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.

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.

Application of DGT/DIFS combined with BCR to assess the mobility and release risk of heavy metals in the sediments of Nansi Lake, China.

The heavy metal contamination of the aquatic ecosystem is still prevalent even after reduction of the external anthropogenic inputs of the metals. The release of labile heavy metals from the sediments into the water is a potential risk, responsible for the contamination of the aquatic system. Herein, samples of sedimentary column cores were collected in Nansi Lake, and the distribution profiles of the labile and soluble metals (Cd, Cu, Ni, Pb, and Zn) were obtained by the diffusive gradient in thin films (DGT) and the high-resolution dialysis (HR-peeper) technique. Furthermore, the mobility, bioavailability and release risk of the heavy metals were assessed using the results of geochemical sequential extraction, DGT as well as the DGT-induced fluxes in sediments (DIFS) model. The results showed that the profile characteristics of the DGT-labile and soluble heavy metals showed irregular distribution in the sediment cores and Cd, Pb, Zn had an obvious positive correlation with Fe/Mn (p < 0.05). Ni, Cu, and Zn existed primarily in the residual fraction (accounting for 58-76%), while Cd and Pb existed in the reducible fraction (accounting for 50-67%). The Cd and Ni (0.027-0.185) had higher mobility coefficients compared with Pb, Cu, and Zn (0-0.011), and positive diffusive fluxes also proved that Cd and Ni were easy to be released from the sediments. In addition, the R values of five metals (0.18-0.85) ranged between Rdiff to 0.95, indicating that all the metals had partially sustained case from the sediments solid phase. Based on the DIFS model, the five metals had weak mobility from the sediment to pore water, but the release risks in the Nansi Lake should also be of concern, especially for the highly mobile Cd and Ni in the Dushan Lake.

Phosphorus availability and dynamics in soil affected by long-term ruzigrass cover crop.

The use of grasses as cover crops in the off-season of cash crops under no-till has been largely adopted. However, soil phosphorus (P) uptake was previously shown to be reduced when ruzigrass is introduced in the rotation, affecting the viability and sustainability of this cropping system. The objective of this study was to assess the effect of ruzigrass on soil P availability and desorption kinetics under different P fertilizer application rates. A long-term field experiment where soybean (Glycine max) has been grown in rotation with ruzigrass (Urochloa ruziziensis) or fallow for 10 years, with the application of 0, 13, and 26 kg ha-1 of P, was evaluated for two consecutive years. Soil P desorption kinetics was assessed using diffusive equilibrium (DET) and gradient in thin films (DGT) techniques, as well as the DGT-induced fluxes in soils model (DIFS). Microbial biomass P (MBP) was assessed to verify if soil solution P (PDET) was reduced due to immobilization by microorganisms. Ruzigrass reduced MBP and PDET especially when P fertilizer was applied. The concentration of labile P (PDGT) was also lower after ruzigrass than in fallow. The soil ability to resupply P to soil solution was lower after ruzigrass regardless of P rates due to a slower desorption in response to the perturbation imposed by DGT. Growing ruzigrass as cover crop in the soybean off-season decreases soil P availability regardless of P fertilizer application rates by fundamentally reducing P mobility and P resupply from soil solid phase into soil solution.

Assessment of labile Zn in reservoir riparian soils using DGT, DIFS, and sequential extraction.

The middle route of the South-to-North Water Diversion project alleviates drought in northern China, especially reducing water shortage pressure in Beijing. However, after submersion, the potential release risk of metals in newly submerged soils into the water in the receiving reservoir remains unclear. Here, we assess the labile Zn in the riparian soils of Miyun Reservoir (MYR) using the diffusive gradients in thin films (DGT), DGT-induced fluxes in soils (DIFS) model, and Community Bureau of Reference (BCR) sequential extraction. The results showed that the average Zn concentrations at three sampling sites (S2, S3, and S5) exceeded soil background value (74.8 mg/kg), indicative of Zn accumulation in the MYR. The concentrations of DGT-labile Zn varied within 39.7-62.4 µg/L (average: 56.7 µg/L), with the greatest value observed at 145 m at sampling site S3, attributed to anthropogenic activities in recreational areas. The DGT-labile Zn showed no correlation with classes of land, elevations, or soil properties. Sequential extraction results demonstrated that Zn predominantly existed in the residual fraction, but still showed a strong capability for resupply from the solid phase (R >1). The DIFS model simulation results showed that Zn underwent irreversible diffusion of intra-particle metals from the solid phase to the soil solution. Therefore, the potential release risk of labile Zn in riparian soils in MYR cannot be ignored, especially for areas experiencing human disturbance.

