Diffusive Gradients In Thin Films Research Articles

An international intercomparison exercise on passive samplers (DGT) for monitoring metals in marine waters under a regulatory context

In order to move forward in the acceptance of a novel contaminant monitoring technique (Diffusive Gradients in Thin-films: DGT) for assessment of marine water bodies, sensu the WFD, an Inter-Laboratories Comparison (ILC) exercise (nine Europeans laboratories) was organized in the framework of the Interreg Atlantic Area MONITOOL project, which focused on the use of the DGT technique for the measurement of WFD priority metals (Cd, Ni and Pb).Reproducible results were obtained for each metal by several laboratories, supporting the assertion that DGT analysis can be performed satisfactorily by laboratories experienced in measuring metals at trace levels in marine environments, even if they have limited practice in DGT analysis.According to the Z-score analysis, among the 9 participating laboratories, 3 had 100 % of satisfactory results for Cd, Ni, and Pb, 3 had >80 % satisfactory results and 2 had about 60 % satisfactory results.This work highlights the need to clearly describe the DGT method in order to control sources of contamination during analytical steps, in particular the resin gel retrieval and the elution steps.Such international intercomparison exercise is an important step to develop the laboratory network involved in DGT analysis and contributes to the improvement of data quality.

Influence of ZnO Particle Size and Soil Characteristics on the Estimation of Long-Term Zn Bioavailability by Chemical Extraction Methods and Diffusive Gradients in Thin-Films (DGT)

The aim of this paper is to explore whether the long-term bioavailability of Zn in different soils can be predicted using operational extraction procedures. Green peas and beetroot were grown in two soils with contrasting physicochemical characteristics. Two Zn sources of different sizes (ZnO-nano or ZnO-bulk) were applied 1 year earlier, at different Zn application rates. The amounts of available Zn were assessed using the diffusive gradients in thin films (DGT) technique and different chemical extraction procedures: water-soluble (WS), CaCl2, rhizosphere-based low-molecular-weight organic acid (LMWOAs), DTPA-TEA, and NH4Ac. The different correlation and regression studies showed that the estimation of availability is dependent on the soil categorical variable, especially in the beetroot crop. Zn-DGT could be used to estimate the Zn concentration of the aerial part of the green pea using a general model for both soil and ZnO sizes. The estimation of long-term Zn bioavailability was successful using either medium-strength extractive solutions or the DGT technique. The extraction methods involving complexing agents or buffered salt solution overestimated the amount of bioavailable Zn in calcareous soil. Further studies will be necessary to know the amounts of Zn associated with the different soil fractions.Graphical abstract

Arsenic extraction from seriously contaminated paddy soils with ferrihydrite-loaded sand columns

Reductive dissolution of iron oxides in flooded paddy soils is the most important cause of arsenic (As) release into soil aqueous solution and thus entry into rice. From the perspective of soil cleanup, however, As release under flooded condition could facilitate labile As removal. In this study, a porous column pre-loaded with ferrihydrite (Fh) was constructed, and its efficiency of soil As extraction was investigated using a purpose-designed mesocosm coupled with diffusive gradients in thin films (DGT) for in situ visualization. With Fh-column deployed in aqueous solution, >90% removal of As(III) was achieved within 5 days at initial As (100 mg L−1) of two orders of magnitude higher than in most paddy soil solutions (1–1538 μg L−1). By applying Fh-column in a seriously contaminated paddy soil (102 mg As kg−1), porewater As showed stepwise decreases from 2727 μg L−1 to 129–1455 μg L−1 at a distance-dependent manner over four intermittent extractions during 91 days. Soil DGT-As exhibited similar spatiotemporal changes to porewater As. After four extractions, 17.8% of total soil As was removed by Fh-column in a 10 cm radius range on average and ∼1/3 of As bound to amorphous and crystalline Fe/Al oxides was depleted, which accounted for 88.7% of decline in total soil As. With the post-extracted soil, a 48% lower As accumulation in rice seedlings and a 65% decline in bulk soil DGT-As were attained. This study provides a conceptual foundation for rapid removal of high soluble As by Fh-columns from flooded soils, improving seriously As-contaminated paddies to sustainable resources for safe food production.

