Occurrence and Ecological Risk Assessment of Highly Toxic Halogenated Byproducts during Chlorination Decolorization of Textile Printing and Dyeing Wastewater.

Textile printing and dyeing wastewater is a substantial source of highly toxic halogenated pollutants because of the chlorination decolorization. However, information on the occurrence and fate of the highly toxic halogenated byproducts, which are produced by chlorination decolorization of the textile printing and dyeing wastewater, is very limited. In this study, the occurrence of six categories of halogenated byproducts (haloacetic acids (HAAs), haloacetonitriles (HANs), N-nitrosamines (NAs), trihalomethanes, halogenated ketones, and halonitromethanes) was investigated along the full-scale treatment processes of textile printing and dyeing wastewater treatment plants. Furthermore, the ecological risk of the halogenated byproducts was evaluated. The results showed that the total concentration of halogenated byproducts increased significantly after chlorination. Large amounts of HAAs (average 122.1 µg/L), HANs (average 80.9 µg/L), THMs (average 48.3 µg/L), and NAs (average 2314.3 ng/L) were found in the chlorinated textile wastewater, and the results showed that the generations of HANs and NAs were positively correlated with the BIX and ß/α index, indicating that the HANs and NAs might form from the microbial metabolites. In addition, HAAs and HANs exhibited high ecological risk quotients (>1), suggesting their high potential ecological risk. The results also demonstrated that most halogenated byproducts could be effectively removed by reverse osmosis treatment processes except NAs, with a lower removal rate of 18%. This study is believed to provide an important theoretical basis for controlling and reducing the ecological risks of halogenated byproducts in textile printing and dyeing wastewater effluents.

Facet-dependent transformation and toxicity of nanoscale zinc oxide in the synthetic saliva.

The nanoscale zinc oxide (n-ZnO) was used in food packages due to its superior antibacterial activity, resulting in potential intake of n-ZnO through the digestive system, wherein n-ZnO interacted with saliva. In recent, facet engineering, a technique for controlling the exposed facets, was applied to n-ZnO, whereas risk of n-ZnO with specific exposed facets in saliva was ignored. ZnO nanoflakes (ZnO-0001) and nanoneedles (ZnO-1010) with the primary exposed facets of {0001} and {1010} respectively were prepared in this study, investigating stability and toxicity of ZnO-0001 and ZnO-1010 in synthetic saliva. Both ZnO-0001 and ZnO-1010 partially transformed into amorphous Zn3(PO4)2 within 1 hr in the saliva even containing orgnaic components, forming a ZnO-Zn3(PO4)2 core-shell structure. Nevertheless, ZnO-1010 relative to ZnO-0001 would likely transform into Zn3(PO4)2, being attributed to superior dissolution of {1010} facet due to its lower vacancy formation energy (1.15 eV) than {0001} facet (3.90 eV). The toxicity of n-ZnO to Caco-2 cells was also dependent on the primary exposed facet; ZnO-0001 caused cell toxicity through oxidative stress, whereas ZnO-1010 resulted in lower cells viability than ZnO-0001 through oxidative stress and membrane damage. Density functional theory calculations illustrated that ·O2- was formed and released on {1010} facet, yet O22- instead of ·O2- was generated on {0001} facet, leading to low oxidative stress from ZnO-0001. All findings demonstrated that stability and toxicity of n-ZnO were dependent on the primary exposed facet, improving our understanding of health risk of nanomaterials.

Generation Mechanism of Perfluorohexanesulfonic Acid from Polyfluoroalkyl Sulfonamide Derivatives During Chloramination in Drinking Water.

Per- and polyfluoroalkyl substances (PFASs), including perfluorohexanesulfonic acid (PFHxS), as emerging persistent organic pollutants widely detected in drinking water, have drawn increasing concern. The PFHxS contamination of drinking water always results from direct and indirect sources, especially the secondary generations through environmental transformations of precursors. However, the mechanism of the transformation of precursors to PFHXS during the drinking water treatment processes remains unclear. Herein, the potential precursors and formation mechanisms of PFHxS were explored during drinking water disinfection. Simultaneously, the factors affecting PFHxS generation were also examined. This study found PFHxS could be generated from polyfluoroalkyl sulfonamide derivatives during chlorination and chloramination. The fate and yield of PFHxS varied from different precursors and disinfection processes. In particular, monochloramine more favorably formed PFHxS. Several perfluoroalkyl oxidation products and decarboxylation intermediates were detected and identified in the chloraminated samples using Fourier-transform ion cyclotron resonance mass spectrometry. Combined with density functional theory calculations, the results indicated that the indirect oxidation via the attack of the nitrogen atom in sulfonamide groups might be the dominant pathway for generating PFHxS during chloramination, and the process could be highly affected by the monochloramine dose, pH, and temperature. This study provides important evidence of the secondary formation of PFHxS during drinking water disinfection and scientific support for chemical management of PFHxS and PFHxS-related compounds.

Recent advances of semiconductor photocatalysis for water pollutant treatment: mechanisms, materials and applications.

