Diffusive Gradients In Thin Films Research Articles

Removal, fate, and bioavailability of fluoroquinolone antibiotics in a phytoremediation system with four wetland plants: Combing dynamic DGT and traditional methods

Phytoremediation is considered an effective technology for remediating antibiotic-contaminated water; however, its underlying mechanisms remain poorly understood. Therefore, this study investigated the phytoremediation potential of fluoroquinolone antibiotics (FQs) by different wetland plant species. The phytoremediation rates of ΣFQs were 46–69 %, and rhizosphere microorganism degradation (accounting for 90–93 %) dominated the FQ removal over that of plant uptake and hydrolysis. Dissipation of the FQs in the hydroponic system followed a first-order kinetic model. The joint action of the more powerful absorptive capacity of plants and stronger microbial degradation ability in the rhizosphere was the reason that Cyperus papyrus showed significantly higher FQ phytoremediation rates than the other three plant species, which implied that the plant species is a critical factor affecting phytoremediation efficiency. The FQ distribution in plant tissues decreased from root > stem > leaf, suggesting that FQs were more concentrated in the roots than in the aboveground tissues. Negative correlations between the diffusive gradient in thin films and root concentrations implied that these wetland plant species took up FQs mainly via active transport mechanism (requiring some vectors, perhaps via exudates); whereas, the process of root-to-stem transfer and upward transport represented passive transport, which mainly depended on transpiration. These results facilitate an improved understanding of phytoremediation processes and improve their future applications.

Effects of sediment resuspension and changes in water nutrient concentrations on the remobilization of lead from contaminated sediments in Klity Creek, Thailand

As Pb-containing sediments in Klity Creek have had negative impacts on the area for more than 20 years, the Supreme Court ordered the Pollution Control Department (PCD) of Thailand to remediate the site. In response to the court order, the PCD decided to reduce the contamination level by dredging the sediments of the creek. Therefore, this study is the first investigation to be conducted on the coupled effects of sediment resuspension caused by dredging and changes in water nutrient concentrations upon the remobilization of Pb from sediments into the water column. The Pb concentrations and speciation in both the water and sediments collected from upstream and downstream regions of the contaminated area were determined. The results showed that the total Pb concentrations in the water taken from all sampling sites in both the dry and wet seasons were lower than the national standard (50 μg/L), and a very low mobility index was found for Pb. The highest total Pb concentration in the sediments (6930 mg/kg) from the downstream site was 23.7- to 30.4-fold greater than those of the sediments collected from the upstream site. The predominant Pb species (organic and residual Pb fractions) in the sediments collected during the dry season were identified. However, carbonate- and Fe–Mn oxide-bound Pb fractions were mainly found in the sediments collected in the wet season. The diffusive gradients in thin films (DGT)-labile Pb concentrations, which reached 2.1 mg/L, indicated potential toxicity to aquatic organisms. A total of nine resuspension scenarios generalizing all changes in water nutrient concentrations in addition to sediment resuspension due to dredging were constructed. The results confirmed that sediment resuspension alone could remobilize Pb from the sediments into the water at levels from 0.06 to 16.9 μg/L. Sediment resuspension in water contaminated with 1 mg/L phosphate (PO43−) led to the dissolution of 28.4–73.0 μg/L Pb in the water column. Nitrate (NO3−) did not significantly remobilize Pb from the sediments into the water. The high ionic strength and activity coefficient of PO43− in the water were expected to cause the retention of dissolved Pb in the water and enhance the remobilization of Pb from the sediments due to the association of Pb with PO43− in the water.