Micro/nanostructured MgO hollow spheres with selective adsorption performance and their application for fluoride monitoring in water

The search for suitable adsorbents for fluoride removal and accurate measurement are important issues in the field of water research. Adsorbents with micro/nanostructure are beneficial to highly efficient adsorption due to their high surface area and structural stability. Inspiredly, novel micro/nanostructured porous MgO hollow spheres were prepared by a hydrothermal and subsequent annealing process. The obtained product exhibited micro/nanostructured porous hollow sphere morphology with a diameter of approximately 5 μm and a BET surface area of 43.10 m2·g−1. Importantly, the hollow spheres showed enhanced adsorption performance toward fluoride ions with a maximum adsorption capacity up to 175.00 mg·g−1 and an adsorption rate of 17.72 mg·g−1 ·min−1 compared with the commercial MgO nanoparticles with such value of 149.19 mg·g−1 and 3.92 mg·g−1·min−1, respectively. Ion-exchange coupled with electrostatic interactions was responsible for the adsorption mechanism. Such micro/nanostructured MgO is suited for use in a diffusive gradient in thin films (DGT) as a binding phase to measure trace fluoride ions in aqueous environments. Laboratory experiments verified that the performance of MgO-DGT was independent of pH and ionic strength. Furthermore, field deployments were achieved in Yihai Lake of our campus with CDGT-YH and Csoln-YH (the active grab sampling) results of CDGT-YH/Csoln-YH = 1.01. Therefore, MgO-DGT can accurately monitor trace fluoride concentration in water bodies. This work not only reveals a strategy for preparing micro/nanostructured MgO with enhanced adsorption performance but also provides a new micro/nanostructured MgO based DGT for fluoride monitoring in natural water bodies.

Bioavailable actinide fluxes to the Irish Sea from Sellafield-labelled sediments

Nuclear discharges to the oceans have given rise to significant accumulations of radionuclides in sediments which can later remobilise back into the water column. A continuing supply of radionuclides to aquatic organisms and the human food chain can therefore exist, despite the absence of ongoing nuclear discharges. Radionuclide remobilisation from sediment is consequently a critical component of the modelled radiation dose to the public. However, radionuclide remobilisation fluxes from contaminated marine sediments have never been quantitatively determined in-situ to provide a valid assessment of the issue. Here, we combine recent advances in the Diffusive Gradients in Thin Films (DGT) sampling technique with ultrasensitive measurement by accelerator mass spectrometry (AMS) to calculate the remobilisation fluxes of plutonium, americium and uranium isotopes from the Esk Estuary sediments (UK), which have accumulated historic discharges from the Sellafield nuclear reprocessing facility. Isotopic evidence indicates the local biota are accumulating remobilised plutonium and demonstrates the DGT technique as a valid bioavailability proxy, which more accurately reflects the elemental fractionation of the actinides in the biota than traditional bulk water sampling. These results provide a fundamental evaluation of the re-incorporation of bioavailable actinides into the biosphere from sediment reservoirs. We therefore anticipate this work will provide a tool and point of reference to improve radiation dose modelling and contribute insight for other environmental projects, such as the near-surface and deep disposal of nuclear waste.

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 - 3cm) than in the bottom layer (- 4 to - 13cm). The depth-averaged labile Cu and Zn concentrations measured by DGT were 1.0 and 3.1µg/L, and labile sulfate, chloride, and DOC concentrations measured by peeper were 1.8, 3.6, and 2.1mg/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.

Application of diffusive gradients in thin films to determine rare earth elements in surface sediments of Daya Bay, China: Occurrence, distribution and ecotoxicological risks

Known as burgeoning contaminants, the bioavailability of rare earth elements (REEs) can be determined using diffusive gradients in thin films (DGT). As Daya Bay (South China) has been under serious anthropogenic influences, the present study examined the distribution of REEs in surface sediments and their possible ecological risks in the bay. The range of DGT-labile concentrations of REEs (∑REEs) was from 5.67 μg/L to 8.41 μg/L, with an average of 7.34 μg/L. Results of assessment of single REE toxicity revealed that the risk quotient (RQ) values of Y, Ce and Yb were >1, indicating that their potential negative impacts on the nearby environment. However, analysis of the integral toxicity of REE mixtures through assessment of probabilistic ecotoxicological risks showed that there was a negligibly low probability of toxicity of PRE surface sediments to aquatic organisms in the study area.

Inhibition of sediment internal phosphorus release in agricultural drainage ditches by ceria nanoparticle capping.

