Search Results (9)

Soil washing is an efficient method to remove polybrominated diphenyl ethers (PBDEs) from contaminated soils. The obtained solutions from soil-washing still contain PBDEs, requiring further treatment before disposal or reuse. Although photolysis is effective for PBDE degradation in solutions, the concurrent formation of toxic polybrominated dibenzofurans (PBDFs) may limit its practical application. In this study, 2,8-dibromodibenzofurans (2,8-BDF) formation rate and mechanisms during 2,4,4′-tribromodiphenyl ether (BDE-28) photolysis in various simulated soil-washing solutions was investigated. Results revealed significant effects of solubilizers on 2,8-BDF formation. The nonionic surfactants polysorbate (TW80), polyoxyethylene octylphenyl ether (TX series), and the cationic surfactant cetyltrimethylammonium bromide (CTAB) resulted in low 2,8-BDF formation rate (1–5%), while the β-cyclodextrin led to the highest 2,8-BDF formation rate (about 28%). The nonionic surfactants polyoxyethylene dodecyl ethers (Brij series), and the anionic surfactants sodium dodecylbenzene sulfonate (SDBS) and sodium dodecyl sulfate (SDS), also showed a high level of 2,8-BDF formation rate (7–17%). Solubilizer structure and its interaction with BDE-28 determined the 2,8-BDF formation. The role of the micelle microenvironment on 2,8-BDF formation was verified via an experiment and molecular dynamics simulation. The organic region of micelle exhibited high hydrogen donation ability, which inhibited 2,8-BDF formation. The results indicated distinct risks of PBDE photolysis in various soil-washing solutions, providing an important reference for solubilizer selection and the application of photolysis on the treatment of soil-washing solutions containing PBDEs. Full article

Polybrominated diphenyl ethers (PBDEs), a type of brominated flame retardant, are of global concern due to their environmental persistence, bioaccumulation, toxicity, and resistance to conventional remediation methods. In this study, the electrochemical reduction of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) with Pd/Metal foam electrodes (Ni, Cu, and Ag) was investigated. The effect of Pd loadings was explored, and the results show that Pd loading enhances the debromination performance, with 15.16%Pd/Ni foam exhibiting the best efficiency, followed by 9.37%Pd/Cu and 10.26%Pd/Ag. The degradation mechanisms for Pd/Ni and Pd/Ag are primarily hydrogen atom transfer, while for Pd/Cu, electron transfer dominates. Among the reduction products, Pd/Ni foam shows the highest debromination capability. The impact of electrolytes, current intensity, and bromination degrees of PBDEs was evaluated for 15.16%Pd/Ni. The results reveal that the presence of electrolytes inhibits BDE-47 degradation; the degradation rate of BDE-47 increases with current density, peaks at 4 mA, and decreases as current rises; and 15.16%Pd/Ni foam can effectively degrade PBDEs with varying bromination levels. Additionally, cycling tests show a decrease in efficiency from 94.3% (first cycle) to 56.58% (fourth cycle), attributed to Pd loss and structural damage. The findings offer valuable insights for developing efficient, sustainable catalytic materials for the electrochemical degradation of PBDEs and other persistent organic pollutants. Full article

Abiotic humification, dominated by catalytic oxidation, is one of the critical mechanisms for organic carbon preservation in nature. However, the effects of biochar catalysis on abiotic humification have not yet been elucidated. This study investigated the catalytic power of biochar from walnut shells at different temperatures (300 °C, 600 °C, and 900 °C) for the abiotic transformation of hydroquinone (HQ) as a representative polyphenol. All the biochar samples catalyzed HQ polymerization, resulting in the formation of humic polymers such as fulvic acids (FAs) and humic acids (HAs). Light and oxygen promoted HA formation. HO^• was detected in the BC600–HQ reaction system, and HO^• quenching resulted in a 41.22% decrease in HA production, indicating that HO^• plays a major role in the oxidative polymerization. In the proposed pathway for the abiotic humification, biochar active sites and generated reactive oxygen species accept an electron from HQ, resulting in oxidation to (semi)quinone radicals, which subsequently undergo cleavage or a coupling reaction to form the oligomerized products. Under BC600 catalysis, the weight-average molecular weight (Mw) of the reaction products of HQ, glucose, and glycine reached 14,449 Da. These findings provide new insights into the application potential of biochar for promoting soil carbon sequestration. Full article