Effects of Five–Year Inorganic and Organic Fertilization on Soil Phosphorus Availability and Phosphorus Resupply for Plant P Uptake during Maize Growth

A better understanding of the P dynamic resupply roles of fertilization from soil solids to solution is urgently required to optimize sustainable P fertilizer management practices for efficient supply. A five–year fertilization experiment was used to investigate the effects on soil P fractions and availability, the kinetic P resupply based on a novel simulation technique (Diffusive gradients in thin films (DGT) and DGT–induced fluxes in sediments and soils (DIFS) ) and to identify dominant factors during the maize season under five treatments (no fertilizer (CK), chemical fertilizer (NPK), chemical fertilizer combined with bone meal fertilizer (NPKC), crop straw (NPKS) and bioorganic fertilizer (NPKM)). The results showed that the NPKC and NPKM treatments had higher enhancement effects on Olsen–P and organic P and inorganic Ca2–P, Ca8–P, Al–P and Fe–P at maize growth stages, and they buffered pH decrease to delay the substantial Fe–P and Al–P release until a late stage. Inorganic Ca2–P, Ca8–P, Al–P and Fe–P heavily effected the Olsen–P levels. The NPKS, NPKC and NPKM treatments yielded higher CDGT–P levels and a stronger resupply capacity, reflected by higher R and CE/Csoln and smaller Tc values. The simulation and path model results revealed that the maize plant P uptake was determined by soil P resupply and an inorganic P supply pool. They were positively dominated by soil organic matter (SOM). Our results suggested that organic fertilization, especially NPKC and NPKM treatments, provided greater enhancement effects on the P supply pool and P resupply for higher plant P uptake, identifying them as highly effective P management practices for developing sustainable agriculture.

Synergistic effect of vermiculite and submerged plants on lake sediments

The synergistic effect of vermiculite and the submerged macrophytes Vallisneria spiralis and Hydrilla verticillata on lake sediment was studied using diffusive gradients in thin films (DGT) technology. The dynamics of phosphorus (P) fractions in sediment, the labile-P and labile-S in the water-sediment continuum, and the microbial community in the rhizosphere were studied. Vermiculite effectively promoted reproduction of microorganisms in the sediments Microbial abundance in treatments containing V. spiralis with sediments containing 10% added vermiculite, and H. verticillata containing 50% added vermiculite being 1.7 and 3.5 times higher than the controls which contained no added vermiculite. Acidobacteria and Proteobacteria populations, which are both beneficial for the sediment microenvironment, were higher in treatment groups containing vermiculite. The bioavailable-P in treatment groups containing added vermiculite was lower at the sediment-water interface, with a correlating decrease of TP by between 63% and 91% in the overlying water. This suggests that vermiculite can affect the release of labile P and facilitate the assimilation of nutrients by macrophyte roots. Additionally, vermiculite can improve the Oxidation-Reduction potential and further reduce sulfide toxicity to plants. These results provide theoretical guidance and technical support for the application of vermiculite combined with submerged plants for the remediation of eutrophic lakes.

Probabilistic ecotoxicological risk assessment of heavy metal and rare earth element mixtures in aquatic biota using the DGT technique in coastal sediments

Heavy metals (HMs) are routine contaminants due to their extensive use worldwide. Rare earth elements (REEs) are emerging contaminants because of their global exploitation for use in the high-tech sector. Diffusive gradients in thin films (DGT) are an effective method for measuring the bioavailable component of pollutants. This study represents the first assessment of the mixture toxicity of HMs and REEs in aquatic biota using the DGT technique in sediments. Xincun Lagoon was chosen as the case study site because it has been contaminated by pollutants. Nonmetric multidimensional scaling (NMS) analysis reveals that a wide variety of pollutants (Cd, Pb, Ni, Cu, InHg, Co, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb) are primarily impacted by sediment characteristics. Appraisal of single HM-REE toxicity reveals that the risk quotient (RQ) values for Y, Yb and Ce notably exceeded 1, demonstrating that the adverse effects of these single HMs and REEs should not be ignored. The combined toxicity of HM-REE mixtures in terms of probabilistic ecological risk assessment shows that the Xincun surface sediments had a medium probability (31.29%) of toxic effects on aquatic biota.

