Prediction of the bioaccessibility and accumulation of cadmium in the soil-rice-human system based on optimized DGT and BCR coupled models.

Cadmium, as a typical heavy metal, has the potential to induce soil pollution and threaten human health through the soil-plant-human pathway. The conventional evaluation method based on the total content in soil cannot accurately represent the content migrated from the food chain to plants and the human body. Previous studies focused on the process of plant enrichment of heavy metals in soil, and very few studies directly predicted human exposure or risk through the labile state of Cd in soil. Hence, a relatively accurate and convenient prediction model of Cd release and translocation in the soil-rice-human system was developed. This model utilizes available Cd and soil parameters to predict the bioavailability of Cd in soil, as well as the in vitro bioaccessibility of Cd in cooked rice. The bioavailability of Cd was determined by the Diffusive Gradients in Thin-films technology and BCR sequential extraction procedure, offering in-situ quantification, which presents a significant advantage over traditional monitoring methods and aligns closely with the actual uptake of heavy metals by plants. The experimental results show that the prediction model based on the concentration of heavy metal forms measured by BCR sequential extraction procedure and diffusive gradients in thin-films technique can accurately predict the Cd uptake in rice grains, gastric and gastrointestinal phase (R2=0.712, 0.600 and 0.629). This model accurately predicts Cd bioavailability and bioaccessibility across the soil-rice-human pathway, informing actual human Cd intake, offering scientific support for developing more effective risk assessment methods.

Characteristics and fractionations of sediment oxygen demand in a complex tidal river network area.

Tidal river networks are affected by the tide and influenced by complex factors related to sediment oxygen demand (SOD). In this study, we used chemical inhibition to measure the oxygen consumption of different types of SOD to explore the specific oxygen consumption mechanism of sediments. Then, we evaluated the diffusion fluxes of the sediment-water interface and factors affecting SOD using diffusive gradients in thin films. Total SOD in the tidal river network area of the Pearl River basin was ∼0.5928 g/m2/day, which was 8.47% higher than that in the non-tidal river network area but lower than that in black and odorous water reported previously. In the tidal river network area, biological SOD was 15.6% higher in summer than in winter, and the difference in total SOD was greatly influenced by human activity. We observed a significant effect of sediment on SOD in winter, whereas there were no significant correlations between sediment and SOD in summer. Different particle-size distributions lead to different organic matter contents, resulting in different biological SOD ratios between seasons. Our study found that seasonal tidal changes can affect ion exchange at the sediment water interface, leading to changes in SOD.These findings will be of great significance for the study of phenomena associated with low dissolved oxygen in tidal river networks and provide directions for future sediment pollution control.

Influence of different cyanobacterial treatment methods on phosphorus cycle in shallow lake microcosms.

Cyanobacterial bloom is a pressing issue affecting water supply security and ecosystem health. Phosphorus (P) released from cyanobacterial bloom during recession is one of the most important components involved in the lake P cycle. However, little is known about the consequences and mechanisms of the P cycle in overlying water and sediment due to the anthropogenic treatments of cyanobacterial blooms. In this study, treatment methods using hydrogen peroxide (H2O2), polyaluminum chloride (PAC), and the feces of silver carp were investigated for their influence on the P cycle using microcosm experiments. Results showed that H2O2 treatment significantly increased the internal cycle of sediment-related P, while PAC treatment showed minor effects. H2O2 and PAC treatment suppressed the release of P from sediment before day 10 but promoted the release of P on day 20, while silver carp treatment suppressed the release of P during the whole experiment. The reductive dissolution of iron oxide-hydroxide was the major factor affects the desorption of P. Path analyses further suggested that overlying water properties such as dissolved oxygen (DO) and oxidation-reduction potential (ORP) play critical roles in the treatment-induced sediment P release. Our results quantify the endogenous P diffusion fluxes across the sediment-water interface attributed to cyanobacterial treatments and provide useful guidance for the selection of controlling methods, with silver carp being the most recommended of the three methods studied.