Comprehensive evaluation of the distribution, transport and ecological risk of heavy metals in intra-urban river sediments using high-resolution techniques.

Determining the distribution trends, transport mechanisms, and ecological risks of heavy metals (HMs) in urban river sediments is essential for the government to conduct appropriate remediation work. In this study, we collected sediment cores from the Yayao Waterway in Foshan City, China. The vertical distribution profiles of dissolved and labile Fe, Mn, Cd, Zn, Cu, Cr, Ni, Pb, As, and Co in the sediments were obtained using the thin-film diffusive gradient (DGT) and high-resolution peeper (HR-Peeper) techniques. In addition, the transport rates, contamination levels, and ecological concerns of the HMs were evaluated using the European Community Bureau of Reference (BCR) sequential extraction technique, the DGT-induced sediment fluxes (DIFS) model, and multiple contamination evaluation metrics. The results showed that most of the DGT-labile HMs were associated with Fe/Mn (hydrogen) oxides, and in particular, Zn, Ni, and Cr showed a significant negative correlation with Fe/Mn (p < 0.001). Additionally, Cd had the highest bioavailability (89.17%), and its net diffusive flux at the sediment-water interface (SWI) was positive, which indicated a high release risk from the sediment. However, the R-value of Cd based on the DGT-induced sediment fluxes (DIFS) operation was extremely low, suggesting that although Cd had the biggest supply pool of releases, its release rate was slow. The majority of sampling sites had significantly higher total HM contents in the surface sediments than the background values. The HM contamination in the sediments originated from human activities, primarily from industrial enterprises and with a large contribution from both agricultural and domestic sources. The most polluted HM with the highest ecological danger was Cd, followed by Cu, Zn, Ni, and As when the results of the four pollution evaluation indicators were combined. Consequently, the risk of contamination by HMs in inner-city river sediments should receive more attention.

Diffusion kinetic processes and release risks of trace metals in plateau lacustrine sediments.

The ecological risk posed by trace metals in the plateau lacustrine sediments of China has attracted worldwide attentions. A better understanding of the kinetic diffusion processes and bioavailability of these metals in plateau lakes is needed. Using the diffusive gradient in thin films (DGT) and Rhizon, concentrations of Mn, Mo, Ni, Cr, and Co in the sediments, labile fractions, and interstitial water of Lake Fuxian were comprehensively analyzed. According to the DGT-induced fluxes in sediments (DIFS) model, fully sustained and unsustained resupplies are possible ways in which metals are released from solids to the solution. Moreover, the resupply characteristics of metals varied at different depths in the sediments and at different sites in the lake. Based on the DIFS model, the effective concentrations (CE) of the trace metals were calculated and all except Cr showed good linear relationships with the DGT-labile concentrations, indicating that the CE values were valuable for predicting metal bioavailability. According to the CE values, the metal contamination released from the sediments was relatively low based on the Monte Carlo simulation. This study provides a comprehensive solution for studying the environmental behavior and potential ecological risks of toxic metals in sedimentary environment.

Coastal degradation regulates the availability and diffusion kinetics of phosphorus at the sediment-water interface: Mechanisms and environmental implications.