Impact of inorganic and organic pollutants from a Belgian wastewater treatment plant on adjacent surface and groundwaters

Under the pressure of global droughts and water shortage, it is essential to evolve toward a sustainable and robust water system. One possible avenue is the maximum reuse of treated wastewater, but the quality of which determines its reuse. Therefore, inorganic (Cd, Pb, Cr, Ni, Cu, and As) and organic (xenoestrogens and polycyclic aromatic contaminants, PACs) contaminants were monthly monitored in an effluent of the wastewater treatment plant (WWTP), the surrounding surface waters and the local groundwater in Belgium. Dissolved and particulate concentrations of inorganic contaminants in these water bodies were analyzed. In addition, Diffusive Gradients in Thin-films (DGT) was used in situ to obtain bioavailable metal fractions. In the WWTP effluent and surface waters, only Ni exceeds the Annual Average-Environmental Quality Standard (AA-EQS), while in the groundwater, dissolved As was the predominant element. Moreover, in the surface and effluent waters the highest lability degrees were observed for Cd and Ni. The concentrations of these metal species in the effluent water were lower than in the other water bodies. Micro-organic pollutants, xenoestrogens and PACs were analyzed by dual Estrogen and Aryl hydrocarbon Receptor - Chemical Activated LUciferase gene eXpression (ER & AhR-CALUX) assays. Since the annual averaged (AA) bioequivalent concentration of E2 (0.18 ng/L) is below the AA-EQS standard (0.4 ng/L), and the bioequivalent concentration of benzo[a]pyrene never exceeded the maximum admissible concentration (MAC), the reclamation and reuse of treated wastewater for groundwater replenishment and agricultural irrigation should pose no environmental problems, at least in a short-term.

Arsenic migration at the sediment-water interface of anthropogenically polluted Lake Yangzong, Southwest China

The lability and controlling factors of arsenic (As) at the sediment-water interface (SWI) are crucial for understanding As behaviors and fates in As-contaminated areas. In this study, we combined high-resolution (5 mm) sampling using diffusive gradients in thin films (DGT) and equilibrium dialysis sampling (HR-Peeper), sequential extraction (BCR), fluorescence signatures, and fluorescence excitation-emission matrices (EEMs)-parallel factor analysis (PARAFAC) to explore the complex mechanisms of As migration in a typical artificially polluted lake, Lake Yangzong (YZ). The study results showed that a high proportion of the reactive As fractions in sediments can resupply pore water in soluble forms during the change from the dry season (winter, oxidizing period) to the rainy season (summer, reductive period). In dry season, the copresence of Fe oxide-As and organic matter (OM)-As complexes was related to the high dissolved As concentration in pore water and limited exchange between the pore water and overlying water. In the rainy season, with the change in redox conditions, the reduction of Fe-Mn oxides and OM degradation by microorganisms resulted in As deposition and exchange with the overlying water. Partial least squares path modelling (PLS-PM) indicated that OM affected the redox and As migration processes through degradation. Based on comprehensive analyses of the As, Fe, Mn, S and OM levels at the SWI, we suggest that the complexation and desorption of dissolved organic matter and Fe oxides play an important role in As cycling. Our findings shed new light on the cascading drivers of As migration and OM features in seasonal lakes and constitute a valuable reference for scenarios with similar conditions.

Geochemical controls on the distribution and bioavailability of heavy metals in sediments from Yangtze River to the East China Sea: Assessed by sequential extraction versus diffusive gradients in thin-films (DGT) technique