Pollution and mobility of heavy metals in the soils of a typical agricultural zone in eastern China.

The pollution of heavy metals (HMs) in agricultural soils profoundly threatens national food safety, and the mobility and environmental behaviors of HMs are closely implicated in crop safety. Here, we assessed the pollution level and mobility of ten HMs and explored their environmental behaviors in the soils of three different land uses from a main crop production zone in eastern China. The concentrations of HMs in the soils were higher in the farmland than the woodland and wasteland, and Cd showed a relatively higher pollution and ecological risk levels compared to other metals. Cadmium was dominated by the reducible (41%) and exchangeable (23%) fractions, and the rest of HMs were mainly in the residual fraction (> 60%). The significant correlation between the exchangeable and DGT-labile Cd indicates relatively higher mobility of Cd in the soils. Soil pH, organic matters and mineral elements had significant correlation with the exchangeable and reducible fractions of most of the HMs (e.g., Cd, Co, Mn, Ni, Pb and V; p < 0.05), indicating their good predictors of the HMs mobility. However, this was not the case for the DGT-labile fraction, which suggests a marked difference in the controlling mechanisms of the mobility versus potential bioavailability of HMs in the soils. The results of this study indicate that both the chemically extracted fractions and the bioavailable fractions of HMs need be considered when effectively assessing the safety of agricultural soils.

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.

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.

Assessment of mercury bioavailability in garden soils around a former nonferrous metal mining area using DGT, accumulation in vegetables, and implications for health risk.

Mercury (Hg) is a toxic, non-essential element for living organisms, frequently present in high concentrations in soils from industrial areas. The total, dissolved, and labile Hg concentrations in garden soils and their accumulation in edible vegetables (onion, garlic, lettuce, and parsley) grown on contaminated soils in localities situated a former mining area were evaluated. The labile Hg fraction was estimated by diffusive gradient in thin films (DGT). The soil-to-vegetable transfer factors, as well as the health risk by exposure to Hg, were calculated based on the labile Hg concentration in soil. The total Hg concentration in soil varied widely (0.11-3.77 mg kg-1), Hg in soil solution ranged between 2.14 and 20.2 µg L-1 and labile Hg between 1.13 and 18.6 µg L-1. About 36-96% (84% on average) of the Hg concentration in soil solution was found in labile form. Multivariate analysis revealed significant correlations between the labile Hg concentration in soil and Hg accumulated in vegetables. The hazard indices showed that, although the study area is affected by legacy pollution, exposure to soil and consumption of locally grown vegetables do not pose health risks.

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.

Development of organic-diffusive gradients in thin films technique for measuring freely dissolved concentrations of tetracyclines using a commercial SPE packing.

The freely dissolved concentrations (FDCs) of pollutants are related to their bioavailability in the environment, and the diffusive gradients in thin films technique (DGT) can obtain the FDC of an analyte. Aiming for the detection of the FDCs of tetracyclines (TCs), we used a polyacrylamide hydrogel comprising acrylamide and acrylaide agarose cross-linker as diffusive and binding gels, and a commercial solid-phase extraction (SPE) packing, namely polymer sorbent (PLS), as an adsorption material in the binding gel for the preparation of the organic-diffusive gradients in thin films (o-DGT) devices. The results showed that the diffusion coefficients of tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC) in the diffusive gels were 1.08 × 10-6, 1.08 × 10-6 and 1.03 × 10-6 cm2/ s at 25 °C, respectively. The binding gel showed excellent performance with adsorption capacities of 534.88-569.42 µg/disc for TC, 527.18-565.98 µg/disc for OTC and 1320.12-1320.86 µg/disc for CTC, respectively. The uptake efficiencies were 94.21-111.12, 71.25-88.44 and 76.10-86.62% for TC, OTC and CTC, respectively, with the TCs concentration of 0.05-10 mg/L. The adsorption kinetics of TCs could be described with a pseudo-second-order model (POSM, R2 >0.97). According to the result of adsorption kinetics, the adsorption rate of TCs in the binding gel was not as fast as that of heavy metals, suggesting that the TCs concentrations at the boundary of binding gels in the o-DGT devices could not decrease to zero. After correction of the boundary concentration, the FDCs accounted for 30.30-56.90, 48.10-64.68 and 16.55-50.16% for TC, OTC and CTC, respectively, while their concentrations ranged from 0.2 to 10.0 mg/L. Our results suggested that SPE packing might be an ideal adsorption material for o-DGT binding gels, and that adsorption kinetics should be corrected when calculating the FDCs of organic pollutants.