Sulfate radicals are increasingly recognized for their potent oxidative capabilities, making them highly effective in degrading persistent organic pollutants (POPs) in aqueous environments. These radicals excel in breaking down complex organic molecules that are resistant to traditional treatment methods, addressing the challenges posed by POPs known for their persistence, bioaccumulation, and potential health impacts. The complexity of predicting interactions between sulfate radicals and diverse organic contaminants is a notable challenge in advancing water treatment technologies. This study bridges this gap by employing a range of machine learning (ML) models, including random forest (DF), decision tree (DT), support vector machine (SVM), XGBoost (XGB), gradient boosting (GB), and Bayesian ridge regression (BR) models. Predicting performances were evaluated using R², RMSE, and MAE, with the residual plots presented. Performances varied in their ability to manage complex relationships and large datasets. The SVM model demonstrated the best predictive performance when utilizing the Morgan fingerprint as descriptors, achieving the highest R² and the lowest MAE value in the test set. The GB model displayed optimal performance when chemical descriptors were utilized as features. Boosting models generally exhibited superior performances when compared to single models. The most important ten features were presented via SHAP analysis. By analyzing the performance of these models, this research not only enhances our understanding of chemical reactions involving sulfate radicals, but also showcases the potential of machine learning in environmental chemistry, combining the strengths of ML with chemical kinetics in order to address the challenges of water treatment and contaminant analysis. Full article

In order to investigate the pollution status of polycyclic aromatic hydrocarbons (PAHs) in the agricultural soil, 240 agricultural soil topsoil samples were collected from nine Pearl River Delta cities from June to September 2019. In addition, 72 samples were collected for vertical soil profiles, which soil profiles were excavated to a depth of 80 cm. After sample preparation, GC-MS was used for the separation of compounds on a HP-5MS quartz capillary column. ArcGIS software was used to map the spatial distribution. Health risk assessment was conducted using USEPA standard. The results showed that the total concentration of 16 PAHs ranged from 43.4 to 5630 ng/g, with an average of 219 ng/g. The spatial distribution showed that most of the seriously polluted areas were in the coastal area, near the port, and there was point source pollution in the Gaoming of Foshan. Vertically distributed display Zhuhai, Jiangmen, Zhaoqing, Shenzhen and Dongguan increased and then decreased from bottom to bottom, showing a low-high-low pattern, the concentration of PAHs in Zhongshan and Foshan decreased with the soil depth, while the concentration of PAHs in Guangzhou and Huizhou was enriched with human activities. The PAHs components in soil samples were mainly medium and high rings (4–6 rings). The analysis of the origin of PAH in soil samples showed that the mixture of incomplete combustion sources of fossil fuels such as coal and biomass and traffic emission sources were the main sources of soil PAHs. A small amount can be attributed to oil sources such as oil spills. The human health risk assessment showed no cancer risk for children, while for adults, may cause a potential risk of cancer, which needs to be noticed. Spearman correlation analysis showed that PAH content was significantly correlated with SOC (p < 0.01) and pH (p < 0.05). Port transport, road emissions and industrial production make the area a pollution hot topic, and supervision should be strengthened to protect the environment and food safety. Full article