This study conducted a comprehensive investigation on the distribution and bioavailability of heavy metals (Cr, Co, Ni, Cu, Zn, Cd and Pb) in sediments along two typical transects from Yangtze River to the East China Sea continental shelf that spanning large physicochemical gradients. Heavy metals were mainly associated with the fine-grained sediments (enriched with organic matter), exhibiting decreasing trends from nearshore to offshore sites. The turbidity maximum zone showed the highest metal concentrations, which evaluated as polluted for some tested metals (especially Cd) using the geo-accumulation index. Based on the modified BCR procedure, the non-residual fractions of Cu, Zn and Pb were higher within the turbidity maximum zone, and significantly negatively correlated with bottom water salinity. The DGT-labile metals all positively correlated with the acid-soluble metal fraction (especially for Cd, Zn and Cr), and negatively correlated with salinity (except Co). Therefore, our results suggest salinity as the key factor controlling metal bioavailability, which could further modulate metal diffusive fluxes at the sediment-water interface. Considering that DGT probes could readily capture the bioavailable metal fractions, and reflect the impacts of salinity, we suggest DGT technique can be used as a robust predictor for metal bioavailability and mobility in estuary sediments.

Combining ultrafiltration and diffusive gradients in thin films techniques for speciation/fractionation of Cu and Zn in cytosol of liver of Nile tilapia (Oreochromis niloticus).

This work aims to evaluate the size and lability of Cu and Zn bound to proteins in the cytosol of fish liver of Oreochromis niloticus by employing solid-phase extraction (SPE), diffusive gradients in thin films (DGT), and ultrafiltration (UF). SPE was carried out using Chelex-100. DGT containing Chelex-100 as binding agent was employed. Analyte concentrations were determined by ICP-MS. Total Cu and Zn concentrations in cytosol (1g of fish liver in 5ml of Tris-HCl) ranged from 39.6 to 44.3ng ml-1 and 1498 to 2106ng ml-1, respectively. Data from UF (10-30kDa) suggested that Cu and Zn in cytosol were associated with ∼70% and 95%, respectively, with high-molecular-weight proteins. Cu-metallothionein was not selectively detected (although 28% of Cu was associated with low-molecular-weight proteins). However, information about the specific proteins in the cytosol will require coupling UF with organic mass spectrometry. Data from SPE showed the presence of labile Cu species of ∼17%, while the fraction of labile Zn species was >55%. However, data from DGT suggested a fraction of labile Cu species only of 7% and a labile Zn fraction of 5%. This data, as compared with previous data from literature, suggests that the DGT technique gave a more plausible estimation of the labile pool of Zn and Cu in cytosol. The combination of results from UF and DGT is capable of contributing to the knowledge about the labile and low-molecular pool of Cu and Zn.

Mercury methylation potential and bioavailability in the sediments of two distinct aquatic systems

This study explored mercury (Hg) methylation potential in two distinct aquatic systems. Fourmile Creek (FMC) was historically polluted with Hg effluents from groundwater as it is a typical gaining stream, where organic matter and microorganisms in streambed are continuously winnowed. The H02 constructed wetland only receives atmospheric Hg and is rich in organic matter and microorganisms. Both systems receive Hg from atmospheric deposition now. Surface sediments were collected from FMC and H02, spiked with inorganic Hg, and cultivated in an anaerobic chamber to stimulate microbial Hg methylation reactions. Total mercury (THg) and methylmercury (MeHg) concentrations were measured at each spiking stage. Mercury methylation potential (MMP, %MeHg in THg) and Hg bioavailability were assessed with the deployment of diffusive gradients in thin films (DGTs). During the methylation process and at the same incubation stage, FMC sediment showed faster increasing rates of %MeHg and higher MeHg concentrations than H02, demonstrating a stronger MMP in the FMC sediment. Similarly, higher Hg bioavailability was observed in FMC sediment compared to the H02 as indicated by DGT-Hg concentrations. In conclusion, the H02 wetland with high levels of organic matter and microorganisms presented low MMP. But the Fourmile Creek as a gaining stream and a historical site of Hg pollution showed strong MMP and high Hg bioavailability. A related study on microbial community activities characterized the microorganisms between FMC and H02, which is attributed to be the main reason for their different methylation capabilities. Our study further brought up the considerations on remediated sites from Hg contamination: Hg bioaccumulation and biomagnification can still be elevated and higher than the surrounding environment due to lagged changes in microbial community structures. This study supported the sustainable ecological modifications of legacy Hg contamination and raised the necessity of long-term monitoring actions even after executing a remediation plan.

