Enhanced arsenic(III) sequestration via sulfidated zero-valent iron in aerobic conditions: Adsorption and oxidation coupling processes.

Sulfidated zero-valent iron (S-ZVI) has shown significant potential for the removal of arsenic(III). However, little attention has been paid to the mechanism of As(III) sequestration enhancement and how the phase transformation for S-ZVI strengthens this process in aerobic conditions. In this work, sulfidated ZVI was created by ball-milling (S-ZVIbm) and liquid-mixing (S-ZVIlm) of ZVI with elemental sulfur(S0) to investigate the performance and mechanisms of As(III) sequestration in air-saturated water. Sulfidation was found to significantly enhance the As(III) removal rate constant, which was 2.8 âˆ¼ 6.7 times (S-ZVIbm) and 3.1 âˆ¼ 17.1 times (S-ZVIlm) higher than that without sulfidation. FeS was identified as the predominant sulfur species in the S-ZVI samples using S K-edge XANES spectra. The enhanced electron transfer and ZVI corrosion after sulfidation were verified via electrochemical tests. XANES and Mössbauer spectra suggested that lepidocrocite(γ-FeOOH) was the predominant corrosion product generated on the ZVI surface with the presence of oxygen, and DFT calculations further confirmed the improved performance of γ-FeOOH for As(III) sequestration. Besides, As(III) oxidation occurred dominantly on the heterogeneous surface rather than in solution, and the As(III) sequestration pathway of adsorption followed by oxidation was proposed. This study provides new insight into the enhanced As(III) sequestration by S-ZVI in aerobic conditions.

Variation in the burden and chemical forms of thallium in non-detoxified tissues of tilapia fish (Oreochromis niloticus) from waterborne exposure.

Thallium (Tl) is highly toxic to aquatic ecosystems, but information about its concentration and distribution characteristics in different fish tissues is limited. In this study, juvenile tilapia (Oreochromis niloticus) were exposed to Tl solutions with different sub-lethal concentrations for 28 days, and the Tl concentrations and distribution patterns in the fish non-detoxified tissues (gills, muscle, and bone) were analyzed. The Tl chemical form fractions, Tl-ethanol, Tl-HCl, and Tl-residual, corresponding to easy, moderate, and difficult migration fraction, respectively, in the fish tissues were obtained by sequential extractant approach. The Tl concentrations of different fractions and total burden were determined using graphite furnace atomic absorption spectrophotometry. Exposure-concentration effect determined the Tl burden in the fish tissues. The average Tl-total concentration factors were 360, 447, and 593 in the bone, gills, and muscle, respectively, and the limited variation during the exposure period indicates that tilapia have a strong ability to self-regulate and achieve Tl homeostasis. However, Tl fractions varied in tissues, and the Tl-HCl fraction dominated in the gills (60.1%) and bone (59.0%), switchover Tl-ethanol fraction dominated in the muscle (68.3%). This study has shown that Tl can be easily taken up by fish during 28-days-period and largely distributed in non-detoxified tissues especially muscle, in which concurrent risks of high Tl-total burden and high levels of Tl in the form of easy migration fraction, posing possible risks to public health.

Degradation efficiency and mechanism of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) by thermally activated persulfate system.

Polybrominated diphenyl ethers (PBDEs) as a typical brominated flame retardant (BFR) have attracted worldwide attention due to the high environmental risk and resistance to conventional remediation processes. In this study, thermally activated persulfate (TAP) process was applied to degrade 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), which is the most toxic and representative PBDEs in e-waste dismantling sites. Impact factors such as PDS dosage, heating temperature, and initial pH were evaluated. Results showed that BDE-47 can be 100% degraded within 180 min under the condition of PDS:BDE-47 = 1000:1, 60 °C, and pH = 7. Quenching experiments combined with EPR analysis further proved the important role of SO4·- in oxidating BDE-47. According to high-resolution mass spectrometry (HRMS) analysis, only one oxidation product of low toxicity was detected during the oxidation process. Theoretical calculations further revealed that the oxidation process mainly involved radical attack at C-Br bond, cleavage of C-Br bond, and fission of ether bond, and HSO4· may also play an important role in BDE-47 degradation in TAP system. In addition, TAP system exhibited universality as all selected PBDE congeners can be degraded, and the degradation rate of PBDEs was greatly affected by the number of substituted Br atoms in a negative trend. Overall, these findings indicate that TAP can be applied as an effective method for removal of PBDEs, and we provide a new insight for the practical application of TAP technology in BDE-47 degradation from experimental and theoretical aspects.

