Effects of nZVI on the migration and availability of Cr(VI) in soils under simulated acid rain leaching conditions.

Hexavalent chromium, Cr(VI), is a ubiquitous toxic metal that can be reduced to Cr(III) by nano-zero-valent iron (nZVI). Finding out effects of continuous rainfall leaching on the Cr(VI) release and availability remains a problem, needing to be addressed. Whether the Cr(VI) reduction by nZVI and continuous rainfall leaching lead to localized heterogeneity in soil is unclear. Therefore, two in situ high-resolution (HR) techniques of the diffusive gradients in thin-films (DGT) and planar optode were combined with ex situ sampling experiments here. Results demonstrate that nZVI decreased Cr(VI) leaching by 5.60-8.50 % compared to control soils. DGT-measured concentrations of Cr(VI), CDGT-Cr(VI), ranged from 7.31 to 19.4 µg L-1 in the control soils, increasing with depth while CDGT-Cr(VI) in nZVI-treated soils (2.41-6.18 µg L-1) decreased or remained stable with depth. However, simulated acid-rain leaching increases CDGT-Cr(VI) by 1.61-fold in nZVI-treated soils, negatively affecting the remediation. DGT measurements in bulk soils using disc devices are better at capturing the change of Cr(VI) availability at different conditions, whereas 2D-HR DGT mappings did not characterize significant mobilization of Cr(VI) at the micro-scale. These findings emphasize the importance of monitoring Cr(VI) release and availability in remediated soil under acid-rain leaching conditions for effective environment management.

Development and evaluation of diffusive gradients in thin-films technique with a novel titanium peroxide binding gel for in situ measurement of Tl in natural waters and sediments.

Speciation of thallium (Tl) controls its fate and biogeochemical behaviors. Thus, a sensitive and accurately approach for Tl monitoring is of great demand due to its ultra-low concentration and sensitivity to redox change. In this study, diffusive gradients in thin-films technique (DGT) assembled with novel titanium peroxide (TP) binding gels (TP-DGT) was developed for in situ measurement of dissolved Tl(I) and Tl(III) in waters and sediments. Laboratory test showed a linear mass accumulation of Tl(I) and Tl(III) on the TP binding gels with the deployment time from 4 to 72 h. A fascinating performance of this novel DGT was achieved in a pH range of 4-9, ionic strength range of 0.1-200 mmol L-1, and humic acid concentration of 0-30 mg L-1 with a low detection limit of 0.3 ng L-1 for Tl(I) and 0.6 ng L-1 for Tl(III). The TP binding gels own excellent stability (1-365 d) and high capacity (73.5 µg Tl disc-1) which are suitable for long-term monitoring. Field application in a river indicated that TP-DGT could work effectively, comparable to the grab sampling in waters. For the first time, the TP-DGT coupled with oxygen optode was successfully applied to map 2D distribution patterns of Tl and oxygen simultaneously in the rhizosphere of M. verticillatum L. This study confirms TP-DGT is a promising tool for routine monitoring of Tl in waters and for investigating biogeochemical processes of Tl in sediments.

Distinct response of arsenic speciation and bioavailability to different exogenous organic matter in paddy soil.

Land application of organic waste has been increasingly encouraged since it could sequester carbon to mitigate climate change. Considering the susceptibility of arsenic (As) bioavailability in soils to organic matter, understanding the influence of different exogenous organic matter on As biogeochemical behavior in rice-soil system is crucial to reasonably recycle organic waste on soils and ensure the food safety. In this study, impacts of two typical organic matter amendments, rice straw and humic substance, on the As speciation and bioavailability in paddy soil were investigated. Results showed that addition of both rice straw and humic substance could increase the dissolved organic carbon (DOC) content in soil solution by 16.4%-34.4% and 21.7%-53.2%, respectively, but the response of As speciation and bioavailability was quite different, showing the decoupling between As release and DOC. Rice straw addition increased As release to porewater by 28.0%-28.4%, particularly at the initial 0-18 days after the soil was flooded, but humic substance presented the opposite effect, decreasing As release by 27.4%-43.1% which was mainly attributable to the AsIII immobilization. This study suggests that the organic matter with high contents of labile heteroaliphatic/aliphatic carbon, being easily to be biodegraded, should not be applied on As contaminated soils.

A Novel In Situ Method for Simultaneously and Selectively Measuring AsIII, SbIII, and SeIV in Freshwater and Soils.