In this study, ceria nanoparticles (CNPs) were introduced as an in-situ capping agent to inhibit the release of phosphorus (P) from sediments of agricultural drainage ditches. High-resolution dialysis (HR-Peeper) and diffusive gradients in thin film (DGT) techniques were used to measure the concentrations of P and iron (Fe) in the overlying water and sediments. The results showed that the CNP capping not only decreased the soluble reactive P (SRP) in the overlying water by 55.36% but also decreased the SRP in the pore water by 30.06%. More importantly, after the CNP capping, the flux of SRP from the pore water to the overlying water decreased by 34.12%, indicating that CNP capping can effectively inhibit the release of P from sediments to the overlying water. In addition, 38.38% of DGT-labile P was immobilized using CNP capping. Furthermore, the results of P speciation showed that CNP capping led to the change of P species from easily released NH4Cl-extractable P (NH4Cl-P) and Na2S2O4/NaHCO3-extractable P (BD-P) to more stable HCl-extractable P (HCl-P) and residual P (Res-P). These results show that CNP capping can further decrease the release of P from sediments to the overlying water. The present study shows that CNP is a feasible and effective capping material to inhibit the release of P from sediments of agricultural drainage ditches.

Crab bioturbation drives coupled iron-phosphate-sulfide cycling in mangrove and salt marsh soils

Coastal wetlands sequestering abundant blue carbon in soils are biogeochemical hotspots and critical habitats for benthic animals like invertebrate fiddler crabs. Here, we reveal how crab bioturbation (i.e., burrowing activity) drives the redox geochemistry of ferrous iron (Fe(II)), phosphate (PO43-), and sulfide (S(-II)) under contrasting vegetation types and hydrological conditions. We used in-situ approaches of diffusive gradients in thin films to perform detailed mm-scale burrow observations in two subtropical wetlands with a vegetation gradient of mudflat-salt marsh-mangrove. Burrow flushing caused a top-down hydrologic connectivity through the crab burrows and thus created a deep depth for the occurrence of Fe(III) reduction and sulfate reduction which were accompanied by P mobilization. The burrow oxidation zone, indicated by lower concentrations of Fe(II), PO43- and S(-II), were shallower in mudflats and salt marshes than in mangroves due to the unique respiratory roots of mangrove plants. The redox of Fe(II), PO43- and S(-II) in crab burrow was insensitive to the convection flow-induced input of dissolved oxygen through the surrounding soil matrix, indicating the burrow soil is an independent microenvironment. Crab burrowing activities favored Fe-S coupling which is conductive the formation of pyrite and alkalinity generation. Overall, our in-situ high-resolution observations and porewater hydraulic dynamics revealed spatially variable soil geochemistry, active coupled cycling of Fe-P-S in crab burrows, and mm-scale hotspots of redox cycling within burrows.

The variations of labile arsenic diffusion driven by algal bloom decomposition in eutrophic lake ecosystems

The vertical labile arsenic (As) concentration and diffusion pattern variations in eutrophic lakes were investigated using in situ techniques of diffusive gradients in thin films (DGT) and high-resolution dialysis (HR-Peeper) in the typical eutrophic system of Lake Taihu in China. In addition, simulation experiments were used to reveal labile As distributions in sediment profiles under the influence of algae blooms and wind fluctuations. Our results indicated that eutrophication could lead to the migration and transformation of As fractions, including increased As bioavailability, as well as varied diffusion patterns. The sulfate released from algae decomposition reduced to H2S and formed FeS, which weak adsorbability contributed to the increased mobility of the As fractions. Meanwhile, further decomposition released a large quantity of algae-derived organic matter which competed with the adsorbed As, leading to more endogenous As migrating to the overlying water. Accordingly, the H2S production presented a likely explanation for the changed distribution of labile As and contributed to labile As concentrations in the sediment profiles significantly increasing at depths of −20 mm to −60 mm in the early stages of the simulation experiment. Moreover, the areas of enhanced diffusion patterns with high concentrations of As obviously expanded. However, following the complete decomposition of the algae, the organic matter component significantly changed, suggesting an explanation for the variations in distribution of labile As. All the diffusion pattern variations showed similar trends. Consequently, variation of labile As diffusion patterns could indicate the decomposition and eutrophication levels of freshwater ecosystems.