Soil-washing is a potential technology for the disposal of soil contaminated by e-waste; however, the produced soil-washing effluent will contain polybrominated diphenyl ethers (PBDEs) and a large number of surfactants, which are harmful to the environment, so the treatment of PBDEs and the recycling of surfactants are the key to the application of soil-washing technology. In this study, coconut shell granular-activated carbon (GAC) was applied to remove PBDEs from Triton X-100 (TX-100) surfactant which simulates soil-washing effluent. The adsorption results show that, GAC can simultaneously achieve effective removal of 4,4′-dibromodiphenyl ether (BDE-15) and efficient recovery of TX-100. Under optimal conditions, the maximum adsorption capacity of BDE-15 could reach 623.19 μmol/g, and the recovery rate of TX-100 was always higher than 83%. The adsorption process of 4,4′-dibromodiphenyl ether (BDE-15) by GAC could best be described using the pseudo-second-order kinetic model and Freundlich isothermal adsorption model. The coexistence ions had almost no effect on the removal of BDE-15 and the recovery rate of TX-100, and the solution pH had little effect on the recovery rate of TX-100; BDE-15 had the best removal effect under the condition of weak acid to weak base, indicating that GAC has good environmental adaptability. After adsorption, GAC could be regenerated with methanol and the adsorption effect of BDE-15 could still reach more than 81%. Density functional theory (DFT) calculation and characterization results showed that, Van der Waals interaction and π–π interaction are dominant between BDE-15 and GAC, and hydrogen bond interactions also exist. The existence of oxygen-containing functional groups is conducive to the adsorption of BDE-15, and the carboxyl group (-COOH) has the strongest promoting effect. The study proved the feasibility of GAC to effectively remove PBDEs and recover surfactants from the soil-washing effluent, and revealed the interaction mechanism between PBDEs and GAC, which can provide reference for the application of soil-washing technology. Full article

Phthalate esters (PAEs) are widely used as plasticizers in industrial and commercial products, and are classified as endocrine-disrupting compounds. In this study, we investigated the contamination characteristics and health risks of PAEs in the soil–plant system in coastal areas of South China. PAEs were detected in soil and plant samples at all 37 sampling sites. The total concentration of the 15 PAEs in soil samples ranged from 0.445 to 4.437 mg/kg, and the mean concentration was 1.582 ± 0.937 mg/kg. The total concentration of the 15 PAEs in plant samples ranged from 2.176 to 30.276 mg/kg, and the mean concentration was 8.712 ± 5.840 mg/kg. Di(2-Ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DnBP) were the major PAEs compounds in all samples. The selected contaminants exhibited completely different spatial distributions within the study area. Notably, higher concentrations of PAEs were found in the coastal Guangdong Province of South China. The average noncarcinogenic risks of Σ6 PAEs were at acceptable levels via dietary and nondietary routes. However, the noncarcinogenic risks posed by DEHP and DBP at some sampling sites were relatively high. Furthermore, dietary and nondietary carcinogenic risks were very low for BBP, but carcinogenic risks posed by DEHP via diet. The results suggest that PAEs in the coastal soil–plant system in South China, through human risk assessment, will induce some adverse effects on human health, especially in children. This study provides an important basis for risk management of PAEs in agriculture, and safety in coastal areas of South China. Full article

Pollution by polybrominated diphenyl ethers (PBDEs) is a major concern due to their bioaccumulation, persistence, and carcinogenicity. This study aimed to investigate the decabrominated diphenyl ether (BDE-209) photodegradation in soil suspensions. The results indicate BDE-209 can degrade in soil suspensions and its degradation follows pseudo-first-order kinetics. The light sources and intensity effects were studied and the photodegradation rates were 500 W Mercury Lamp > 300 W Mercury Lamp > 500 W Xenon Lamp > 300 W Xenon Lamp, which indicates UV light is the main reason for BDE-209 degradation. Soil particle inhibits BDE-209 photodegradation due to the light-shielding effect. BDE-209 photodegradation rates increased from 0.055 to 0.071 h⁻¹ with pH value increasing from 3.5 to 9.5. This may be because the products are more easily produced in higher pH soil suspensions. The presence of humic acid (HA) may inhibit BDE-209 photodegradation by photo-shielding. Fe³⁺ and Cu²⁺ have an adverse effect on BDE-209 photodegradation due to the photo competition. The •OH and ¹O₂ were detected in soil solutions. Analysis of the photoproducts of BDE-209 by gas chromatography mass spectrometry (GC-MS) and liquid chromatography time of flight mass spectrometry (LC-TOF-MS) showed that BDE-209 was mainly debrominated to the lower-brominated BDEs and the reactive oxygen radicals may not lead to BDE-209 degradation. Full article