The influence of pH on the efficacy of oxidation-reduction potential (ORP) to predict chlorine disinfection of surrogate bacteria, Escherichia coli O157:H7 and Listeria monocytogenes in oxidant demand free conditions and fresh produce wash water.

Oxidation-reduction potential (ORP) is commonly used as a rapid measurement of the antimicrobial potential of free chlorine during industrial fresh produce washing. The current study tested the hypothesis that ORP can act as a "single variable" measurement of bacterial (vegetative and endospores) inactivation effectiveness with free chlorine irrespective of the water pH value. This situation has on occasion been assumed but never confirmed nor disproven. Chlorine-dosed pH 6.5 and 8.5 phosphate buffer solutions were inoculated with Escherichia coli (E. coli), Listeria innocua (L. innocua), or Bacillus subtilis (B. subtilis) endospores. ORP, free chlorine (FC), and log reduction were monitored after 5 s (for E. coli and L. innocua) and up to 30 min (for B. subtilis spores) of disinfection. Logistic and exponential models were developed to describe how bacteria reduction varied as a function of ORP at different pH levels. Validation tests were performed in phosphate buffered pH 6.5 and 8.5 cabbage wash water periodically dosed with FC, cabbage extract and a cocktail of Escherichia coli O157:H7 (E. coli O157:H7) and Listeria monocytogenes (L. monocytogenes). The built logistic and exponential models confirmed that at equal ORP values, the inactivation of the surrogate strains was not consistent across pH 6.5 and pH 8.5, with higher reductions at higher pH. This is the opposite of the well-known free chlorine-controlled bacterial inactivation, where the antibacterial effect is higher at lower pH. The validation test results indicated that in the cabbage wash water, the relationship between disinfection efficiency and ORP was consistent with the oxidant demand free systems. The study suggests that ORP cannot serve as a reliable single variable measurement to predict bacterial disinfection in buffered systems. When using ORP to monitor and control the antibacterial effectiveness of the chlorinated wash water, it is crucial to take into account (and control) the pH.

Chlorine Water Taste Threshold and Acceptability among Indigenous and Non-Indigenous Populations in Rural Panama.

Although gains in access to water services over the past two decades have been large, more than two billion people still lack access to safely managed drinking water. This study examines and compares free chlorine taste and acceptability thresholds of rural Indigenous Ngäbe and rural Latino Panamanians to study if taste aversion may be a limiting factor in chlorination of community systems in Panama using the three-alternative forced choice test methodology. This study is the first to establish a best-estimate taste threshold for a rural Indigenous group and the only study in Latin America to report best-estimate taste thresholds using those methods. Median taste thresholds were 0.87 mg/L Cl2 for Indigenous Ngäbe participants (n = 82) and 1.64 mg/L Cl2 for Latino participants (n = 64), higher than both the minimum concentration for biologically safe water (0.2 mg/L) and the recommended concentration range in Panama (0.3-0.8 mg/L). Median acceptability thresholds were established much higher than taste thresholds at 3.45 mg/L Cl2. The results show that the ability to accurately taste chlorine may not be the limiting factor for adoption of safe water initiatives in remote and Indigenous communities.

How to achieve adequate quenching for DBP analysis in drinking water?