Application of bovine bone meal and oyster shell meal to heavy metals polluted soil: Vegetable safety and bacterial community.

The development of efficient, environmentally friendly soil amendments is necessary in order to minimize the risk of metal contaminants (Cd, Pb, Cu, and Zn) to the soil ecosystem. As soil amendments, bovine bone meal (BM) and oyster shell meal (OS) reduced the mobility and bioavailability of metals primarily by increasing soil pH. Soil geochemical properties (pH, EC, CEC, Ca, P, and K) after amendment supplementation were more likely to affect metal migration than enzyme activity. Furthermore, BM and OS were found to suppress the Cd and Pb uptake by water spinach, keeping them below international standards for safe utilization. The protein and sugar content and peroxidase (POD) activity showed a significant negative correlation with the amount of metal in water spinach, whereas superoxide dismutase (SOD), ascorbate peroxidase (APX) activities and malondialdehyde (MDA) content exhibited a positive correlation with metal content in water spinach. We also found that BM and OS had less perturbation to phylum-level and genus-level bacterial composition during the remediation of heavy metals contaminated soil. Based on the above, we assume that BM and OS are eco-friendly soil amendments, which could improve soil nutrients contents, stabilize heavy metals and regulate bacterial community structure. Our research contributes to resource utilization of waste and holds promise for widespread application in current agricultural systems.

Remediation of Cd-, Pb-, Cu-, and Zn-contaminated soil using cow bone meal and oyster shell meal.

To understand the environmental friendliness and high efficiency of organic materials during remediating soil polluted by heavy metals by assessing the feedback of soil ecosystems after organic materials were put into polluted soil. Incubation research was undertaken to examine the impact of amendments ranging from 0.1% to 3.0% (w/w), including single cow bone meal (BM), single oyster shell meal (OS), and a composite of 50% BM mixed with 50% OS (BO) on soil biochemical properties. The findings revealed that the implementation of BM and OS increased soil pH, the content of certain nutrients, and the activities of catalase (S-CAT), and urease (S-UE) while decreasing the availability of Cd, Pb, Cu, and Zn. Overall, the immobilization effect on Cd and Zn after a 108-day incubation was ranked as follows: BM group > OS group ≥ BO group, and the order of the immobilization effect of Pb and Cu was OS group > BO group > BM group. In addition, the dominant bacterial community flora shifted toward alleviating the re-dissolution of metal ions from the soil and promoting nutrient recycling in soil within 108 days of cultivation. RNA analyses showed that the strongest determinants for microbial communities between BM application and OS application at the genus level were soil pH, CEC, and heavy metal (Cd, Pb). These results increase our understanding of the leaching performance of Cd, Pb, Cu and Zn and the evolution trend of microorganisms when organic amendments remediate heavy metal contaminated soil.

Removal efficiency, kinetic, and behavior of antibiotics from sewage treatment plant effluent in a hybrid constructed wetland and a layered biological filter.