In-situ biochar amendment mitigates dietary risks of heavy metals and PAHs in aquaculture products

Heavy metals (HMs) and polycyclic aromatic hydrocarbons (PAHs) are two common contaminant groups of concern in aquaculture products. While biochar amendment can be one of the solutions to immobilize these contaminant in pond sediment, its in situ effectiveness in mitigating the bioavailability, tissue residue, and dietary risk of these contaminants is yet to be tested. In this study, we added wheat straw biochar in sediments of three aquaculture ponds with polyculture of fish and shrimps and employed passive sampling techniques (i.e., diffusive gradient in thin film for HMs and polydimethylsiloxane for PAHs) to assess the diffusion flux and bioavailability throughout the culturing cycle. Reduction in HM concentrations in organisms by biochar after 28 weeks ranged from 17% to 65% for benthic organisms and from 6.0% to 47% for fish. ΣTHQs values of HMs dropped from 2.5 to 2.1 and 1.2 to 0.91 for the two organisms with the initial ΣTHQs value above 1.0. The decrease rates of both the concentrations and ΣTHQs values followed the order of Cu > Cr > Pb > Cd, which was closely correlated with the speciation of HMs in the sediments. ΣPAHs values dropped significantly at the growth stage (20th week) and the mature stage (28th week), and, on average, by 34% across all the organisms. Carcinogenic PAHs in aquaculture products decreased dramatically at the seedling stage (12th week), while there was no significant change observed for the Incremental Lifetime Cancer Risk values. By comparing the freely-dissolved concentrations in pore water of sediments and the overlying water, consistently enhanced diffusion fluxes of HMs and PAHs from water to sediment over the whole culturing cycle were obtained. Our results demonstrated the in situ applicability of biochar amendment to remediating chemical pollution in aquaculture environment and safeguarding quality of aquatic products.

Seasonal variation in release characteristics and mechanisms of sediment phosphorus to the overlying water in a free water surface wetland, southwest China

Geochemical cycling of iron (Fe) mediated by sediment microbes drives the remobilization of phosphorus (P). Understanding the underlying mechanism is essential for the evaluation of P retention by wetlands. The diffusive gradients in thin film (DGT) and 16S rDNA sequencing techniques were combined to explore seasonal variations in the remobilization mechanism of sediment P in a free water surface wetland in southwest China. A significantly positive correlation between labile P and Fe concentrations was found from the sediment profiles, indicating coupled remobilization of Fe and P in the sediment. Fe-reducing bacterial genera, particularly Sphingomonas and Geothermobacter, were responsible for the reductive dissolution of Fe oxides and subsequent P release in sediment. The efflux of sediment P was higher in the rainy season (95 ± 87 ng cm−2 d−1) than in the dry season (39 ± 29 ng cm−2 d−1). Based on the significantly positive relationship between the efflux and total concentration of sediment P, we propose a promising regression equation for quantifying the release risk of sediment P. The Luoshijiang Wetland exhibited a higher release potential as indicated by a greater regression slope (0.558) compared to the other water bodies (0.055), which was mainly attributed to the lower labile Fe:P molar ratio in the sediment. Based on estimations of the diffusive flux of P at the sediment-water interface, sediment contributed more than 172 and 413 g of P per day to the water column in the dry and rainy seasons, respectively, accounting for 14.0% and 1.9% of the P mass in the surface water of the wetland.

Dual diffusive gradients in the thin films (DGT) probes provide insights into speciation and mobility of sediment chromium (Cr) from the Xizhi River basin, South China

Investigation of the speciation and remobilization mechanisms of chromium (Cr) in sediment is essential for accurate estimation of its ecological risks in aquatic systems. In this work, a three-step chemical extraction procedure and diffusive gradient in thin films (DGT) technique were combined to investigate the geochemical speciation, mobility potentials, and release characteristics of sediment Cr. The geochemical speciation of sediment Cr decreased in the following order: oxidizable > reducible > residual > acid-soluble fraction. Dissociation of OM-bound Cr(III) and oxidation by Mn oxides contributed to higher labile Cr(III) and Cr(VI) levels in winter, with the labile Cr(III) being the dominant species and accounting for 48.1%65.5% of the total concentration of labile Cr; whereas, reductive dissolution of Mn oxides was responsible for the remobilization of labile Cr(VI) in summer, leading to a shift in dominant Cr species to Cr(VI) (48.9%65.7%) due to rapid precipitation of Cr(III). Sediment acted as a major sink for labile Cr(VI) in two sampling campaigns. For labile Cr(III), sediment converted from source in winter to sink in summer. The diffusive release of labile Cr(III) deserves preferential concern due to its potential to be re-oxidized to more toxic Cr(VI) under the oxic conditions of river water in winter.

