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.

Development and Validation of a Novel Stability Indicating Reverse Phase High Performance Liquid Chromatographic Method for Related Substances and Assay Analysis of Molnupiravir Drug Substance and Drug Product

Molnupiravir, a broad-spectrum antiviral is an isopropyl ester prodrug of beta-D-N4-hydroxycytidine. Molnupiravir targets RNA-dependent RNA-polymerase enzyme of the viruses. A new stability-indicating HPLC-method was developed to determine related substances and assay of molnupiravir. Separation was achieved by using Shim-pack GWS C18 column. The method was validated according to current ICH requirements. The calibration plot gave a linear relationship for all known analytes over the concentration range from LOQ to 200%. LOD and LOQ for all known analytes were found in 0.05-0.08 microg mL-1 and 0.12-0.20 microg mL-1, respectively, the mean recovery was found to be 97.79-102.44 %. Study showed that the method, results of robustness, solution stability studies are precise and within the acceptable limits. Molnupiravir was found to degrade in acid, alkali, and oxidative conditions, and was stable in thermal, moisture, and photolytic degradation condition. The method is simple, accurate, precise, and reproducible for routine purity analysis of drug-samples.Copyright © 2022 Indian Drug Manufacturers' Association. All rights reserved.

Occurrence and Treatment of Antibiotic-Resistant Bacteria Present in Surface Water.

According to the World Health Organization, antibiotic resistance is one of the main threats to global health. The excessive use of several antibiotics has led to the widespread distribution of antibiotic-resistant bacteria and antibiotic resistance genes in various environment matrices, including surface water. In this study, total coliforms, Escherichia coli and enterococci, as well as total coliforms and Escherichia coli resistant to ciprofloxacin, levofloxacin, ampicillin, streptomycin, and imipenem, were monitored in several surface water sampling events. A hybrid reactor was used to test the efficiency of membrane filtration, direct photolysis (using UV-C light emitting diodes that emit light at 265 nm and UV-C low pressure mercury lamps that emit light at 254 nm), and the combination of both processes to ensure the retention and inactivation of total coliforms and Escherichia coli as well as antibiotic-resistant bacteria (total coliforms and Escherichia coli) present in river water at occurrence levels. The membranes used (unmodified silicon carbide membranes and the same membrane modified with a photocatalytic layer) effectively retained the target bacteria. Direct photolysis using low-pressure mercury lamps and light-emitting diode panels (emitting at 265 nm) achieved extremely high levels of inactivation of the target bacteria. The combined treatment (unmodified and modified photocatalytic surfaces in combination with UV-C and UV-A light sources) successfully retained the bacteria and treated the feed after 1 h of treatment. The hybrid treatment proposed is a promising approach to use as point-of-use treatment by isolated populations or when conventional systems and electricity fail due to natural disasters or war. Furthermore, the effective treatment obtained when the combined system was used with UV-A light sources indicates that the process may be a promising approach to guarantee water disinfection using natural sunlight.

The photolytic behavior of COVID-19 antivirals ribavirin in natural waters and the increased environmental risk.

Increasing drug residues in aquatic environments have been caused by the abuse of antivirals since the global spread of the COVID-19 epidemic, whereas research on the photolytic mechanism, pathways and toxicity of these drugs is limited. The concentration of COVID-19 antivirals ribavirin in rivers has been reported to increase after the epidemic. Its photolytic behavior and environmental risk in actual waters such as wastewater treatment plant (WWTP) effluent, river water and lake water were first investigated in this study. Direct photolysis of ribavirin in these media was limited, but indirect photolysis was promoted in WWTP effluent and lake water by dissolved organic matter and NO3-. Identification of photolytic intermediates suggested that ribavirin was photolyzed mainly via C-N bond cleavage, splitting of the furan ring and oxidation of the hydroxyl group. Notably, the acute toxicity was increased after ribavirin photolysis owing to the higher toxicity of most of the products. Additionally, the overall toxicity was greater when ARB photolysis in WWTP effluent and lake water. These findings emphasize the necessity to concern about the toxicity of ribavirin transformation in natural waters, as well as to limit its usage and discharge.