Anthropogenic and climatic perturbations redistribute arsenic (As), antimony (Sb), and selenium (Se) within the environment. The speciation characteristics of these elements determine their behavior and biogeochemical cycling, but these redox-sensitive species are challenging to capture, with few methods able to harmonize measurements across the whole plant-soil-ecosystem continuum. In this study, we developed a novel diffusive gradient in thin films (DGT) method based on aminopropyl and mercaptopropyl bi-functionalized mesoporous silica spheres (AMBS) to achieve in-situ, simultaneous, and selective quantification of AsIII, SbIII, and SeIV, three typical/toxic but difficult to measure inorganic species. When used for environmental monitoring within a river catchment, AMBS-DGT exhibited stable/accurate predictions of these species despite varying water chemistries (ionic strength 0.01-200 mmol L-1 NO3-, pH 5-9 for AsIII and SbIII, and pH 5-7.5 for SeIV). Furthermore, river deployments also showed that time-averaged species concentrations by AMBS-DGT were reproducible compared with high-frequency sampling and measurement by high performance liquid chromatography coupled with inductively coupled plasma mass spectroscopy. When AMBS-DGT was used for sub-mm scale chemical imaging of soil solute fluxes, the method resolved concomitant redox-constrained spatial patterns of AsIII, SbIII, and SeIV associated with root O2 penetration within anaerobic soil. Improved capabilities for measurement of compartment interfaces and microniche features are critical alongside the measurement of larger-scale hydrological processes that dictate the fine-scale effects, with the AMBS-DGT achieving this for AsIII, SbIII, and SeIV.

Validation and Assessment of Diffusive Gradients in Thin-Films (DGT) Technique for Measuring Nutrients in Taihu Lake Water with Algae Bloom.

DGT (diffusive gradients in thin films) technique has been developed for measuring nitrogen in freshwaters and applied to assess the bioavailability of phosphorus in soils/sediments. These two elements are the main nutrients causing algae bloom, but DGT has never been used in the field water conditions with algae bloom. In our study, a pair of DGT devices were used in comparison with grab sampling to characterize the performance of this technique to measure labile NO3-N, NH4-N, and PO4-P concentrations in algae-cultivated Taihu Lake water. The results showed that DGT measurement was highly affected by algae bloom and the environmental conditions using the current assemblies, especially for NH4-N measurement. For in situ measurement of nutrients in the real environment, an improvement to the DGT technique is required. The comprehensive assessment of the level of eutrophication needs to consider a variety of environmental factors rather than just the concentration of nutrients.

Development and Applications of Novel DGT Passive Samplers for Measuring 12 Per- and Polyfluoroalkyl Substances in Natural Waters and Wastewaters.

Extensive and long-term use of per- and polyfluoroalkyl substances (PFASs) has caused their widespread distribution in aquatic systems. A new diffusive gradients in thin-films (DGT) passive sampling method based on weak anion exchanger (WAX) binding layer is developed here for monitoring five perfluoroalkyl carboxylic acids (PFCAs), five perfluoroalkanesulfonic acids (PFSAs) and two PFASs (6:2 FTSA and GenX) in waters. Performance of WAX-DGTs was independent of environmental conditions, namely pH (3.03-8.96), ionic strength (1-500 mM), and DOM content (4-30 mg L-1). Diffusion coefficients (D) of the 12 PFASs in the diffusive gels were measured, 9 for the first time. Linear correlations between D and perfluoroalkyl chain lengths (CF2) were established to obtain D for congener chemicals with the similar functional group and structure. The binding capacity of the WAX-DGT sampler was at least 440 µg PFASs per sampler, sufficient for applications in waters across a wide range of conditions and PFASs concentrations. Successful applications of WAX based DGT samplers in a wastewater treatment plant (WWTP) and three rivers has demonstrated that DGT is a powerful tool for monitoring, surveillance and research of these 12 PFASs in aquatic systems, and can be extended to wider suites of PFs in future.

Rice Rhizospheric Effects on the Bioavailability of Toxic Trace Elements during Land Application of Biochar.

Land application of biochar, the product of organic waste carbonization, can improve soil fertility as well as sequester carbon to mitigate climate change. In addition, biochar can greatly influence the bioavailability of toxic trace elements (TTEs) in soils resulting from its large internal surface areas, abundance in organic carbon, and ability to modify soil pH. Most research to date employs batch leaching tests to predict how biochar addition impacts TTE bioavailability, but these ex situ tests rarely considered the rhizospheric effect which might offset or intensify the changes induced by organic residue addition. This is especially so in rice rhizospheres because of strong clines in localized redox conditions. In this study, we adopted in situ high-resolution (HR) diffusive gradients in thin films (DGT) as well as rhizo-bag porewater sampling experiments to depict an overall picture of the difference in TTE (As, Cd, Cu, Ni, and Pb) bioavailability between the rice rhizosphere and bulk soils during land application of biochar. Porewater sampling experiments revealed that biochar additions stimulated TTE release due to the increase of dissolved organic carbon (DOC) and H+ concentrations. In the rhizosphere, although biochar still promoted As, Cd, and Ni release into porewaters, the rhizospheric effect was one of dampening/reduction compared with the bulk soil. When we focused on the localized changes of TTE bioavailability in the rhizosphere using an in situ HR-DGT approach, on the contrary, flux maxima of Cd, Cu, and Ni occurred near/on the root surface, and hot spots of As can be observed at peripheries of the rooting zone, which demonstrated the high heterogeneity and complexity of the rhizosphere's influence on TTE bioavailability.