Semiconductor photocatalysis has become an increasing area of interest for use in water treatment methods. This review systematically presents the recent developments of emerging semiconductor photocatalysis system and their application in the removal of water pollutants. A brief overview of the semiconductor photocatalysis mechanism involved with the generation of reactive oxygen species (ROS) is provided first. Then a detailed explanation of the development of TiO2-based, g-C3N4-based, and bismuth-based semiconductor materials and their applications in the degradation of water pollutants are highlighted with recent illustrative examples. Furthermore, the future prospects of semiconductor photocatalysis for water treatment are critically analyzed.

COVID-19 Pandemic Impacts on Humans Taking Antibiotics in China.

The outbreak of the novel coronavirus 2019 (COVID-19) pandemic has resulted in the increased human consumption of medicines. Antibiotics are of great concern due to their adverse effects, such as increased bacterial resistance and dysbiosis of gut microbiota. Nevertheless, very little is known about the changes in self-medication with antibiotics during the COVID-19 pandemic and the resultant potential health risks. Herein, we examined the concentration profiles of some commonly used antibiotics in human urine collected from several geographical regions in China between 2020 and 2021. Antibiotics were found in 99.2% of the urine samples at concentrations ranging from not detected (nd) to 357 000 (median: 10.2) ng/mL. During the COVID-19 pandemic, concentrations of urinary antibiotics were remarkably higher than those found either before the pandemic or in the smooth period of the pandemic. Moreover, elevated levels of antibiotics were determined in urine samples from the regions with more confirmed cases. The exposure assessment showed that hazard index values >1 were determined in 35.2% of people. These findings show that human exposure to antibiotics increased during the COVID-19 pandemic, and further research is imperative to identify the public health risks.

Effect of polar/non-polar facets on the transformation of nanoscale ZnO in simulated sweat and potential impacts on the antibacterial activity.

The use of nanoscale zinc oxide (n-ZnO) in the personal care products would cause interactions between n-ZnO and human sweat. Facet engineering has been applied to n-ZnO to improve its activity. Nevertheless, it is not clear whether the exposed facet would affect transformation of n-ZnO in sweat. Herein, we prepared ZnO nanoneedles with the dominant (1010) non-polar facet (i.e., ZnO-1010) and ZnO nanoflakes with the dominant (0001) polar facet (i.e., ZnO-0001), respectively. We found that n-ZnO can undergo chemical transformation in the simulated sweat within 168 h or 24 h, transforming into amorphous materials and Zn3(PO4)20.4 H2O and/or Na(ZnPO4)·H2O. Given the rate constant (e.g., 0.093 h-1 for ZnO-0001 vs. 0.033 h-1 for ZnO-1010) of ZnO depletion and components of the precipitate from the simulated sweat, nevertheless, the transformation is highly dependent on the dominant exposed facet of n-ZnO. The ZnO-0001 relative to ZnO-1010 would likely undergo chemical transformation, demonstrating that the (0001) polar facet compared to (1010) non-polar facet had a superior activity to the dihydrogen phosphate anions in the simulated sweat, which is supported by density functional theory calculations. The chemical transformation can affect the antibacterial activity of n-ZnO to E. coli, moderating the toxicity due to a great decrease in the concentration of the dissolved zinc. In total, our findings provided insights into the facet-dependent transformation for n-ZnO in the simulated sweat, improving our understanding of potential risk of n-ZnO.

Identification and Speciation of Nanoscale Silver in Complex Solid Matrices by Sequential Extraction Coupled with Inductively Coupled Plasma Optical Emission Spectrometry.

Nanoscale silver (n-Ag) including silver nanoparticles (Ag-NPs), silver chloride nanoparticles (AgCl-NPs), and silver sulfide nanoparticles (Ag2S-NPs) and their corresponding ionic counterpart, namely, dissolved Ag, may coexist in soils. X-ray absorption near edge spectroscopy (XANES) is used to elucidate the speciation of n-Ag in soils, whereas it possesses drawbacks like high costs, rare availability of the instrument, and providing semiquantitative data. We developed a new method for the identification and speciation of n-Ag in soils and sediments based on a sequential extraction technique coupled with inductively coupled plasma optical emission spectrometry. Extraction conditions were first evaluated, establishing the optimal extraction procedure; Ag-NPs, AgCl-NPs, and dissolved Ag in soil were simultaneously extracted by using an aqueous solution of 10 mM tetrasodium pyrophosphate, followed by selective isolation and quantification via AgCl-NPs dissolution (4.45 M aqueous ammonia), centrifugation (Ag-NPs), and detection. The Ag2S-NPs remaining in the soil were then extracted with Na2S solution at pH 7.0 through selective complexation. Optimal recoveries of Ag-NPs, AgCl-NPs, Ag2S-NPs, and dissolved Ag were 99.1 ± 2.4%, 112.0 ± 3.4%, 96.4 ± 4.0%, and 112.2 ± 4.1%, respectively. The method was validated to investigate the speciation of n-Ag in soils and sediments, exhibiting the distribution of Ag-NPs, AgCl-NPs, Ag2S-NPs, and dissolved Ag in each sample, wherein Ag2S-NPs, the major species of n-Ag, accounted for 35.42-68.87% of the total Ag. The results of n-Ag speciation in soil are comparable to those obtained through the linear combination fitting of XANES. This method thus is a powerful, yet convenient, substitute for XANES to understand the speciation of n-Ag in complex solid matrices.