Interest of a new large diffusive gradients in thin films (L-DGT) for organic compounds monitoring: On-field comparison with conventional passive samplers

In this work, the performances of a Large Diffusive Gradients in Thin films (L-DGT, i.e., a DGT based on a Chemcatcher® holder with a 5-fold larger sampling area) were compared on-field with the conventional DGT and the Polar Organic Chemical Integrative Sampler (POCIS) for the monitoring of a wide range of organic contaminants (i.e., 65 pesticides and metabolites, 53 pharmaceuticals and 12 hormones). These three passive samplers were simultaneously deployed in four rivers during 14 days. Their performances were then evaluated according to their detection and quantification capacities and their physical robustness. The results obtained confirm the advantages of the L-DGT over the conventional DGT regarding its sensitivity but also its robustness during field deployment. The POCIS provides the higher sensitivity, allowing the detection of more organic compounds compared to the DGT and, to a lesser extent, the L-DGT. However, both L-DGT and DGT reduces the uncertainty on the determination of the time-weighted average concentrations (CW), mainly due to the narrow range of variation of their calibration parameters. Indeed, for a given compound, CW can vary up to only a 3-fold factor with DGT and L-DGT compared to a 2 to 10-fold factor (up to 50) with POCIS. Thus, the L-DGT appears to be more suitable than DGT in low-contaminated contexts, which require higher sensitivity, or than POCIS when a CW determination is needed. For a qualitative evaluation however, the POCIS remains the most suitable passive sampler.

DGT method for the in situ measurement of triazines and the desorption kinetics of atrazine in soil.

Triazines are frequently detected in nature water and agricultural soils worldwide. They are considered harmful to plants, animals, and the human health. In this study, diffusive gradients in thin films (DGT) method was developed for the assessment of several triazines. DGT device was used for the in situ measurement of atrazine in a pesticide factory and obtained reliable data. The atrazine concentrations measured by DGT, and solvent extraction method was in a constant ratio. The DIFS model was coupled with DGT technique to study the desorption kinetics of atrazine in four kinds of different soils. The yellow-brown soil was more inclined to adsorb atrazine than other three soils. 2_D DIFS model was used to obtain the partition coefficient for labile atrazine (Kdl), the values of the response time (Tc), and desorption/adsorption rates (k1 and k-1). The yellow-brown soil has a larger labile pool size, and a faster resupply speed of atrazine. The 1_D DIFS model was used to simulate the profiles of atrazine concentrations in soil solution and solid phase. The results show that the desorption of atrazine in soil was limited by kinetic limitation at short time, and was limited by the solid phase reservoir at long time.

Diffusive gradients in thin films for transfer of phosphorus, nitrate and ammonium in lake sediments

There is a lack of the understanding of the transfer of phosphate (PO4-P), ammonium (NH4-N) and nitrate (NO3-N) at the millimeter scale in sediments related to internal loadings in the semi-arid and cold Lake Hulun in China. In this paper, a passive sampling technique-diffusion gradients in thin films (DGT) has been used for the biogeochemical behaviors and dynamic transfer of PO4-P, NH4-N and NO3-N in sediments in this lake. The two-sided DGT probe (AMP-TH&ZrO-Chelex) and ZrO DGT piston are designed for sediment/water interface. Based on change characters of DGT concentration profiles (nutrients, Fe and Mn) related to redox status and chemical properties, N and P mobilizations are derived. The reductive dissolution of Mn(IV) or Fe(III) (oxyhydr)oxides accounts for subsequent P release is corresponded with the oxic or anoxic status in sediment layers; Fe(III)-reduction is the main reason for P remobilization. The breakdown of algae biomass deposited on the uppermost sediment and phosphatase enzymes activity enhanced by NH4-N also lead to P remobilization. In sub-anoxic or anoxic layer, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) induce exchangeable ammonium (NH4ex) enrichment and NH4-N release, while, anammox depletes NH4-N mobility. Aerobic nitrification results in NO3-N remobilization. Organic matter favors NH4-N release. DGT induced fluxes in sediments (DIFS) model is used to derive the labile P pool (51.5–465.5 cm3 g−1), resupply constant (0.186–0.734), response time (54–11,070 s) and Dspt rate (32–382,517 nmol cm−3 d−1) for describing dynamic P transfers with two opposite types of “slow” and “fast” resupplies. The diffusive fluxes across sediment/water interface in ranges of 67.9–498.7 μg m−2 d−1 (PO4-P), −1416–106.8 (NH4-N) and –2147–301.1 μg m−2 d−1 (NO3-N) and DIFS parameters can be used for release risks in lake regions and the sediment remediation strategies are recommended.