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.

Use of diffusive gradients in thin films (DGT) to measure potentially bioavailable metals in southeastern USA blackwater streams.

We used diffusive gradients in thin films (DGT) to measure potentially bioavailable metals in coastal plain streams in the southeastern USA that exhibited strong to moderate blackwater characteristics. Metals were partitioned into particulate metals, DGT-inert metals (i.e., colloidal and refractory organic complexes not accumulated by DGT), and DGT-labile metals (i.e., free metal ions, small inorganic complexes, and labile organic complexes). We also examined the influence of different DGT deployment times using data collected from the field and a follow-up laboratory study. The DGT-measured fraction of dissolved metals in the streams was 15% for Cd, 21% for Zn, 33% for Cu, 37% for Pb, and 98% for Mn. Metals bound to particulates predominated only for Pb. Most of the Cd, Pb, Zn, and Cu were associated with colloids, refractory organic complexes, or particles. Relatively small amounts were in free ion or labile complexes likely to be bioavailable through respiratory surfaces. Modeled concentrations of free and inorganically bound Cu and Pb were lower than the DGT fraction indicating that DGT accumulated some organically bound Cu and Pb that might not have been bioavailable. DGT-exposure times in excess of 5 days may have contributed to the accumulation of partly labile organic-metal complexes and were associated with substantial biofouling that caused metal uptake by DGT to depart from linearity.

Metal fluxes at the sediment-water interface in a free water surface constructed wetland.

Metal biogeochemistry in the sediment, water, and the sediment-water interface (SWI) was studied in a free water surface constructed wetland. Concentrations of labile copper (Cu), zinc (Zn), sulfate, chloride, and dissolved organic carbon (DOC) were measured with the diffusive gradients in thin film (DGT) and peeper. A good agreement between peeper- and DGT-measured metals was observed for Cu (regression r2 = 0.3, 95% CI of the slopes > 0), but not for Zn (95% CI of the slopes overlapped with 0), which was attributed to the different complexed compounds between Cu and Zn in porewater. The depth profile of labile metals in sediment porewater varied with time and was consistent with the solid-phase metal deposition, showing higher concentrations in the surface layer (3 to - 3 cm) than in the bottom layer (- 4 to - 13 cm). The depth-averaged labile Cu and Zn concentrations measured by DGT were 1.0 and 3.1 µg/L, and labile sulfate, chloride, and DOC concentrations measured by peeper were 1.8, 3.6, and 2.1 mg/L, respectively. A sharp decrease in sulfate occurred in September when sulfate concentrations became the lowest among sampling months. This was caused by the seasonal sulfur cycles in the wetland, where the dominant sulfur reaction is sulfate reduction in warm seasons and sulfide oxidation in cold seasons. Different metal-removal mechanisms were observed in the two wetland cells; sulfur dynamics controlled the removal processes in the cell without frequent disturbance but failed to influence metal removal in the cell with frequent disturbance due to the interruption of anoxic layers. The flux ratios that compare labile element concentrations between the water column and the SWI (R-Cu, R-Zn, R-DOC, R-sulfate, and R-chloride) were generated to determine metal diffusive fluxes at the interface. Labile Zn was mostly transported from the water to the SWI during all seasons (R-Zn < 1 for all months except January). Labile Cu moved from the SWI to the water during the warm months (R-Cu < 1), which was explained by the bioturbation-induced transport of organic matter based on the positive correlations between R-Cu and R-DOC. In general, sediment can serve either as a sink or a source depending on the environmental conditions, metal speciation, and presence of living organisms. Metal flux at the SWI is a key component in the biogeochemical cycling of a constructed wetland.