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), 17β-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.

Biogeochemical behavior of P in the soil and porewater of a low-salinity estuarine wetland: Availability, diffusion kinetics, and mobilization mechanism

Estuarine wetlands, which typically store large amounts of phosphorus (P), are experiencing increased salinity as well as changed environmental factors caused by rising sea levels. In this study, the seasonal dynamics of P speciation, availability, and biogeochemical couplings with iron (Fe)-sulfur (S) in soil and porewater were measured in a low-salinity estuarine wetland using in situ high-resolution diffusive gradients in thin films (DGT) and dialysis (HR-Peeper) techniques. The diffusion kinetics and resupply capacity of P from the soil phase to solution were simulated using a DGT-induced fluxes in soils (DIFS) model. The transition from freshwater to brackish wetlands reduced soil P pools and shifted to more recalcitrant speciation. The concentration of DGT-labile P across the soil-water profiles ranged from 0.002 to 0.039 (mean: 0.015) mg L−1, which increased with increasing salinity in both the field and mesocosm experiments. The distributions of labile and soluble P showed high heterogeneity across the profiles, and there were some sharp peak values below the soil-water interface (SWI), which significantly increased the concentration and lability of P. The strong coupling between labile P and Fe (S) provided direct evidence for the coexistence of iron reduction (IR) and sulfate reduction (SR) in the estuary, while IR might predominate in P mobilization in the brackish environment because of higher labile Fe concentrations and stronger Fe-P couplings. The diffusion fluxes of P were positive at both sites, demonstrating that the kinetics of P were from the soils to the overlying water. Higher R and k-1 values fitted in the DIFS model implied that a stronger resupply capacity and desorption rate and thus faster remobilization kinetics of P occurred with increasing salinity. Our findings indicated that increased salinity (even at low levels) can alter the desorption rate and resupply capacity of soil P in estuarine wetlands and accelerate P remobilization and release by regulating the IR and SR processes, thereby leading to the deterioration of water quality.

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.

Novel hyphenation of DGT in-situ passive sampling with YES assay to ascertain the potency of emerging endocrine disruptors in water systems in New Zealand

This study represents the first attempt to investigate selected estrogenic compounds that include 17α-ethynylestradiol (EE2), 17β-estradiol (E2) bisphenol A (BPA), and bisphenol AF (BPAF) along the drinkable water, from river-to-tap, and wastewater, from effluent-to-treated wastewater, treatment processes of the Hamilton City Council and the monitoring of the freshwater, from source-to-outfall, of the Waikato River in New Zealand. This was accomplished by the adoption of a novel combination of diffusive gradients in thin films (DGTs) in-situ passive sampling coupled with high-performance liquid chromatography/mass spectrometry analysis (HPLC/MS) and the Yeast Estrogen Screen (YES). Estradiol equivalency quantities, integrated in time, were evaluated theoretically (cEEQ) by DGT-HPLC/MS and experimentally (EEQ) by DGT-YES assay. cEEQ and EEQ highlighted that primary treatments are not suitable for estrogens and bisphenolic plastics removal both at drinkable and wastewater treatment plants in Hamilton where they worsen the water quality in terms of estrogenicity making these pollutants more available in the water phase. All downstream sites monitored along the Waikato River showed higher cEEQ and EEQ, moreover the Waikato River water quality showed a moderate worsening moving from Taupo (source) to Tuakau (outfall). The most polluted sites were downstream of Hamilton city and Huntly township wastewater treatment plants that serve the main conurbations in the area. cEEQ and EEQ generally showed good agreement at low concentrations but differed substantially at more polluted sites where cEEQ consistently underestimated estrogenic potency, possibly due to DGT accumulation of estrogenic compounds not quantified by HPLC/MS.