Assessing the bioavailability of antibiotics in soil with the diffusive gradients in thin films (DGT)

The diffusive gradients in thin films (DGT) technique is an excellent method for investigating the dynamic processes of antibiotics in soils. However, whether it is applicable in antibiotic bioavailability assessment is yet to be disclosed. This study employed DGT to determine the antibiotic bioavailability in soil, and compared the results with plant uptake, soil solutions, and solvent extraction methods. DGT exhibited predictive capability for plant taking in antibiotics proved by the significant linear relationship between the DGT based concentration (CDGT) and antibiotic concentration in roots and shoots. Although the performance of soil solution was acceptable based on linear relationship analysis, its stability was weaker than DGT. The results based on plant uptake and DGT indicated the bioavailable antibiotic contents in different soils were inconsistent because of the distinct mobility and resupply of sulphonamides and trimethoprim in different soils, as represented by Kd and Rds, which were affected by soil properties. Plant species played an important role in antibiotic uptake and translocation. Antibiotic uptake by plants depends on antibiotic, plant and soil. These results confirmed the capability of DGT in determining antibiotic bioavailability for the first time. This work provided a simple and powerful tool for environmental risk evaluation of antibiotics in soils.

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.

Effects of overwintering cyanobacteria on phosphorus and iron regeneration across the sediment-water interface: A pilot simulation experiment

Cyanobacterial blooms are a major environmental problem in eutrophic reservoirs in China. Algal cells can migrate to the sediment surface in winter and maintain biological activity, which could further affect the cycling process of sediment phosphorus (P) and iron (Fe). In this study, a pilot simulation experiment was conducted to investigate the effect of overwintering cyanobacteria (Owc) on P and Fe regeneration across the sediment-water interface (SWI). Owc esterase activity ranged from 16.4 to 26.6 nmol (FDA)/(L·h), with a fluctuating increasing trend within the incubation time. Compared with the control (no Owc), Owc treatment increased the redox potential value (Eh) at the SWI but slightly decreased the pH during the first stage of this experiment (0–24 d); however, the Eh at the SWI under Owc treatment decreased to 50.9 % of that of the control on day 90. The Fe(II) could rapidly oxidized to Fe (oxyhydro)oxides and combine with phosphate in high Eh environments, and Owc inhibited P and Fe release at the SWI within 24 days; however, the continuous decrease in Eh resulted in the reduction of Fe(III). Thus, the Fe concentration measured via diffusive gradients in thin films in the Owc-treated interstitial water gradually increased to 1.92 times that of the control, promoting the release of Fe and P across the SWI. For 13 days after Owc addition, the amount of mobile P in the sediment was significantly higher than that in the control, and it gradually decreased from day 24 to 90, with the lowest being approximately 74.1 % of the amount in the control. The reactive Fe concentration in the sediment showed a similar variation trend. These results indicate that mobile P and reactive Fe in the sediment could be the main sources of regeneration across the SWI in the presence of Owc.