Diffusive gradients in thin films (DGT) probe for effectively sampling of per- and polyfluoroalkyl substances in waters and sediments.

The passive sampling technique, diffusive gradients in thin films (DGT) has attracted increasing interests as an in-situ sampler for organic contaminants including per- and polyfluoroalkyl substances (PFAS). However, its effectiveness has been questioned because of the small effective sampling area (3.1 cm2). In this study, we developed a DGT probe for rapid sampling of eight PFAS in waters and applied it to a water-sediment system. It has a much larger sampling area (27 cm2) and as a result lower method quantification limits (0.15 - 0.21 ng/L for one-day deployment and 0.02 - 0.03 ng/L for one-week deployment) and much higher (by > 10 factors) sampling rate (100 mL/day) compared to the standard DGT (piston configuration). The sampler could linearly accumulate PFAS from wastewater, was sensitive enough even for a 24 hr deployment with performance comparable to grab sampling (500 mL). The DGT probe provided homogeneous sampling performance along the large exposure area. The use of the probe to investigate distributions of dissolved PFAS around the sediment-water interface was demonstrated. This work, for the first time, demonstrated that the DGT probe is a promising monitoring tool for trace levels of PFAS and a research tool for studying their distribution, migration, and fate in aquatic environments including the sediment-water interface.

Millimetre-resolution mapping of citrate exuded from soil-grown roots using a novel, low-invasive sampling technique.

The reliable sampling of root exudates in soil-grown plants is experimentally challenging. This study aimed at developing a citrate sampling and mapping technique with millimetre-resolution using DGT (diffusive gradients in thin films) ZrOH-binding gels. Citrate adsorption kinetics, DGT capacity, and stability of ZrOH gels were evaluated. ZrOH gels were applied to generate 2D maps of citrate exuded by white lupin roots grown in a rhizotron in a phosphorus-deficient soil. Citrate was adsorbed quantitatively and rapidly by the ZrOH gels; these gels can be stored after sampling for several weeks prior to analysis. The DGT capacity of the ZrOH gel for citrate depends on the ionic strength and the pH of the soil solution, but was suitable for citrate sampling. We generated for the first time 2D citrate maps of rhizotron-grown plants at a millimetre resolution to measure an illustrated plant response to phosphorus fertilization, demonstrating that DGT-based citrate sampling is suitable for studying root exudation in soil environments, at high spatial resolution. The change of binding material would also allow sampling of other exudate classes and exudation profiles of entire root systems. These aspects are crucial in cultivar breeding and selection.

Phosphorus removal from sediments by Potamogeton crispus: New high-resolution in-situ evidence for rhizosphere assimilation and oxidization-induced retention.

Macrophytes are usually chosen for phytoremediation tools to remove P in eutrophic aquatic ecosystems, but the lack of test methods hinders the understanding of removal mechanism and application. In this study, we used the novel technologies combined of Diffusive gradients in thin films (DGT), Planar optode (PO), and Non-invasive micro-test technology (NMT) to explore P dynamics in water-sediment continuum and rhizosphere of Potamogeton crispus over time. Results of the high-resolution in situ measurement showed that labile P(LPDGT) fluxes at the surficial sediment significantly decreased from approximate 120, 140, and 200 pg/ (cm2•sec) via 30 days incubation period to 17, 40, and 56 pg/(cm2•sec) via that of 15 days. Obvious synchronous increase of LPDGT was not detected in overlying water, suggesting the intense assimilation of dissolve reactive P via root over time. PO measurement indicated that O2 concentration around the rhizosphere remarkably increased and radially diffused into deeper sediment until 100% saturation along with the root stretch downwards. NMT detection of roots showed the obvious O2 inflow into root tissue with the uppermost flux of 30 pmol/(cm2•sec) from surroundings via aerenchyma on different treatment conditions. Different from previous reports, gradually saturating O2 concentrations around the rhizosphere was principally driven by O2 penetration through interspace attributing to root stretch downward rather than root O2 leakage. Increased O2 concentrations in deep sediment over time finally induced the oxidization of labile Fe(II) into Fe(III) bound P and local P immobilization.