Simultaneous degradation of p-arsanilic acid and inorganic arsenic removal using M-rGO/PS Fenton-like system under neutral conditions.

In this study, magnetic material based reduced graphene oxide (M-rGO) was prepared through co-precipitation and displayed high catalytic efficiency together with persulfate (PS) for simultaneous p-arsanilic acid (p-ASA) decomposition and arsenic removal. Linear sweep voltammetry and chronoamperometric measurements with M-rGO revealed that PS was effectively bound to M-rGO surface and probably formed charge transfer complex, in which M-rGO was pivotal in mediating facile electron transfer. The effects of pH, temperatures, anions, p-ASA concentration, PS, and M-rGO dosages on p-ASA decomposition were studied in the system. Excellent degradation of p-ASA was carried out at a wide range of pH values, which was unattainable by other Fenton-like processes. Under optimal conditions, M-rGO exhibited prominent removal of both p-ASA (98.8 %) and inorganic arsenic (89.8 %). M-rGO had reasonably excellent repeatability and stability, and 77.7 % p-ASA degraded in the third recovered catalyst. The advantages of environmental friendliness, short reaction time, and straightforward synthesis of M-rGO will facilitate the development of heterogeneous Fenton-like catalysts under neutral conditions.

In Situ Selective Measurement Based on Diffusive Gradients in Thin Films Technique with Mercapto-Functionalized Mesoporous Silica for High-Resolution Imaging of SbIII in Soil.

In situ monitoring of Sb speciation improves the understanding of Sb biogeochemistry and toxicity in ecosystems. Precise measurement of Sb is a challenge due to its instability of oxidation and ultratrace concentration. The development of simple and reliable methods specific to SbIII measurement is not only appealing but essential for implementing regulations. Here, we present an in situ speciation analysis method for SbIII, using the diffusive gradients in thin films (DGT) technique, combined with mercapto-functionalized SBA-15 mesoporous silica nanoparticles (MSBA). Laboratory performance tests confirmed MSBA-DGT uptake was independent of pH (4-9) and ionic strength (0.1-200 mmol L-1). DGT devices equipped with MSBA-based binding gels showed a theoretically linear accumulation of SbIII and exhibited a high capacity for SbIII at 65 µg/gel disc, with negligible accumulation of SbV over a 72 h deployment. Compared with commercial 3-mercaptopropyl-functionalized silica (MFS), the nanosized MSBA facilitate its even distribution in the binding gels. Furthermore, the good selectivity and high homogeneity of the MSBA gel enabled it to be applied in a rice rhizosphere in conjunction with AgI gel to investigate the effects of sulfur application on the SbIII solubility. In summary, the newly developed MSBA-DGT provides a selective measurement of SbIII, showing potential for environmental monitoring and further application in understanding the biogeochemical process of Sb.

Current progress in the adsorption, transport and biodegradation of antibiotics in soil.

Antibiotic residues in soil may cause potential risks to human health and soil ecosystems. To avoid these potential risks, comprehensive study of the adsorption, transport and biodegradation of antibiotics in soil is very imperative. This review provided current views about the most recent studies, which have been conducted toward the adsorption, transport and biodegradation of antibiotics in soil. The influencing factors affecting the adsorption behaviors of antibiotics in soil, including the antibiotics properties (e.g., molecular structure, hydrophobicity, polarity, polarizability, and spatial configuration) and the soil characteristics (e.g., soil type, soil pH, coexisting ions, and soil organic matter), were discussed. The effects of fertilizer colloids, porous media, and pH of soil on the transport behaviors of antibiotics were analyzed. The biodegradation of antibiotics in soil were also highlighted by investigating the effects of soil microbiome, soil pH, soil temperature, and interactions between antibiotics. Prospects of antibiotics adsorption, transport and biodegradation were also proposed.

Electrocatalytic properties of N-doped graphite felt in electro-Fenton process and degradation mechanism of levofloxacin.

The degradation of antibiotic levofloxacin was investigated by dimensionally stable anode as well as modified cathode using low-cost chemical reagents of hydrazine hydrate and ethanol for electro-Fenton in an undivided cell at pH 3.0 under room temperature. Comparison of unmodified and modified cathode was performed. The apparent rate constant of levofloxacin decay was found to be 0.2883 min-1 for graphite felt-10 with the best performance at 200 mA, which is lower than graphite felt at 400 mA. The optimum modified cathode showed a significant improvement of complete mineralization of levofloxacin, reaching a 92% TOC removal at 200 mA for 480 min higher than unmodified one at twice the current. Surface physicochemical properties and morphology were investigated by scanning electron microscope, contact angle and X-ray photoelectron spectroscopy. The electrochemical characterization of hydrogen evolution reaction was adopted to clarify a possible pathway for the higher mineralization of levofloxacin, indicating a potential pilot-scale study to the pollution with the similar structure.