Simultaneous determination of heavy metal concentrations and toxicities by diffusive gradient in thin films containing Acinetobacter whole-cell bioreporters (Bio-DGT)

Heavy metal contaminations may cause severe toxic impacts to ecological systems and human health. Measurements of metals' bioavailable concentrations and toxicities simultaneously and in-situ in environments can advance the understanding of their hazardous effects. The diffusive gradients in thin-films (DGT) is an in-situ technique can measure metal speciation and labile concentrations, but cannot yet provide the direct toxicity information. The whole-cell bioreporter Acinetobacter baylyi ADPWH_recA was successfully incorporated into the DGT device to develop a novel technique, Bio-DGT, for assessing the toxicity of metals at the same time of measuring their labile concentrations. The bioassay used in Bio-DGT can sense the mixture toxicity from multiple contaminants and the DGT can assist in identifying which toxicants may be causing the toxicity. Cadmium was used as the model metal to test the performance of Bio-DGT in waters and soils. The masses of Cd accumulated in Bio-DGT increased linearly and theoretically with time for 7 days deployment, indicating little influences from bioreporter cells on DGT performance. A positive relationship between bioluminescent signals towards Cd demonstrated the sensitive and active bioreporters' response. The sensitive of Bio-DGT, indicated by Cd concentrations causing the response, is 0.01 mg/L. The stable response from Bio-DGT under various conditions (pH 4–8, ionic strengths 0.01–0.5 M) and 30 days storage time suggest the applicability of the technique in real environments. The deployment of Bio-DGT in contaminated soils demonstrated that Cd toxicity was regulated by labile concentration, showing its potential application for the risk assessment of heavy metal contaminations, and its further feasibility in using Bio-DGT for measuring integration of multiple contaminants’ effects and simultaneously determine the main toxicity driver(s).

Geochemistry and release risk for nutrients in lake sediments based on diffusive gradients in thin films.

A comprehensive understanding of the mobility of both nitrogen (N) and phosphorus (P) and the inter-relationships between P, N, and iron (Fe) in sediments is important for controlling the "internal loadings" of nutrients in lakes. In this research, diffusive gradients in thin film (DGT) assemblies with binding layers (ZrO-AT, chelex, and ZrO) were designed for PO4-P, Fe, ammonium (NH4-N), and nitrate (NO3-N) at sediment/water interface (SWI) in Western Lake Taihu (China). The biogeochemical processes of N and P related to the physicochemical properties, the dynamic P transfer, the distribution characteristics of P microniches, and the estimation of the release risks in sediments in Western Lake Taihu were simultaneously revealed by the passive sampling technique-DGT with the high spatial resolutions (millimeter and sub-millimeter). Based on DGT concentration (CDGT) related to physicochemical properties in sediments, (1) P biogeochemical reactions included P release from Fe-bound P during Fe reduction, algae biomass decomposition, and phosphatase enzyme activity increased by NH4-N; (2) denitrification and dissimilatory nitrate reduction to ammonium (DNRA) led to exchangeable ammonium (NH4ex) enrichment and NH4-N release; anammox depleted NH4-N transfer; organic matter (OM) mineralization favored NH4-N release; and (3) aerobic nitrification led to NO3-N remobilization; denitrification and DNRA reduced NO3-N release. Redox status, OM, Fe, aluminum, or calcium influenced mobilization of nutrients. The numerical model of DGT-induced fluxes in sediments was used for dynamic P transfers with resupply types ("slow" ~ "fast") controlled by labile P pool, resupply constant, response time, and Dspt rate. The formation of P microniches in two dimensions was revealed. Sediment P release risk index (0.49 ~ 36.85 [lg (nmol cm-3 d-1)]) with "light" ~ "high" risks and diffusive fluxes across SWI (µg m-2 d-1) of 15.0 ~ 639 (PO4-P), - 1403 ~ 5010 (NH4-N), and - 1395 ~ 149 (NO3-N) were derived and lake management strategies were provided. The DGT technique provides the characterization of the mobilization of nutrients and evidence for biogeochemical processes at the fine spatial scales for control of internal loadings in sediments.