Quenching is an important step to terminate disinfection during preparation of disinfected water samples for the analysis of disinfection byproducts (DBPs). However, an incomplete quenching might result in continued reactions of residual chlorine, whereas an excessive quenching might decompose target DBPs. Therefore, an adequate quenching to achieve simultaneous disinfection termination and DBP preservation is of particular importance. In this study, the two-stage reaction kinetics of chlorine and three commonly used quenching agents (i.e., ascorbic acid, sodium thiosulfate, and sodium sulfite) were determined. Stopping quenching during the first stage prevented interactions of residual chlorine with natural organic matter. Complete quenching was achieved by minimizing the quenching time for ascorbic acid and sodium sulfite, while limiting the quenching time to less than 3 min for sodium thiosulfate. At the optimized quenching times, the molar ratios (MRs) of quenching agent to chlorine were 1.05, 1.10, and 0.75 for ascorbic acid, sodium sulfite, and sodium thiosulfate, respectively. The destructive effects of the three quenching agents on total organic halogen (TOX) followed the rank order of ascorbic acid (33.7-64.8 %) < sodium sulfite (41.6-72.8 %) < sodium thiosulfate (43.3-73.2 %), and the destructive effects on aliphatic DBPs also followed the rank order of ascorbic acid (29.5-44.5 %) < sodium sulfite (34.9-51.9 %) < sodium thiosulfate (46.9-53.2 %). For total organic chlorine (TOCl) and aliphatic DBPs, the quenching behavior itself had more significant destructive effect than the quenching agent type/dose and quenching time, but for total organic bromine (TOBr), the destructive effect caused by quenching agent type/dose and quenching time was more significant. High-dose, long-duration quenching enhanced the reduction of TOX, but had little effect on aliphatic DBPs. Additionally, the three quenching agents reduced the levels of halophenols (except for tribromophenol), while maintained or increased the levels of tribromophenol, halobenzoic/salicylic acids, and halobenzaldehydes/salicylaldehydes. To achieve adequate quenching for overall DBP analysis in chlorinated water samples, it is recommended to use ascorbic acid at a quenching agent-to-chlorine MR of 1.0 for a quenching time of < 0.5 h.

The formation and control of disinfection by-products by two-step chlorination for sewage effluent: Role of organic chloramine decomposition among molecular weight fractions.

With the increasing discharge of wastewater effluent to natural waters, there is an urgent need to achieve both pathogenic microorganism inactivation and the mitigation of disinfection by-products (DBPs) during disinfection. Studies have shown that two-step chlorination, which injected chlorine disinfectant by splitting into two portions, was more effective in inactivating Escherichia coli than one-step chlorination under same total chlorine consumption and contact time. In this study, we observed a substantial reduction in the formation of five classes of CX3R-type DBPs, especially highly toxic haloacetonitriles (HANs), during two-step chlorination of secondary effluent when the mass ratio of chlorine-to-nitrogen exceeded 2. The shift of different chlorine species (free chlorine, monochloramine and organic chloramine) verified the decomposition of organic chloramines into monochloramine during second chlorination stage. Notably, the organic chloramines generated from the low molecular weight (< 1 kDa) fraction of dissolved organic nitrogen in effluent organic matter tended to decompose during the second step chlorination leading to the mitigation of HAN formation. Furthermore, the microbiological analysis showed that two-step chlorinated effluent had a slightly lower ecological impact on surface water compared to one-step chlorination. This work provided more information about the two-step chlorination for secondary effluent, especially in terms of organic chloramine transformation and HAN control.

Verification of chlorine exposure via LC-MS/MS analysis of base hydrolyzed chlorophenols from chlorotyrosine-protein adducts.

Inhalation of chlorine gas, with subsequent hydrolysis in the airway and lungs to form hydrochloric acid (HCl) and hypochlorous acid (HOCl), can cause pulmonary edema (i.e., fluid build-up in the lungs), pulmonary inflammation (with or without infection), respiratory failure, and death. The HOCl produced from chlorine is known to react with tyrosine to form adducts via electrophilic aromatic substitution, resulting in 3-chlorotyrosine and 3,5-dichlorotyrosine adducts. While several analysis methods are available for determining these adducts, each method has significant disadvantages. Hence, a simple and sensitive ultra-high performance liquid chromatography-tandem mass spectroscopy (UHPLC-MS/MS) method was developed for the determination of chlorotyrosine adducts. The sample preparation involves base hydrolysis of isolated plasma proteins to form 2-chlorophenol (CP) from monochlorotyrosine adducts and 2,6-dichlorophenol (2,6-DCP), from dichlorotyrosine adducts, as markers of chlorine exposure. The chlorophenols are extracted with cyclohexane prior to UHPLC-MS/MS analysis. The method produced excellent sensitivity for 2,6-DCP with a limit of detection of 2.2 µg/kg, calibration curve linearity extending from 0.054-54 mg/kg (R2 ≥ 0.9997 and %RA > 94), and accuracy and precision of 100 ± 14 %, and <15 % relative standard deviation, respectively. The sensitivity of the method for 2-CP was relatively poor, so it was used only as a secondary marker for severe chlorine exposure. The method successfully detected elevated levels of 2,6-DCP from hypochlorite-spiked plasma protein and plasma protein isolated from chlorine-exposed rats.