Wheat yield prediction by zero sink and equilibrium-type soil phosphorus tests

Diffusive gradients in thin films (DGT) measurements have been shown to outperform other phosphorus (P) tests in soils with strong P sorption, but this has not been confirmed for moderately weathered European soils. We compared the performance of DGT in predicting wheat grain yield in Swedish long-term fertility experiments with those of standard intensity (water-extractable P (P-H 2 O)) and quantity (ammonium lactate-extractable P (P-AL)) tests. A Mitscherlich-type model was used to fit wheat yield response to P application rates (0, 15, 30 or 35, and 45 kg P ha -1 year -1 ) in each individual trial replicate to estimate the maximum yield. For trials with clear plateau-type yield responses and the goodness of fit ( R 2 ) > 0.75, relative yields (RYs) were calculated for each P treatment and plotted against the soil P test results ( n = 143). The goodness of the Mitscherlich-type fits decreased in the following order: DGT-measured P (P-DGT) ( R 2 = 0.35) > P-H 2 O ( R 2 = 0.18) > P-AL ( R 2 = 0.13). When excluding soils with P-AL:P-DGT ≥ 0.1 L g -1 , R 2 was considerably improved to 0.55 for P-AL, 0.46 for P-H 2 O, and 0.65 for P-DGT ( n = 61). At 95% of maximum yield, the upper limit of P deficiency for P-DGT was 44.8 (the soils with P-AL:P-DGT < 0.1 L g -1 ) and 61.9 μg L -1 (all soils), falling within the range reported for other European and Australian soils (6.0–142 μg L -1 ). We show that in the investigated Swedish soils, DGT performed better than the quantity and intensity tests, which is attributed to its ability to capture P diffusion and resupply from the soil solid phase, similar to plant roots in the rhizosphere.

Risk on assessment of 15 REEs and mixtures by DGT in Songhua River system sediments of China's largest old industrial base

Rare earth elements (REEs) are increasingly used in the high-tech sectors in the world and are therefore called burgeoning contaminants. As diffusive gradients in thin films (DGT) can be used to assess the bioavailability of inorganic matters, in this paper, we evaluated, for the first time, the ecotoxicology risks of REEs and their mixtures in river sediments of China's old industrial base by DGT. During our research, taking the Songhua River system (SRS) as an example, we detected its surficial sediments, of which the DGT-labile concentration of REEs (∑REEs) was 2.07–8.76 μg/L. As for the single toxicity, the risk quotient (RQ) values of Y at all sites were significantly greater than 1; while the values of Nd and Pr in some upstream reaches were all significantly greater than the threshold (1), indicating that these adverse effects of single REEs were not neglected. In terms of the combined toxicity of REEs mixtures, we carried out an assessment of the risks of probabilistic ecotoxicology, which showed that the SRS superficial sediments had a low probability of toxicity to aquatic organisms (0.54%).

The mechanistic investigation of geochemical fractionation, bioavailability and release kinetic of heavy metals in contaminated soil of a typical copper-smelter

Identifying the bioavailability and release-desorption mechanism of heavy metals (HMs) in soil is critical to understand the release risk of HMs. Simultaneously, the mechanistic investigation of affecting the bioavailability of HMs in soil is necessary, such as the grain-size distribution and soil mineralogy. Herein, the bioavailability of HMs (Cu, Cd, Ni, Pb, and Zn) in different area soils near a typical copper-smelter was evaluated by the sequential extraction technique (BCR), diffusive gradients in thin-films (DGT), and DGT-induced fluxes in sediments (DIFS) model. Results showed that the HMs proportion of the residual fraction in all soils was the highest. The average bioavailability concentration (CDGT) of Cu and Cd in industrial soil was the highest, with 45.12 μg· L−1 and 9.06 μg· L−1. The result of DIFS model revealed that the decreased order of the mean value of desorption rate constant (K-1) was Cd > Zn > Ni > Cu > Pb, 5.91 × 10−5, 4.96 × 10−5, 2.89 × 10−5, 9.64 × 10−6, and 8.69 × 10−6, respectively. According to the spatial distribution of release potential (R-value), the release potential of labile-Cu in agricultural soil was the highest, which was mainly attributed to fertilizer application in farmland. Simultaneously, the reduced hydroxyl was also related to the agricultural activities, resulting in the weakened adsorption capacity of HMs by soil. Redundancy analysis (RDA) results showed that the bioavailability of Cd, Ni, and Zn was mainly driven by soil pH, while the bioavailability of Cu and Pb was primarily driven by dissolved organic carbon (DOC). Meanwhile, carbonate minerals had a positive correlation with the bioavailability of Cd, Ni, and Zn, which could promote the release of HMs in mining soil as chemical weathering progresses. In conclusion, this study provides a structured method which can be used as a standard approach for similar scenarios to determine the geochemical fractionation, bioavailability, and release kinetics of heavy metals in soils.