Degradation of natural organic matter and disinfection byproducts formation by solar photolysis of free available chlorine.

Environment disinfection effectively curbs transmission of the Severe Acute Respiratory Syndrome Coronavirus-2 (SARS-CoV-2). However, elevated concentration of free available chlorine (FAC) in disinfectants can be discharged into surface water, generating toxic disinfection byproducts (DBPs). The impact of solar photolysis of FAC on natural organic matter (NOM) to form DBPs has not been well studied. In this work, solar photolysis of FAC was found to result in higher formation of DBPs, DBPs formation potential (DBPsFP), total organic chlorine (TOCl) and lower specific ultraviolet absorbance at 254 nm (SUVA254), compared to dark chlorination. In solar photolysis of FAC, formation of total DBPs was promoted by pH=8, but hindered by the addition of HCO3-, radical scavenger or deoxygenation, while addition of NO3-and NH4+both enhanced the formation of nitrogenous DBPs. Differences in the formation of DBPs in solar photolysis of FAC under various conditions were influenced by reactive species. The formation of trichloromethane (TCM) and haloacetic acids (HAAs) in solar photolysis of FAC positively correlated with the steady-state concentrations of ClO• and O3. The steady-state concentrations of •NO and •NH2 positively correlated with the formation of halonitromethanes (HNMs). HAAs and haloacetonitriles (HANs) mainly contributed to calculated cytotoxicity of DBPs. This study demonstrates that solar photolysis of FAC may significantly impact the formation of DBPs in surface water due to extensive use of disinfectants containing FAC during SARS-CoV-2 pandemic.

Formation of Larger Molecular Weight Disinfection Byproducts from Acetaminophen in Chlorine Disinfection.

Acetaminophen is widely used to treat mild to moderate pain and to reduce fever. Under the worldwide COVID-19 pandemic, this over-the-counter pain reliever and fever reducer has been drastically consumed, which makes it even more abundant than ever in municipal wastewater and drinking water sources. Chlorine is the most widely used oxidant in drinking water disinfection, and chlorination generally causes the degradation of organic compounds, including acetaminophen. In this study, a new reaction pathway in the chlorination of acetaminophen, i.e., oxidative coupling reactions via acetaminophen radicals, was investigated both experimentally and computationally. Using an ultraperformance liquid chromatograph coupled to an electrospray ionization-triple quadrupole mass spectrometer, we detected over 20 polymeric products in chlorinated acetaminophen samples, some of which have structures similar to the legacy pollutants "polychlorinated biphenyls". Both C-C and C-O bonding products were found, and the corresponding bonding processes and kinetics were revealed by quantum chemical calculations. Based on the product confirmation and intrinsic reaction coordinate computations, a pathway for the formation of the polymeric products in the chlorination of acetaminophen was proposed. This study suggests that chlorination may cause not only degradation but also upgradation of a phenolic compound or contaminant.

Mechanistic insights into the generation and control of Cl-DBPs during wastewater sludge chlorination disinfection process.

Chlorination disinfection has been widely used to kill the pathogenic microorganisms in wastewater sludge during the special Covid-19 period, but sludge chlorination might cause the generation of harmful disinfection byproducts (DBPs). In this work, the transformation of extracellular polymeric substance (EPS) and mechanisms of Cl-DBPs generation during sludge disinfection by sodium hypochlorite (NaClO) were investigated using multispectral analysis in combination with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The microorganism Escherichia coli (E. coli) was effectively inactivated by active chlorine generated from NaClO. However, a high diversity of Cl-DBPs were produced with the addition of NaClO into sludge, causing the increase of acute toxicity on Q67 luminous bacteria of chlorinated EPS. A variety of N-containing molecular formulas were produced after chlorination, but N-containing DBPs were not detected, which might be the indicative of the dissociation of -NH2 groups after Cl-DBPs generated. Additionally, the release of N-containing compounds was increased in alkaline environment caused by NaClO addition, resulted in more Cl-DBPs generation via nucleophilic substitutions. Whereas, less N-compounds and Cl-DBPs were detected after EPS chlorination under acidic environment, leading to lower cell cytotoxicity. Therefore, N-containing compounds of lignin derivatives in sludge were the major Cl-DBPs precursors, and acidic environment could control the release of N-compounds by eliminating the dissociation of functional groups in lignin derivatives, consequently reducing the generation and cytotoxicity of Cl-DBPs. This study highlights the importance to control the alkalinity of sludge to reduce Cl-DBPs generation prior to chlorination disinfection process, and ensure the safety of subsequential disposal for wastewater sludge.