Release of biochar-derived dissolved organic matter and the formation of chlorination disinfection by-products: Effects of pH and chlorine dosage.

Transformation, fragmentation, dissolution, and oxidation of biochar are inevitable in the environment, which will undoubtedly accelerate the release of biochar-derived dissolved organic matter (BDOM) into various water bodies. In addition, biochar may affect disinfection by-products (DBPs) during water treatment and subsequent disinfection. In this study, biochars were derived at three selected pyrolysis temperatures (350 °C, 500 °C, and 650 °C) from rice husk, wheat straw, and shrimp shell, and BDOM was extracted from biochar-derived in artificial seawater and ultrapure water. The TOC analyzer results showed that the concentrations of three BDOM decreased with increasing pyrolysis temperature. The BDOM derived from rice husk biochar and wheat straw biochar in seawater was lower than that in ultrapure water, while that of shrimp shell biochar showed an opposite trend, being released in seawater at nearly twice the extent of that in ultrapure water at 350 °C. Moreover, BDOM showed a catalytic effect on chlorination, and GC analysis showed that the concentrations of its DBPs were affected by pH. The concentration of halogenated acetic acid reached the highest value (54.51 µg/L) in weak acidic environment, while the concentrations of trihalomethane and halogenated acetonitrile had the highest values (23.63 and 47.53 µg/L, respectively) in alkaline conditions. The concentrations of all the three DBPs were lowest under neutral pH conditions. In addition, the volatile halogenated DBPs such as dichloroacetone and trichloroacetone were easily hydrolyzed under alkaline conditions. Therefore, it is something be aware of the release of BDOM and the effects of chlorination DBPs when biochar is used for water treatment or water purification.

Molecular insight of dissolved organic matter and chlorinated disinfection by-products in reclaimed water during chlorination with permanganate preoxidation.

Permanganate is a common preoxidant applied in water treatment to remove organic pollutants and to reduce the formation of disinfection by-products. However, the effect of permanganate preoxidation on the transformation of dissolved effluent organic matter (dEfOM) and on the formation of unknown chlorinated disinfection by-products (Cl-DBPs) during chlorination remains unknown at molecular level. In this work, the molecular changes of dEfOM during permanganate preoxidation and subsequent chlorination were characterized using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Permanganate preoxidation was found to decrease the DBE (double bond equivalent) and AImod (modified aromaticity index) of the dEfOM. The identity and fate of over 400 unknown Cl-DBPs during KMnO4-chlorine treatment were investigated. Most Cl-DBPs and the precursors were found to be highly unsaturated aliphatic and phenolic compounds. The Cl-DBPs precursors with lower H/C and lower O/C were preferentially removed by permanganate preoxidation. Additionally, permanganate preoxidation decreased the number of unknown Cl-DBPs by 30% and intensity of unknown Cl-DBPs by 25%. One-chlorine-containing DBPs were the major Cl-DBPs and had more CH2 groups and higher DBEw than Cl-DBPs containing two and three chlorine atoms. 60% of the Cl-DBPs formation was attributed to substitution reactions (i.e., +Cl-H, +2Cl-2H, +3Cl-3H, +ClO-H, +Cl2O3-2H). This work provides detailed molecular level information on the efficacy of permanganate preoxidation on the control of overall Cl-DBPs formation during chlorination.

