technique.

Arsenic (As) has been observed to co-exist with atrazine (ATR) in soils worldwide. ATR, as an organic chemical, may affect the availability of As and further influence its uptake by organisms. Here we used a novel passive sampling technique, DGT (diffusive gradients in thin-films), to compare with other two conventional sampling approaches (soil solution extraction and 'Olsen As' measurement) to investigate the influence of ATR addition (normal recommended level and contaminated level) on the availability of As in soils, to further interpret the potential risk of As in soil environment. The effect of adding ATR on the behaviour of As in soils was limited. When the concentration of ATR was much higher, the availability of As in soils was supressed, the labile pool size was also affected, but the R value did not change much. The properties of the soils also played an important role by affecting the states of the compounds.