Environmentally relevant concentrations of microplastic exhibits negligible impacts on thiacloprid dissipation and enzyme activity in soil.

Microplastics (MPs) as a type of emerging contaminant in the environment have attracted extensive attentions in recent years, and understanding the impacts of MPs on soil biodiversity and functioning are thus increasingly urgent. Nevertheless, few studies were performed to investigate potential effects of MPs on decay of soil organic pollutants in particular pesticides and enzyme activities. Herein, three types of MPs including polystyrene fragments (PS-50) and polyvinyl chloride beads (PVC-42000 and PVC-10) were added to soil at environmentally relevant concentrations (0.2 and 1.0%) to study their impacts on dissipation of thiacloprid and activities of urease, acid phosphatase, invertase and catalase. MPs exhibited negligible impacts on thiacloprid dissipation regardless of MPs type and content, being probably attributed to the unaltered bioavailability of thiacloprid in soil even after an addition of MPs, which was documented by using the hydroxypropyl-ß- cyclodextrin (HPCD) extraction method. Batch sorption experiments also exhibited the comparable adsorption capacity of thiacloprid to soil with and without MPs, along with Kf valuses of 3.44-3.77. Besides, MPs exerted negligible effects on enzyme activities of soil. Taken together, this study showed negligible impacts of MPs at environmentally relevant concentrations on thiacloprid dissipation and enzyme activity, expanding our knowledge on impacts of MPs at the environmentally relevant concentrations on pesticide dissipation in soil.

Defect-Abundant Covalent Triazine Frameworks as Sunlight-Driven Self-Cleaning Adsorbents for Volatile Aromatic Pollutants in Water.

Covalent triazine frameworks (CTFs) with high adsorption potential and photocatalytic ability features are expected to be designed as a new class of adsorbents that can regenerate themselves just by harnessing sunlight. To simultaneously improve both the adsorption and photocatalytic regeneration performance, a defect-abundant CTF-m was designed and tuned effectively by varying the lengths of benzene ring chains incorporated into the CTF backbone. It has been demonstrated that two kinds of defects in terms of broken benzene rings and pyrrole nitrogen were newly generated, other than the normal benzene rings and triazine units in the CTF-m skeleton. Benefiting from these defects, the adsorption sites with high energy for adsorbing volatile aromatic pollutants were significantly increased, which are reflected by higher saturated adsorption capacities of CTF-m (3.026 mmol/g for benzene (BEN), 1.490 mmol/g for naphthalene (NAP), and 0.863 mmol/g for phenol (PHE)) compared with those of CTF-1 and CTF-2. Furthermore, these defects narrowed the band structure and facilitated the separation of photogenerated charge carries, thus promoting photocatalytic regeneration. The percentage of CTF-m regenerated was still higher than 90% in the fourth cycle. These experimental results, together with the density functional theory (DFT) studies, soundly corroborated that the defects could optimize the adsorption and regeneration property of CTF-m. The present work highlights the potential of fabrication of defective CTFs as solar-driven self-cleaning adsorbents to remove pollutants from water.

A universal aptasensing platform based on cryonase-assisted signal amplification and graphene oxide induced quenching of the fluorescence of labeled nucleic acid probes: application to the detection of theophylline and ATP.

This study describes a universal fluorometric method for sensitive detection of analytes by using aptamers. It is based on the use of graphene oxide (GO) and cryonase-assisted signal amplification. GO is a strong quencher of FAM-labeled nucleic acid probes, while cryonase digests all types of nucleic acid probes. This makes the platform widely applicable to analytes for which the corresponding aptamers are available. Theophylline and ATP were chosen as model analytes. In the absence of targets, dye-labeled aptamers are in a flexible single strand state and adsorb on the GO. As a result, the probes are non-fluorescent due to the efficient quenching of dyes by GO. Upon the addition of a specific target, the aptamer/target complex desorbed from the GO surface and the probe becomes fluorescent. The released complex will immediately become a substrate for cryonase digestion and subsequently releasing the target to bind to another aptamer to initiate the next round of cleavage. This cyclic reaction will repeat again and again until all the related-probes are consumed and all fluorophores light up, resulting in significant fluorescent signal amplification. The detection limits are 47 nM for theophylline and 22.5 nM for ATP. This is much better than that of known methods. The assay requires only mix-and-measure steps that can be accomplished rapidly. In our perception, the detection scheme holds great promise for the design enzyme-aided amplification mechanisms for use in bioanalytical methods. Graphical abstract A cryonase-assisted signal amplification (CASA) method has been developed by using graphene oxide (GO) conjugated with a fluorophore-labeled aptamer for fluorescence signal generation. It has a large scope because it may be applied to numerous analytes.