Sewage treatment plant (STP) is the major point source of antibiotic contamination, yet the advanced treatment of antibiotic polluted STP effluent has not been given necessary attention. This study is conducted to evaluate the removal efficiency, kinetic, and behavior of sulfonamides, quinolones, tetracyclines, and macrolides antibiotics from STP effluent in a hybrid constructed wetland (HCW) and a layered biological filter (LBF) at different hydraulic loading rates (HLRs). The results showed that the removal efficiency of antibiotics in all the HLRs was ranked as follow: quinolones of HCW (70-95%) > macrolides of HCW (58-77%) > tetracyclines of both systems (59-67%) > quinolones of LBF (28-64%) > macrolides of LBF (13-25%) > sulfonamides of both systems (<0%). The optimal HLR is 1.0 m/day for quinolones and 2.0 m/day for tetracyclines-macrolides in the HCW, and 6.4 m/day for quinolones-tetracyclines in the LBF, respectively. Although HCW performed better on the removal of most antibiotics, LBF exhibited stronger total loading toleration and higher removal loading ability to antibiotics. Among them, quinolones were markedly removed by multiple effect of substrate adsorption, microbial anaerobic degradation, and photolysis in the HCW (planted), and by filter sorption and interception in the LBF (unplanted); adsorption is the dominant elimination approach for tetracyclines in both systems; plant uptake plays a significant role on the removal of macrolides in the HCW.

Effects of ferric ion on the photo-treatment of nonionic surfactant Brij35 washing waste containing 2,2',4,4'-terabromodiphenyl ether.

The effects of ferric iron on the photo-treatment of simulated BDE-47 (2,2',4,4'- terabromodiphenyl ether)-Brij35 (Polyoxyethylene lauryl ether) washing waste were studied to evaluate the influences of ferric iron on BDE-47 removal and Brij35 recovery. The results show that Fe3+ accelerated BDE-47 degradation at lower concentrations (<0.5 mM) but attenuated it at higher concentrations (0.5-5 mM) and that Brij35 loss was increased with increasing Fe3+. These results likely are caused by changes in the rate of •OH production due to the ferric ion, association of Fe3+ and electron transfer from Brij35, and light attenuation at high concentration. The BDE-47 and Brij35 had different degradation rates at different pH values and at different dissolved oxygen concentrations. The BDE-47 products were identified by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS). The results indicated that BDE-47 transformed into mainly lower-brominated products, a few bromodibenzofurans, some rearrangement products, and some hydroxylated polybrominated diphenyl ethers. A series of Brij35 oxidization products were detected by ultra-performance liquid chromatography-high resolution mass spectrometry (UPLC-HRMS), including hydroxylation products, carboxylation products, and some hydrophilic chain-breaking products. Brij35 was mainly oxidized by Fe3+ and/or reactive oxygen species (ROS) with the final products of CO2 and H2O. The iron ions apparently cycled from ferric to ferrous ions in the micelles such that the Fe3+-Brij35 complex dominated the main redox reaction, leading to both BDE-47 and Brij35 degradation. It appears that in any applied soil washing system, the ferric ions in the washing waste need to be removed because of the adverse effects on BDE-47 removal and eluate reuse.

Effects of surfactant on the degradation of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) by nanoscale Ag/Fe particles: Kinetics, mechanisms and intermediates.

Surfactants are known to enhance the degradation of halogenated organics by nanoscale zerovalent iron (n-ZVI) or n-ZVI-based bimetallic particles, but the mechanism of the promotion is not well understood. In this study, we used nanoscale Ag/Fe particles (n-Ag/Fe) to degrade 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) in different surfactant solutions. The results show that the nonionic surfactant TX-100 had the best promoting effect, which might be attributed to the decrease in particle agglomeration and improvement of mass transfer efficiency after the adsorption of TX-100 on n-Ag/Fe. The distribution analysis of BDE-47 in solid and liquid phases indicates that when the concentration of TX-100 in aqueous solution was above critical micelle concentration, BDE-47 started to dissolve in the liquid phase. Thus, TX-100 micelles can enhance the mass transfer efficiency of BDE-47. However, a too high concentration of TX-100 (above 1.0 mM) would influence the promotion effect of BDE-47 degration, which might be attributed to the excessive and thicker micelles of TX-100 hindering the contact between BDE-47 and n-Ag/Fe. We also studied the degradation pathway of BDE-47 and its products, and found that surfactants did not change the degradation pathway of BDE-47.