Substantial increase in P release following conversion of coastal wetlands to aquaculture ponds from altered kinetic exchange and resupply capacity

The reclamation of wetlands and its subsequent conversion to aquaculture may alter regional nutrient (im)mobilization and cycling, although direct assessments of phosphorus (P) cycling and its budget balance following wetland conversion are currently scarce. Here, parallel field experiments were conducted to investigate and compare the availability and mobilization mechanisms of P from natural coastal wetlands and the adjacent converted aquaculture ponds based on high-resolution diffusive gradient in thin films (DGT) and dialysis (HR-Peeper) techniques and the DGT-induced fluxes in sediments (DIFS) model. The study found that the conversion of wetland to pond strongly reduced the sediment P pool by changing its forms and distribution. High-resolution data showed that concentrations of labile P and soluble reactive P across the sediment–water profiles were markedly enhanced by the converted aquaculture pond, although they exhibited large spatiotemporal heterogeneity. Moreover, the synchronous distribution of labile P, iron (Fe) and sulfur (S) across profiles in coastal wetlands indicated that the dissolution of Fe (III) oxyhydroxide–phosphate complexes coupled with sulfate reduction were the main mechanisms regulating sediment P mobilization in coastal areas. However, the converted aquaculture pond weakened or even reversed this dependence by decoupling the Fe-S-P reactions by changing the sediment structure and nutrient balance. Substantial increases in labile P, Fe and S fluxes in the pond suggested the conversion of wetland to aquaculture facilitated the internal release of P, Fe and S from sediment into water. The high resupply parameter (R) and desorption rate (k-1) combined with low response time (Tc) in the pond, as fitted by DIFS model, indicated the strong resupply capacity and fast kinetic exchange of sediment P across the sediment–water interface, which is consistent with the high P diffusion fluxes recorded in the pond. It was concluded that converted aquaculture ponds act as an important source of P release in coastal areas, potentially exacerbating water quality degradation and eutrophication. Specific initiatives and actions are therefore urgently needed to alleviate the internal P-loading during aquaculture.

Nonmetric multidimensional scaling and probabilistic ecological risk assessment of trace metals in surface sediments of Daya Bay (China) using diffusive gradients in thin films

This research is one main objective to assess combined toxicity of trace metal mixtures in aquatic biota in coastal sediments. Coastal sediments around the world are a major reservoir of trace metals from industrial wastewater discharge. Our case study site, Daya Bay in southern China, was selected because it has been under severe man-made impacts. Diffusive gradients in thin films (DGT) technique has proven to be a good method for measuring the bioavailability of trace metals. The bioavailability and distribution of trace metals in surface sediments were investigated along with their possible biological risks. The average bioavailable (DGT-labile) concentrations (μg/L) were 0.44 (V), 0.51 (Cr), 52.49 (Mn), 0.10 (Co), 1.36 (Ni), 0.74 (Cu), 14.53 (Zn), 0.97 (As), 0.14 (Se), 6.73 (Mo), 0.17 (Cd), 0.27 (Sb), 0.10 (W), and 1.32 (Pb). Nonmetric multidimensional scaling (NMS) is a robust multivariate ordination method that makes no assumptions about the distribution of the underlying data. NMS was used to explore that DGT-labile concentrations of trace metals were influenced by sediment properties. NMS results indicated that most DGT- labile trace metals influenced by sediment properties. Risk assessment of single trace metal toxicity revealed that risk quotient (RQ) values for Mn, Cu, Zn and Pb significantly exceeded 1, demonstrating that the toxic effects of these trace metals should be not ignored. The probabilistic ecological risk assessment for integral toxicity of one mixture of 14 trace metals revealed that Daya Bay surface sediments had a low probability (9.04 %) of adverse effects on aquatic biota.