Coastal wetlands have experienced considerable loss and degradation globally. However, how coastal degradation regulates sediment phosphorus (P) transformation and its underlying mechanisms remain largely unknown in subtropical coastal ecosystems. This study conducted seasonal field measurements using high-resolution diffusive gradient in thin films (DGT) and dialysis (Peeper) techniques, as well as a DGT-induced fluxes in sediments (DIFS) model, to evaluate the mobilization and diffusion of P along a degradation gradient ranging from pristine wetlands to moderately and severely degraded sites. We observed that sediment P is diminished by coastal degradation, and severely degraded sites exhibit a decline in the concentration of available P, despite the presence of distinct seasonal patterns. High-resolution data based on DGT/Peeper analysis revealed that labile P and soluble reactive P (SRP) concentrations varied from 0.0006 mg L-1 to 0.084 mg L-1 (mean 0.0147 mg L-1) and from 0.0128 mg L-1 to 0.1677 mg L-1 (mean 0.0536 mg L-1), respectively. Coastal degradation had a substantial impact on increasing SRP and labile P concentrations, particularly at severely degraded sites. Although severely degraded wetlands appeared to be P sinks (negative P flux at these sites), we did also observe positive diffusive flux in October, indicating that coastal degradation may accelerate the diffusion and remobilization of sediment P into overlying water. The simulations of the DIFS model provided compelling proof of the high resupply capacity of sediment P at severely degraded sites, as supported by the increased R and k-1 values but decreased Tc values. Taken together, these results suggest coastal degradation reduces the sediment P pool, primarily attributed to the strong remobilization of P from the sediment to porewater and overlying water by enhancing the resupply capability and diffusion kinetics. This acceleration induces nutrient loss which adversely impacts the water quality of the surrounding ecosystem. To reduce the adverse effects of coastal degradation, it is essential to adopt a combination of conservation, restoration, and management efforts designed to mitigate the risk of internal P loading and release, and ultimately maintain a regional nutrient balance.

Mercury distribution, mobilization and bioavailability in polluted sediments of Scheldt Estuary and Belgian Coastal Zone.

In this study, the vertical distribution of mercury (Hg) in estuarine and marine sediment porewaters and solid phases was assessed by conventional and passive sampling techniques in the historically polluted Scheldt Estuary and Belgian Coastal Zone (BCZ). The Diffusive Gradients in Thin-films (DGT) measured labile Hg concentrations (HgLA) were mostly lower than the porewater Hg concentrations (HgPW), and they also presented different vertical distribution patterns. Still high Hg concentrations in the sediment solid phases, comparable to the historical ones, were observed. Even though pH, redox potential and dissolved sulfide concentration could influence the Hg biogeochemical behaviour, organic matter (OM) played a key role in governing Hg mobilization from sediment solid phase to porewater and in its partitioning between porewater and solid phase over depth. In the marine sediments, where OM had a marine signature, higher labile Hg concentrations in the porewater and faster resupply from the solid phase were observed. The DGT technique showed significant potential not only for the measurement of bioavailable Hg fractions in porewater, but also for the assessment of kinetic parameters governing the release of labile Hg species from the solid phase with the assistance of the DGT Induced Fluxes in Sediments (DIFS) model.

Principles, applications, and limitations of diffusive gradients in thin films induced fluxed in soils and sediments.

The diffusive gradients in thin films (DGT) technique serves as a passive sampling method, inducing analyte transport and concentration. Its application is widespread in assessing labile components of metals, organic matter, and nutrients across various environmental media such as water, sediments, and saturated soils. The DGT devices effectively reduce the porewater concentration through irreversible binding of solutes, consequently promoting the release of labile species from the soil/sediment solid phase. However, the precise quantification of simultaneous adsorption and desorption of labile species using DGT devices alone remains a challenge. To address this challenge, the DGT-Induced Fluxes in Soils and Sediments (DIFS) model was developed. This model simulates analyte kinetics in solid phases, solutions, and binding resins by incorporating factors such as soil properties, resupply parameters, and kinetic principles. While the DIFS model has been iteratively improved to increase its accuracy in portraying kinetic behavior in soil/sediment, researchers' incomplete comprehension of it still results in unrealistic fitting outcomes and an oversight of the profound implications posed by kinetic parameters during implementation. This review provides a comprehensive overview of the optimization and utilization of DIFS models, encompassing fundamental concepts behind DGT devices and DIFS models, the kinetic interpretation of DIFS parameters, and instances where the model has been applied to study soils and sediments. It also highlights preexisting limitations of the DIFS model and offers suggestions for more precise modeling in real-world environments.