Debromination of polybrominated diphenyl ethers (PBDEs) and their conversion to polybrominated dibenzofurans (PBDFs) by UV light: Mechanisms and pathways.

Polybrominated diphenyl ethers (PBDEs) are typical flame retardant that have arose widely environmental concerns. Previous studies have found that PBDEs can generate lower BDEs and polybrominated dibenzofuran (PBDFs) under UV exposure, but these two processes were not well understood. In this study, we have investigated them through the case study of three BDE congeners (i.e. BDE-29, BDE-25 and BDE-21), which all have an ortho-, a meta- and a para-bromine substituents. The results shows that the vulnerability rank order of brominated position for these three BDE congeners are totally different, the bromine substituent at each position (ortho-, meta- or para-) can be preferentially removed, indicating it is not scientific to summarize the debromination pathways of PBDEs by comparing the brominated position. The lowest unoccupied molecular orbital (LUMO) of PBDEs in first excited state are well consistent with their actual debromination pathways, suggesting it is a good descriptor to predict the photodebromination pathways of PBDEs. In addition, the PBDEs with an ortho-bromine substituent can generate lower PBDFs, and the first step is to generate lower BDEs with an ortho-carbon radical, followed by ring closure reaction to generate PBDFs.

Debromination of polybrominated diphenyl ethers (PBDEs) by zero valent zinc: Mechanisms and predicting descriptors.

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants that are ubiquitous in the environment. The physical and chemical properties of PBDEs make them difficult to degrade, with the conventional remediation methods being relatively inefficient. In this study, the reactivity of zero valent zinc (ZVZ) toward 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) was evaluated under aqueous solution. First-order rate constants (kobs) for BDE-47 disappearance increased with decreased pH, which is attributed to the dissolution of surface zinc oxides that promote the contact between the active site on zinc surface and BDE molecules. The kobs of ten investigated PBDEs in ZVZ system are positively correlated with the energy of lowest unoccupied orbitals (ELUMO) of PBDEs (R2 = 0.902). The debromination pathways of BDE-47 in ZVZ system are: BDE-47 → BDE-28 → BDE-15 → BDE-3 → DE, which is the same to the debromination pathways of BDE-47 in zero valent iron (ZVI) in previous study. In addition, the singly occupied molecular orbitals (SOMOs) of the BDE anions can well reflect the actual debromination pathways of PBDEs by comparing the size of the CBr antibonding characterized lobes. Our results suggest that the debromination of PBDEs by ZVZ is based on the electron transfer mechanism, and the SOMOs of BDE anions can be used to predict the debromination pathways of untested PBDEs.

Determination of decabrominated diphenyl ether in soils by Soxhlet extraction and high performance liquid chromatography.

This study described the development of a method based on Soxhlet extraction combining high performance liquid chromatography (Soxhlet-HPLC) for the accurate detection of BDE-209 in soils. The solvent effect of working standard solutions in HPLC was discussed. Results showed that 1:1 of methanol and acetone was the optimal condition which could totally dissolve the BDE-209 in environmental samples and avoid the decrease of the peak area and the peak deformation difference of BDE-209 in HPLC. The preliminary experiment was conducted on the configured grassland (1 µ g/g) to validate the method feasibility. The method produced reliable reproducibility, simulated soils (n = 4) RSD 1.0%, and was further verified by the analysis e-waste contaminated soils, RSD range 5.9-11.4%. The contamination level of BDE-209 in burning site was consistent with the previous study of Longtang town but lower than Guiyu town, and higher concentration of BDE-209 in paddy field mainly resulted from the long-standing disassembling area nearby. This accurate and fast method was successfully developed to extract and analyze BDE-209 in soil samples, showing its potential use for replacing GC to determinate BDE-209 in soil samples.