In situ high-resolution measurement of phosphorus, iron and sulfur by diffusive gradients in thin films in sediments of black-odorous rivers in the Pearl River Delta region, South China.

The cycling of phosphorus (P), iron (Fe) and sulfur (S) in sediments has been previously investigated, but its impacts on the formation of black-odorous waterbodies remains unclear. Here, high-resolution (i.e., 2 mm for P and Fe, and 0.042 mm for S of 2D presentation) simultaneous measurements of P, Fe, and S profiles in river sediments based on the diffusive gradients in thin-films (DGT) technique were conducted in the Pearl River Delta region, South China. Similar distribution trends and significant positive correlations (R = 0.67-0.93, p < 0.01) were observed between Fe and P. Considering the high diffusion fluxes of Fe and P together, it revealed that P release was promoted by the Fe reduction. The two-dimensional labile S profiles showed that their concentrations in sediments were higher by factors of 1.6-20 than those in overlying water. The minor diffusion fluxes of S and the accumulation of acid volatile sulfide indicated that S2- combining with Fe2+ occurred prior to diffusion. Furthermore, the formation mechanisms of black-odorous waterbodies were explored: (i) oxygen depletion by COD and NH4+‒N and large amounts of sulfate input were the main exogenous driving factors. (ii) Reduction of Fe and S to form ferrous sulfide accompanied with P release in sediments were the dominant endogenous causes. These observations together with mechanism analysis can provide a basis for the governance of black-odorous rivers.

Arsenic redox transformations and cycling in the rhizosphere of Pteris vittata and Pteris quadriaurita.

Pteris vittata (PV) and Pteris quadriaurita (PQ) are reported to hyperaccumulate arsenic (As) when grown in Asrich soil. Yet, little is known about the impact of their unique As accumulation mechanisms on As transformations and cycling at the soil-root interface. Using a combined approach of two-dimensional (2D), sub-mm scale solute imaging of arsenite (AsIII), arsenate (AsV), phosphorus (P), manganese (Mn), iron (Fe) and oxygen (O2), we found localized patterns of AsIII/AsV redox transformations in the PV rhizosphere (AsIII/AsV ratio of 0.57) compared to bulk soil (AsIII/AsV ratio of ≤0.04). Our data indicate that the high As root uptake, translocation and accumulation from the As-rich experimental soil (2080 mg kg-1) to PV fronds (6986 mg kg-1) induced As detoxification via AsV reduction and AsIII root efflux, leading to AsIII accumulation and re-oxidation to AsV in the rhizosphere porewater. This As cycling mechanism is linked to the reduction of O2 and MnIII/IV (oxyhydr)oxides resulting in decreased O2 levels and increased Mn solubilization along roots. Compared to PV, we found 4-fold lower As translocation to PQ fronds (1611 mg kg-1), 2-fold lower AsV depletion in the PQ rhizosphere, and no AsIII efflux from PQ roots, suggesting that PQ efficiently controls As uptake to avoid toxic As levels in roots. Analysis of root exudates obtained from soil-grown PV showed that As acquisition by PV roots was not associated with phytic acid release. Our study demonstrates that two closely-related As-accumulating ferns have distinct mechanisms for As uptake modulating As cycling in As-rich environments.

Evaluation of selenium bioavailability to Brassica juncea in representative Chinese soils based on diffusive gradients in thin-films (DGT) and chemical extraction methods.

