Sorption of cadmium by layered double hydroxides: Performance, structure-related mechanisms, and sequestration stability assessment.

Layered double hydroxides (LDHs) have been recognized to have great potential for the treatment of heavy metals in wastewater and soil through various mechanisms. Isomorphic substitution is an important mechanism for the sorption of heavy metal cations with LDH reconstruction and highly stable product formation. However, sorption performance, structure-related relationships, and, more importantly, stability are still poorly understood. In this study, a series of LDHs with different structures were synthesized to evaluate their cadmium (Cd) sorption performance and stability concerning the isomorphic substitution mechanism. Divalent cation types in the LDH lattice determined the Cd sorption capacity as well as the isomorphic substitution possibility, following the order of hydroxide solubility of divalent cations (MII): Ca2+>Mg2+>(Cd2+) > Ni2+>Zn2+. In addition, CaAl-LDH exhibited a super-high Cd sorption capacity of 625.0 mg g-1. Cd sorption by LDHs with different interlayer anion types and divalent/trivalent cation molar ratios varied due to crystallite size-related MII release through cation-exchange/isomorphic substitution. Coexisting cations (e.g., Zn2+, Ni2+, Mg2+) influence the sorption performance of MII-LDH mainly through isomorphic substitution mechanism, largely depending on the solubility of MII(OH)2 with a trend of stable product formation. Furthermore, Mg2.9Cd0.1AlCl-LDH was fabricated, and limited Cd dissolution without destruction of the LDH structure was observed under various conditions. For example, only 7.69%, 2.16% and 0.96% of Cd was released from as-prepared Mg2.9Cd0.1AlCl-LDH in NaCl solution (0.02 mol L-1, pH 5), soil extract, and soil matrix, respectively. The very low leaching of Cd from Cd-containing LDHs indicated the high stability of LDH-sorbed Cd via isomorphic substitution and feasible practical application in Cd sequestration in wastewater treatment and soil remediation.

Quantitative identification of halo-methyl-benzoquinones as disinfection byproducts in drinking water using a pseudo-targeted LC-MS/MS method.

Halobenzoquinones (HBQs) as disinfection byproducts (DBPs) in drinking water is prioritized for research due to their prevalent occurrence and high toxicity. However, only fifteen HBQs can be identified among a high diversity using targeted LC-MS/MS analysis in previous studies due to the lack of chemical standards. In this study, we developed a pseudo-targeted LC-MS/MS method for detecting and quantifying diverse HBQs. Distinct fragment characteristics of HBQs was observed according to the halogen substituent effects, and extended to the development of a multiple-reaction-monitoring (MRM) method for the quantification of the 46 HBQs that were observed in simulated drinking water using non-targeted analysis. The fragmentation mechanism was supported by the changes of Gibbs free energy (ΔG), and a linear relationship between the ΔG and the ionization efficiency of analytes was developed accordingly for quantification of these 46 HBQs, 30 of which were lack of chemical standards. It is noted that 29 of the 30 newly-identified HBQs were halo-methyl-benzoquinones (HMBQs), which were predicted to be carcinogens related with drinking-water bladder cancer risk and be more toxic than non-methyl HBQs. Using the new method, twelve HMBQs were detected in actual drinking water samples with concentrations up to 100.4 ng/L, 3 times higher than that reported previously. The cytotoxicity in CHO cells of HMBQs was over 1-fold higher than that of non-methyl-HBQs. Therefore, HMBQs are an essential, highly toxic group of HBQs in drinking water, which deserve particular monitoring and control.

[Pollution Characteristics and Health Risk Assessment of Perfluorinated Compounds in PM2.5 in Zhejiang Province].

As typical new pollutants, perfluorinated compounds (PFCs) have been widely concerned by environmental workers in recent years. This study was carried out to investigate the pollution characteristics of perfluorinated compounds in atmospheric particulate matter (PM2.5) in Zhejiang Province. The chemical extraction of PM2.5 was performed using the accelerated solvent extraction (ASE) method with mixed dichloromethane and acetone (2:1). The chemical analysis was implemented by ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The results showed that the daily average concentration of the sum of 12 PFCs (Σ12 PFCs) ranged from 131.63 pg·m-3 to 578.53 pg·m-3, which was slightly higher in winter compared to that in autumn. The concentrations of perfluorosulfonic acids (PFSAs) were much lower than those of perfluorocarboxylic acids (PFCAs). PFOS was the primary contaminant among PFASs, with an average concentration of 12.90 pg·m-3. The content of PFCAs exhibited a trend of PFOA>PFHxA>PFHpA, and the detection rate of long-chain PFCs was much lower than that of short-chain PFCs. The hysplit-4 model was used to calculate the QZ air mass transport trajectory. The results indicated that the backward trajectory of this point was significantly different along time, and the source of air mass rarely affected the concentration. The forward trajectory confirmed that PFCs can be transmitted over long distances in the atmosphere in a short time. The correlation coefficient between PFUdA and PFTeDA was evaluated to be 0.68, and that between PFHxS and PFOS was 0.66, suggesting the same sources of these chemicals. The content of PFCs was positively correlated with PM2.5, indicating that people might suffer from higher health risks on haze days. The risk quotient estimation implied no health risk of PFCs in PM2.5 in Zhejiang Province.

