Effective defluorination of novel hexafluoropropylene oxide oligomer acids under mild conditions by UV/sulfite/iodide: mechanisms and ecotoxicity.

It has recently been discovered that HFPO-TA (a processing aid in the production of fluoropolymers) has high levels of bioaccumulation and biotoxicity. Hydrated electrons (eaq-) have been proposed to be potent nucleophiles that may decompose PFAS. Unlike previous studies in which the generation of eaq- was often restricted to anaerobic or highly alkaline environments, in this study, we applied the UV/SO32-/I- process under mild conditions of neutrality, low source chemical demand, and open-air, which achieved effective degradation (81.92 %, 0.834 h-1) and defluorination (48.99 %, 0.312 h-1) of HFPO-TA. With I- as the primary source of eaq-, SO32- acting as an I- regenerator and oxidizing substances scavenger, UV/SO32-/I- outperformed others under mild circumstances. The eaq- were identified as the main active species by quenching experiments and electron paramagnetic resonance (EPR). During degradation, the first site attacked by eaq- was the ether bond (C6-O7), followed by the generation of HFPO-DA, TFA, acetic and formic acid. Degradation studies of other HFPOs have shown that the defluorination of HFPOs was accompanied by a clear chain-length correlation. At last, toxicological experiments confirmed the safety of the process. This study updated our understanding of the degradation of newly PFASs and the application of eaq- mediated photoreductive approaches under mild conditions.

Hydrated electron based photochemical processes for water treatment.

Hydrated electron (eaq-) based photochemical processes have emerged as a promising technology for contaminant removal in water due to the mild operating conditions. This review aims to provide a comprehensive and up-to-date summary on eaq- based photochemical processes for the decomposition of various oxidative contaminants. Specifically, the characteristics of different photo-reductive systems are first elaborated, including the environment required to generate sufficient eaq-, the advantages and disadvantages of each system, and the comparison of the degradation efficiency of contaminants induced by eaq-. In addition, the identification methods of eaq- (e.g., laser flash photolysis, scavenging studies, chemical probes and electron spin resonance techniques) are summarized, and the influences of operating conditions (e.g., solution pH, dissolved oxygen, source chemical concentration and UV type) on the performance of contaminants are also discussed. Considering the complexity of contaminated water, particular attention is paid to the influence of water matrix (e.g., coexisting anions, alkalinity and humic acid). Moreover, the degradation regularities of various contaminants (e.g., perfluorinated compounds, disinfection by-products and nitrate) by eaq- are summarized. We finally put forward several research prospects for the decomposition of contaminants by eaq- based photochemical processes to promote their practical application in water treatment.

Adsorption of nitrate from interflow by the Mg/Fe calcined layered double hydroxides.

Nitrate loss in interflow caused serious nitrate pollution of neighboring water bodies in the purple soil region of China's Sichuan Province. In this study, Mg/Fe(Al)-calcined layered double hydroxides (Mg/Fe(Al)-CLDHs) with varied Mg/Fe(Al) ratios were synthesized for nitrate removal from interflow, and 3:1 Mg/Fe CLDH exhibited the best adsorption performance. The effects of initial pH, adsorbent dosage and co-existing anions on the adsorption performance were investigated by batch experiments. The best-fitting kinetic and isothermal models for nitrate adsorption were the pseudo-second-order model and Freundlich model, respectively, indicating that the adsorption process was a physical-chemical multilayer process. The maximum adsorption capacity of nitrate was 73.36 mg/g, which was higher than that of many other commonly used adsorbents. The adsorbents were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscope (TEM) and Brunauer-Emmett-Teller (BET) techniques, and the XRD and FT-IR results revealed that the adsorption mechanism involved original layered structure reconstruction and ion-exchange interaction. Under the coexistence of SO42- and Cl-, 75.63% nitrate in interflow could be removed after 6 h of adsorption. Overall, the synthesized Mg/Fe CLDH is an effective and low-cost nitrate adsorbent for in-situ nitrate removal.

Ecological risk assessment of toxic metal(loid)s for land application of sewage sludge in China.

Sewage sludge, including those after biological or thermochemical treatments, has the potential to be used as fertilizers for recycle of resources. However, its potential ecological risk is also of great concern to policy making. This study employed comprehensive ecological risk assessment (ERA) methods to evaluate the risk caused by the toxic metal(loid)s in sewage sludge throughout China. The conventional geo-accumulation index and potential ecological risk index revealed that cadmium (Cd) and mercury (Hg) were of significant concern in treating sewage sludge before land application, but chromium (Cr) and zinc (Zn) were preferred by potential affected proportion (PAF) and overall risk probability (ORP) of species sensitivity distribution (SSD). Because SSD considered both the community and the ecotoxicity of toxic metal(loid)s, it was more advantageous and promising in assessing ecological risks caused by land application of sewage sludge. Based on the predicted no-effect concentration (PNEC) of toxic metal(loid) calculated by hazardous concentration that cause death of 50% of species (HC50) by SSD, the maximum allowable disposal amount (MADA) of sewage sludge in the whole China indicated that chromium (Cr) should be totally eliminated because of its high risks in the present background soil. After excluding Cr, the MADA of sewage sludge in China was 3.24 × 106 t and 6.47 × 107 t under land application scenarios with high and low ecological risks, respectively. Additionally, the MADA could be increased by mixing sewage sludge with deeper soil in wider areas. This study emphasized that local laws and regulations on land application of sewage sludge and the subsequent ERA system need to be addressed in the future.

Toxic metals in soil due to the land application of sewage sludge in China: Spatiotemporal variations and influencing factors.

Land application has become a promising method for recycling energy and resources from sewage sludge; however, the changes that occur to the toxic metal concentrations in soil following the application of sewage sludge have been poorly investigated in China. The present study attempted to investigate the spatiotemporal variations of toxic metal concentrations in soil due to the land application of sewage sludge and the critical influencing factors. Overall, the results indicated that an increasing ratio of sewage sludge for land application, the concentrated disposal measures, and a shallower soil may lead to elevated toxic metal concentrations in soil. The worst scenario simulation showed that the cumulative discharge of toxic metals through sludge disposal were ranked as: Zn > Cu > Cr > Pb > Ni > As > Cd > Hg. After sewage sludge was applied to previously unaffected soil, i.e., background soil, the toxic metal concentrations in the soil increased annually over the period from 2006 to 2017. However, with respect to the affected soil, the concentrations of Zn and Cu increased, whereas the concentrations of As, Cd, Cr, and Pb decreased annually over the period from 2006 to 2017. The results indicate that, in practice, the selection of soil for sewage sludge disposal depends on the background and actual concentrations of toxic metals in a soil as well as the stress caused by the amount of sewage sludge application to cultivated land. We propose to use sewage sludge containing relatively lower concentrations of metals than the disposal soil for land application. Furthermore, land application of sewage sludge should be suited to local conditions in the future sewage sludge management.