Concentrations and inventories of polycyclic aromatic hydrocarbons and organochlorine pesticides in watershed soils in the Pearl River Delta, China.

The concentration levels, source, and inventories of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) in 55 surface vegetable soils in the watershed of the Pearl River Delta (PRD) were analyzed and compared with those of the surface sediments in the Pearl River Estuary (PRE) and northern South China Sea (SCS). The 16 priority PAHs on US EPA list range from 58 to 3,077 microg/kg (average: 315 microg/kg). The concentrations of DDTs and HCHs range from 3.58 to 831 microg/kg (average: 82.1 microg/kg) and from 0.19 to 42.3 microg/kg (average: 4.42 microg/kg). The ratios of DDT/ (DDD+DDE) are higher than 2 in majority of the soil samples, suggesting that DDT contamination still exists. The PAH ratios suggest that the source of PAHs is petroleum, and combustion of fossil fuel, biomass, and coal. The average concentrations of PAHs and the linear regression slope between PAHs and TOC for the soils and the sediments are quite similar. It was estimated that the soil mass inventories at 0-20 cm depth are 1,292 metric tons for PAHs and 356 metric tons for OCPs in the studied region. The average PAHs inventory per unit area for the soil samples investigated in PRD is about 0.86 time that of surface sediments in the Pearl River Estuary, and about 2.43 times that of surface sediments in the northern South China Sea. PAHs in the soils in PRD have similar source to those of the surface sediments in PRE. All of those may suggest that PAHs in PRE and SCS are probably mainly inputted from the soils in PRD via soil erosion and river transport.

Polybrominated diphenyl ethers in watershed soils of the Pearl River Delta, China: occurrence, inventory, and fate.

Soils play an important role in the distribution and biogeochemical cycling of polybrominated diphenyl ethers (PBDEs) as they are a major reservoir and sink for PBDEs due to their large sorption capacity. In this study, concentrations, compositional profiles, mass inventories, and fate of sigma9PBDEs (28, 47, 66, 100, 99, 154, 153, 138, 183) and BDE 209 were investigated in 33 surface soils, six profile soils, and three point-source polluted soils (close to e-waste dismantling sites) from the Pearl River Delta (PRD), China. The concentrations of sigma9PBDEs and BDE 209 in the surface soils ranged from 0.13 to 3.81 ng/g with an average of 1.02 ng/g and from 2.38 to 66.6 ng/g with an average of 13.8 ng/g, respectively, and ranged from 1.93 to 19.5 ng/g and from 25.7 to 102 ng/g, respectively, in the point-source contaminated soils. The PBDE compositional patterns in the surface soils indicated deca-BDE, penta-BDE, and octa-BDE products as the main sources, but those in the point-source samples suggested deca-BDE and octa-BDE technical mixtures as the dominant sources. The mass inventories of PBDEs in soils of the PRD were estimated at 3.98 and 44.4 t for sigma9PBDEs and BDE 209, respectively. The average loading of PBDEs in the soils was comparable to that in the sediments of the Pearl River Estuary, suggesting that soil erosion and surface runoff are an important mode to transport PBDEs from terrestrial sources to oceans in the PRD. Individual BDE congeners, sigma9PBDEs, and PBDE 209, were significantly correlated with total organic carbon (TOC), and a good regression (except for BDE 47) between the logarithms of TOC-normalized BDE average concentrations and their log K(ow) was also obtained, indicating that sorption of PBDEs on soil organic matter governed their spatial distribution, transportation, and fate in the soils. Predicted aqueous and gaseous concentrations of PBDEs were derived from the soil-water and soil-air partitioning models, respectively, and good agreements were obtained between the predicted and previously reported values. BDE 47 and/or 28 did not appear to follow the same trend for these models, an indication that an portion of them was likely the biodegradation byproducts in soils.