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 between the bioavailability of Se in soil and its uptake in edible parts of vegetables. This study investigated Se bioavailability of Brassica juncea in six representative Chinese soils treated with different concentrations of exogenous selenate fertilizer (0-2 mg·kg-1) by comparing diffusive gradients in thin-films (DGT) and chemical extraction methods. The correlation coefficients between the Se uptake by Brassica juncea and soil available Se determined by different extraction methods was as follows: DGT > KCl > Water > EDTA > KH2PO4 > NaHCO3 extractions. In addition, soil properties were correlated between Brassica juncea and soil Se concentrations determined by chemical extraction methods, while the DGT method was independent of soil properties. DGT was more suitable for the measurement of Se thresholds for Udic Ferrisols, Mollisols, Stagnic Anthrosols, Fluviogenic Loamy Paddy soil, Silty Loam soil, and Calcaric Regosols with values of 373.34, 648.68, 436.29, 589.84, 295.35, and 464.95 µg·L-1, respectively. Thus, DGT may be an effective method for the prediction and evaluation of Se bioavailability to Brassica juncea in different soil types.

Distribution, risk and bioavailability of metals in sediments of Lake Yamdrok Basin on the Tibetan Plateau, China.

Total contents of metals in soil and sediments on the Tibetan Plateau of China have been widely analyzed, but existing information is insufficient to effectively evaluate metal ecological risk because of a lack of metal bioavailability data. In this study, distribution, potential risk, mobility and bioavailability of metals in sediments of Lake Yamdrok Basin in Tibet of China were explored by combined use of total digestion, sequential extraction and the diffusive gradient in thin-films (DGT). Average concentrations of Cr, Ni, Cu, Zn, As, Cd and Pb in surface sediments were 31.25, 30.31, 22.00, 45.04, 31.32, 0.13 and 13.39 mg/kg, respectively. Higher levels of metals were found near the inflowing rivers. Residual form was dominant in Cr, Ni, Zn, Cd and Pb, and reducible form was dominant in As and Cd. Metals in surface sediments showed a low enrichment degree overall, but Cd and As had higher ecological risk levels than the other metals. Furthermore, there was a larger average proportion of exchangeable form of As (20.4%) and Cd (9.0%) than the other metals (1.7%-3.3%), implying their higher mobility and release risk. Average DGT-labile concentrations of Cr, Ni, Cu, Zn, As, Cd and Pb were 0.5, 4.5, 0.7, 25.1, 60.0, 0.22 and 1.0 µg/L, respectively. The DGT-labile As was significantly correlated with extractable As forms (p< 0.01), suggesting that extractable As in sediments acts as a "mobile pool" for bioavailable As. These results suggest potential risks of As and Cd, especially As, deserve further attention in Lake Yamdrok Basin.

Distribution trend of trace elements in digestate exposed to air: Laboratory-scale investigations using DGT-based fractionation.

The use of digestate as amendment for agricultural soils has already been proposed as an alternative to mineral fertilizers or undigested organic matter. However, little information is available concerning the effect of digestate atmospheric exposure on trace elements speciation and, consequently, on their mobility and bio-accessibility when digestate is stored in open tanks or handled before land spreading. In this study, we investigated at laboratory-scale the effect of digestate aeration on the distribution of Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Se and W using the diffusive gradients in thin films technique (DGT)-based fractionation. For this purpose, experiments were performed to assess the variation in distribution between the labile, soluble and particulate fractions over time in digested sewage sludge during passive and forced aeration. Results showed that aeration promoted a dissolution of Al, As, Co, Cr, Cu, Fe, Mn, Mo and Pb, suggesting a possible increase in their mobility that may likely occur during storage in open tanks or handling before land spreading. Labile elements' fraction increased only during forced aeration (except for Fe and Mn), suggesting that their short-term bio-accessibility can increase only after significant aeration as the one assumed to occur when land spreading takes place.