Model Evaluation of Secondary Chemistry due to Disinfection of Indoor Air with Germicidal Ultraviolet Lamps

Air disinfection using germicidal ultraviolet light (GUV) has received increasing attention during the COVID-19 pandemic. GUV uses UVC lamps to inactivate microorganisms, but it also initiates photochemistry in air. However, GUV's indoor-air-quality impact has not been investigated in detail. Here, we model the chemistry initiated by GUV at 254 ("GUV254”) or 222 nm ("GUV222”) in a typical indoor setting for different ventilation levels. Our analysis shows that GUV254, usually installed in the upper room, can significantly photolyze O3, generating OH radicals that oxidize indoor volatile organic compounds (VOCs) into more oxidized VOCs. Secondary organic aerosol (SOA) is also formed as a VOC-oxidation product. GUV254-induced SOA formation is of the order of 0.1-1 μg/m3 for the cases studied here. GUV222 (described by some as harmless to humans and thus applicable for the whole room) with the same effective virus-removal rate makes a smaller indoor-air-quality impact at mid-to-high ventilation rates. This is mainly because of the lower UV irradiance needed and also less efficient OH-generating O3 photolysis than GUV254. GUV222 has a higher impact than GUV254 under poor ventilation due to a small but significant photochemical production of O3 at 222 nm, which does not occur with GUV254. © 2022 American Chemical Society.

Changes in tropospheric ozone concentration over Indo-Gangetic Plains: the role of meteorological parameters

This study seeks to understand and quantify the changes in tropospheric ozone (O3) in lower troposphere (LT), middle troposphere (MT) and upper middle troposphere (UMT) over the Indo-Gangetic Plains (IGPs), India during the COVID-19 lockdown 2020 with that of pre-lockdown 2019. The gridded datasets of ozone from the European Centre for Medium-range Weather Forecasts (ECMWF) reanalysis product, ERA5 in combination with statistical interpolated (IDWs) surface NO2 observations, present a consistent picture and indicate a significant tropospheric ozone enhancement over IGP during COVID-19 lockdown restrictions in May 2020. The Paper also examines the influencing role of meteorological parameters on increasing ozone concentration. Over LT, an increase in O3 concentration (23%) is observed and in MT to UMT an enhancement of about 9–18% in O3 concentration have been seen during May 2020 with respect to May 2019. An investigation on causes of increasing  ozone concentration (35–85 ppbv) from MT to UMT during May 2020 reveals that there was significant rise (by 1–6%) in low cloud cover (LCC). Notably, higher LCC increases the backscattering of upward solar radiation from the top of the atmosphere. A positive difference of 5–25 W/m2 in upward solar radiation (USR) is observed across the entire study region. The result suggests that higher LCC significantly contributed to the enhanced USR. Thereby, resulting in higher photolysis rate that lead to an increase in mid tropospheric ozone concentration during May 2020. The results highlight the importance of LCC as an important pathway in ozone formation and aid in scientific understanding of it.

Detection and Treatment of Persistent Pollutants in Water: General Review of Pharmaceutical Products

Environmental problems of great complexity arise from the enormous number of toxic substances that are generated by anthropogenic activities. Seemingly, society encounters new issues every day thus these problems seem to be endless. Now in the face of the COVID‐19 pandemic and the SARS‐CoV‐2 crisis, a large number of emerging treatment compounds generated by pharmaceutical companies worldwide makes future issues even more treacherous. For this reason, there is an increasing need to detect and treat emerging compounds to prevent them from becoming persistent pollutants. This review describes the advances in the use of electrochemical sensors with modified carbon‐based electrodes among other issues, to determine antibiotics, anti‐inflammatories and antidepressants levels in the environment. It further explores technologies suggested for cleaning wastewater polluted by pharmaceutical products using biological or advanced oxidation processes including photolysis, photocatalysis, microwave heating, ultrasound, Fenton, electro‐Fenton, photoelectro‐Fenton and various combined treatments.We, the authors, dedicate this report, with love, to all the people afflicted by COVID-19 during the pandemic arising from SARS-CoV-2. In particular, we wish to honor the medical people who have and continue to help affected patients, and the medical researchers who generate the medicines and vaccines for all of us.