Quantitative study on the fate of antibiotic emissions in China.

China, the largest producer and user of antibiotics in the world, discharges excessive amounts of these substances into the environment, without prior treatment. This results in ubiquitous distribution of these substances, as well as increased levels of drug-resistant bacteria, that will eventually cause unimaginable consequences to the environment and to humans. However, most of the research on antibiotics has focused on residue analysis of single medium such as wastewater and landfills. There is paucity of research that systematically investigates the fate of antibiotics after excretion, and specifically of end-treatment processes. In this paper, the fate of antibiotic emissions is systematically calculated. The results show that human and livestock feces account for 57.6% and 42.6% of the discharge of medicinal antibiotics and veterinary antibiotics, respectively. Of these feces types, pig feces accounted for 98.7% of antibiotic residues in livestock feces. The above conclusions can be used to clarify the direction of the tracking and supervision of antibiotic residues and provide new ideas for the treatment of antibiotics, especially their terminal removal.

Self-cleaning liner for halogenated hydrocarbon control in landfill leachate.

Sorptive landfill liners can prevent the migration of the leachate pollutants. However, their sorption ability will decrease over time. A method should be developed to maintain the sorption ability of landfill liners. In this study, we combined cetyltrimethylammonium bromide-bentonite (CTMAB-bentonite) and zero-valent iron (ZVI) to develop a self-cleaning liner that can retain its sorption ability for a long period. Batch experiments and calculation simulations were employed to analyse the sorption ability of this liner material and the ecological risk of halogenated hydrocarbons. The results showed that CTMAB-bentonite could sorb halogenated hydrocarbons well, with saturated sorption capacities (Q m) of 10.2, 14.5, 6.69, 18.5, 29.4, and 49.7 mg·g-1 for dichloroethane (DCA), trichloroethane (TCA), dichloroethene (DCE), trichloroethylene (TCE), tetrachloroethylene (PCE), and 1,3- dichloropropene (1,3-DCP), respectively. Using the mixture of 0.5 g iron and 0.5 g CTMAB-bentonite could dramatically increase the removal efficiency of DCE, TCE, and PCE. The reaction with ZVI did not change the structure of CTMAB-bentonite and its sorption ability remained consistent. Calculation results suggested that the self-cleaning landfill liner would dramatically decrease the hazard index (HI) of the eluate. However, the humic acid and salt in leachate would cause a reduction in the removal of halogenated hydrocarbons.

Durability of organobentonite-amended liner for decelerating chloroform transport.

Chloroform is added to landfill for suppressing methane generation, which however may transport through landfill liners and lead to contamination of groundwater. To decelerate chloroform transport, the enhanced sorption ability of clay liners following organobentonite addition was tested. In this study, we used batch sorption to evaluate sorption capacity of chloroform to organobentonite, followed by column tests and model simulations for assessing durability of different liners. Results show that adding 10% CTMAB-bentonite (organobentonite synthesized using cetyltrimethylammonium bromide) increased the duration of a bentonite liner by 88.5%. CTMAB-bentonite consistently showed the highest sorption capacity (Qm) among six typical organobentonites under various environmental conditions. The removal rate of chloroform by CTMAB-bentonite was 3.6-23 times higher than that by natural soils. According to the results derived by model simulation, a 70-cm 10% CTMAB-bentonite liner exhibited much better durability than a 100-cm compact clay liner (CCL) and natural bentonite liner evidenced by the delayed and lower peak of eluent concentration. A minimum thickness of 65.8 cm of the 10% CTMAB-bentonite liner could completely sorb the chloroform in a 100-m-high landfill. The 10% CTMAB-bentonite liner exhibiting much better durability has the promise for reducing environmental risk of chloroform in landfill.