[Pollution Characteristics and Risk Assessment of DBPs in Typical Drinking Water Sources in Wuhan Under the COVID-19 Pandemic].

In order to reveal the pollution characteristics and risk levels of DBPs in typical drinking water sources in Wuhan under the COVID-19 pandemic, 26 sampling sites were selected in typical drinking water sources in Wuhan. N,N-diethyl-1,4-phenylenediamine spectrophotometry and gas chromatograph-micro-cell electron capture detector (GC-µECD) methods were used to detect residual chlorine disinfectants and DBPs in water, respectively, and their health and ecology risks were assessed. The results showed that free chlorine or total residual chlorine were detected in 16 of the 26 water samples, and the maximum concentration was 0.04 mg·L-1, which exceeded the limit of the surface water standard in China. The concentration of residual chlorine was higher in sampling sites near the outfall of a municipal sewage plant. There were 34 types of DBPs measured in 10 sampling sites, and 24 types of substances were detected with the detection rate of 10.00%-100.00%. The ρ (total DBPs) was in the range of 0.11-104.73 µg·L-1, with an average value of 7.26 µg·L-1. The concentration of chloroform was the highest among all the DBPs, ranging from 9.98 µg·L-1 to 11.15 µg·L-1, with an average value of 10.47 µg·L-1. The concentration of 2-bromo-2-iodoacetamide was the lowest, ranging from ND-0.11 µg·L-1, with an average value of 0.01 µg·L-1. The overall detection level of the DBPs area was low in this study area, and the result of the health risk assessment showed that the DBPs had no carcinogenic or non-carcinogenic health risks to human body. However, the results of the ecological risk assessment showed that chloroform presented a high ecological risk to aquatic organisms.

Impacts of COVID-19 pandemic on the aquatic environment associated with disinfection byproducts and pharmaceuticals.

In this study, concentrations of disinfection byproducts (DBPs) and COVID-19 related pharmaceuticals in wastewater effluents and surface water were measured two weeks, three months and eight months after the lockdown in Wuhan. Little temporal variation in DBP concentrations suggested intensified disinfection during the COVID-19 pandemic had limited impacts on the occurrence of DBPs in the aquatic environment. In contrast, the pandemic led to a significant increase in concentrations of lopinavir and ritonavir in wastewater effluents and surface water. The high detection frequency of these pharmaceuticals in surface water after the lockdown highlighted their mobility and persistence in the aquatic environment. The initial ecological risk assessment indicated moderate risks associated with these pharmaceuticals in surface water. As the global situation is still rapidly evolving with a continuous surge in the number of confirmed COVID-19 cases, our results suggest a pressing need for monitoring COVID-19 related pharmaceuticals as well as a systematic evaluation of their ecotoxicities in the aquatic environment.

Study on the influence of operational and management processes of a water reclamation plant since COVID-19 situation.

Reusing treated wastewater can effectively alleviate water shortages and water contamination problems but depends on ensuring the safety of the reclaimed water that is produced. The operating and management conditions for water reclamation plants in China have been changed since the outbreak of the COVID-19 epidemic in China at the end of 2019 to prevent emerging viruses being spread through wastewater treatment processes and the reclaimed water that is produced. Removal of pathogens and trace organic compounds (e.g., pharmaceuticals and personal care products and endocrine disrupting chemicals) in a real water reclamation plant after the start of COVID-19 epidemic was studied. Disinfection byproduct formation caused by chlorine being added to meet disinfection requirements was also assessed. The pathogenic microorganism concentrations in effluent were <2 (most probable number)/L, and the removal rates for most trace organic compounds were >80% when advanced treatments were performed using ozone, ultraviolet light, and chlorine doses of 2 mg/L, 20.5 mJ/cm2, and 2-3 mg/L, respectively. The main disinfection byproduct produced at a chlorine dose of 2 mg/L and a residence time of 1 h was chloroform (at concentrations <15 µg/L). The results indicated that the water reclamation processes with modified conditions gave high pathogen and trace organic compound removal rates and reasonably well-controlled disinfection byproduct concentrations.