Plasma bioscience for medicine, agriculture and hygiene applications.

Nonthermal biocompatible plasma (NBP) sources operating in atmospheric pressure environments and their characteristics can be used for plasma bioscience, medicine, and hygiene applications, especially for COVID-19 and citizen. This review surveyed the various NBP sources, including a plasma jet, micro-DBD (dielectric barrier discharge) and nanosecond discharged plasma. The electron temperatures and the plasma densities, which are produced using dielectric barrier discharged electrode systems, can be characterized as 0.7 ~ 1.8 eV and (3-5) × 1014-15 cm-3, respectively. Herein, we introduce a general schematic view of the plasma ultraviolet photolysis of water molecules for reactive oxygen and nitrogen species (RONS) generation inside biological cells or living tissues, which would be synergistically important with RONS diffusive propagation into cells or tissues. Of the RONS, the hydroxyl radical [OH] and hydrogen peroxide H2O2 species would mainly result in apoptotic cell death with other RONS in plasma bioscience and medicines. The diseased biological protein, cancer, and mutated cells could be treated by using a NBP or plasma activated water (PAW) resulting in their apoptosis for a new paradigm of plasma medicine.

Revealing the toxicity of lopinavir- and ritonavir-containing water and wastewater treated by photo-induced processes to Danio rerio and Allivibrio fischeri.

In coronavirus disease 2019 (COVID-19), among many protocols, lopinavir and ritonavir in individual or combined forms with other drugs have been used, causing an increase in the concentration of antiviral drugs in the wastewater and hospital effluents. In conventional wastewater treatment plants, the removal efficiency of various antiviral drugs is estimated to be low (<20%). The high values of predicted no-effect concentration (PNEC) for lopinavir and ritonavir (in ng∙L-1) reveal their high chronic toxicity to aquatic organisms. This indicates that lopinavir and ritonavir are current priority antiviral drugs that need to be thoroughly monitored and effectively removed from any water and wastewater samples. In this study, we attempt to explore the impacts of two photo-induced processes (photolysis and photocatalysis) on the toxicity of treated water and wastewater samples containing lopinavir and ritonavir to zebrafish (Danio rerio) and marine bacteria (Allivibrio fischeri). The obtained results reveal that traces of lopinavir in water under photo-induced processes may cause severe problems for Danio rerio, including pericardial edema and shortening of the tail, affecting its behavior, and for Allivibrio fischeri as a result of the oxygen-depleted environment, inflammation, and oxidative stress. Hence, lopinavir must be removed from water and wastewater before being in contact with light. In contrast, the photo-induced processes of ritonavir-containing water and wastewater reduce the toxicity significantly. This shows that even if the physicochemical parameters of water and wastewater are within the standard requirements/limits, the presence of traces of antiviral drugs and their intermediates can affect the survival and behavior of Danio rerio and Allivibrio fischeri. Therefore, the photo-induced processes and additional treatment of water and wastewater containing ritonavir can minimize its toxic effect.

Amphiphilic Janus Microspheres Prepared by Caged Photoactivatable Alkoxysilane

A simple photolysis route was proposed to prepare Amphiphilic Janus Particles (AJP) based on SiO2 microspheres. The surface of SiO2 microspheres were modified by photoactive alkoxysilane, which was synthesized by dealcoholization condensation of 6-nitroveratroyloxycarbonyl and isocyanatopropyl-triethoxysilane. UV irradiation caused eater-breaking allowed for the precise control of hydrophilic modification of the hemispherical exposed particles surfaces. The component and morphology of the obtained particles were characterized by fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy, and the Janus feature was evaluated by scanning electron microscopy, transmission electron microscopy, and dispersity in the oil–water dual-phases. The following results were obtained. The AJP with 450 nm size processes the hydrophilic amino groups on one side and the hydrophobic 6-nitroveratryloxycarbonyl moieties on the other. Additionally, the AJP were located at the phase boundary between water and n-hexane, and the negative charged gold nanoparticles with 25 nm size were adsorbed only onto the side with the positive charged amino groups. The AJP have interfacial adsorption energies that can be as much as three times larger than that of homogeneous particles and thus exhibit excellent surface activities.

Insights on In-Situ Photochemistry Associated with Ozone Reduction in Guangzhou during the COVID-19 Lockdown

Increases in ground-level ozone (O3 ) have been observed during the COVID-19 lockdown in many places around the world, primarily due to the uncoordinated emission reductions of O3 precursors. In Guangzhou, the capital of Guangdong province in South China, O3 distinctively decreased during the lockdown. Such a phenomenon was attributed to meteorological variations and weakening of local O3 formation, as indicated by chemical transport models. However, the emission-based modellings were not fully validated by observations, especially for volatile organic compounds (VOCs). In this study, we analyzed the changes of O3 and its precursors, including VOCs, from the pre-lockdown (Pre-LD) to lockdown period (LD) spanning 1 week in Guangzhou. An observation-based box model was applied to understand the evolution of in-situ photochemistry. Indeed, the ambient concentrations of O3 precursors decreased significantly in the LD. A reduction of 20.7% was identified for the total mixing ratios of VOCs, and the transportation-related species experienced the biggest declines. However, the reduction of O3 precursors would not lead to a decrease of in-situ O3 production if the meteorology did not change between the Pre-LD and LD periods. Sensitivity tests indicated that O3 formation was limited by VOCs in both periods. The lower temperature and photolysis frequencies in the LD reversed the increase of O3 that would be caused by the emission reductions otherwise. This study reiterates the fact that O3 abatement requires coordinated control strategies, even if the emissions of O3 precursors can be significantly reduced in the short term. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

Measurement report: Fast photochemical production of peroxyacetyl nitrate (PAN) over the rural North China Plain during haze events in autumn

Photochemical pollution over the North China Plain (NCP) is attracting much concern. We usually view peroxyacetyl nitrate (PAN) as the second most important photochemical pollutant featuring high mixing ratios during warm seasons. Our observations at a background site in the NCP identified high PAN concentrations, even during haze events in autumn. The substantial increasing ratios of PAN, by 244 % and 178 %, over the morning hours (08:00–12:00 local time) on 20 and 25 October 2020 were 10.6 and 7.7 times larger than those on clean days. Polluted days are characterized by higher temperature, higher humidity, and anomalous southerly winds compared with clean days. Enhanced local photochemistry has been identified as being the dominant factor that controls the PAN increase in the morning at the rural site, as the time when prevailing wind turns to a southerly wind is too late to promote direct transport of PAN from the polluted urban region. By removing the effect of direct transport of PAN, we provide a quantitative assessment of net PAN chemical production rate of 0.45 ppb h-1 for the mornings of polluted days, also demonstrating the strong local photochemistry. Using observations and calculated photolysis rates, we find that acetaldehyde oxidation by hydroxyl radical (OH) is the primary pathway of peroxyacetyl radical formation at the rural site. Acetaldehyde concentrations and production rates of HOx (HOx= OH + HO2) on polluted days are 2.8 and 2 times as large as those on clean days, leading to a remarkable increase in PAN in the morning. Formaldehyde (HCHO) photolysis dominates the daytime HOx production, thus contributing to fast photochemistry of PAN. Our observational results suggest the cause of a rapid increase in PAN during haze events in autumn at a rural site of the NCP and provide evidence of important role of HCHO photolysis in secondary pollutants at lower nitrogen oxide emissions. This highlights the urgency of carrying out strict volatile organic compound controls over the NCP during the cold season and not just in summer.