Effect of booster disinfection on the prevalence of microbial antibiotic resistance and bacterial community in a simulated drinking water distribution system.

Booster disinfection was often applied to control the microorganism's growth in long-distance water supply systems. The effect of booster disinfection on the changing patterns of antibiotic resistance and bacterial community was investigated by a simulated water distribution system (SWDS). The results showed that the antibiotic resistance bacteria (ARB) and antibiotic resistance genes (ARGs) were initially removed after dosing disinfectants (chlorine and chloramine), but then increased with the increasing water age. However, the relative abundance of ARGs significantly increased after booster disinfection both in buck water and biofilm, then decreased along the pipeline. The pipe materials and disinfectant type also affected the antibiotic resistance. Chlorine was more efficient in controlling microbes and ARGs than chloramine. Compared with UPVC and PE pipes, SS pipes had the lowest total bacteria, ARB concentration, and ARB percentage, mainly due to higher disinfectant residuals and a smoother surface. The significant correlation (rs = 0.77, p < 0.001) of the 16S rRNA genes was observed between buck water and biofilm, while the correlations of targeted ARGs were found to be weak. Bray-Curtis similarity index indicated that booster disinfection significantly changed the biofilm bacterial community and the disinfectant type also had a marked impact on the bacterial community. At the genus level, the relative abundance of Pseudomonas, Sphingomonas, and Methylobacterium significantly increased after booster disinfection. Mycobacterium increased after chloramination while decreased after chlorination, indicating Mycobacterium might resist chloramine. Pseudomonas, Methylobacterium, and Phreatobacter were found to correlate well with the relative abundance of ARGs. These results highlighted antibiotic resistance shift and bacterial community alteration after booster disinfection, which may be helpful in controlling potential microbial risk in drinking water.

Magnetic porous carbon material derived from imine-linked covalent organic frameworks for magnetic solid phase extraction of trace chlorine-containing herbicides in soil.

Here, imine-linked covalent organic frameworks coated Fe3O4 microspheres were fabricated and employed as the self-template to prepare magnetic porous carbon material. The magnetic solid phase extraction (MSPE) performance of such magnetic covalent organic frameworks derived porous carbons (CMCOFs) were studied for the first time, and the improved MSPE performance was verified. The variations of chemical and material properties in the carbonization processes were studied, and it was found that the CMCOFs carbonated at 400°C exhibited highest adsorption efficiencies for chlorine-containing herbicides due to the formation of nitrile components at this stage. The CMCOFs retained high adsorption efficiencies (above 90 %) to chlorine-containing herbicides at wide pH range (3-12) and high salt concentration. The CMCOFs-based MSPE coupled with HPLC technique was in good potential for analysis of trace chlorine-containing herbicides in soil samples. Under the optimized conditions, this approach displayed short extraction and elution time (5 and 8 min) and low limits of detection (0.35-5.5 ng/mL) for chlorine-containing herbicides. The recoveries of spiked analytes and the relative standard deviations in real soil samples were 81.86 %-110.9 % and less than 5.92 %, respectively. This study provides an efficient method for the analysis of trace chlorine-containing herbicides in complex samples, as well as give some inspiration on material modulation by controlled carbonization to achieve improved sorption performances.

Composition of active bacterial communities and presence of opportunistic pathogens in disinfected and non-disinfected drinking water distribution systems in Finland.

Many factors, including microbiome structure and activity in the drinking water distribution system (DWDS), affect the colonization potential of opportunistic pathogens. The present study aims to describe the dynamics of active bacterial communities in DWDS and identify the factors that shape the community structures and activity in the selected DWDSs. Large-volume drinking water and hot water, biofilm, and water meter deposit samples were collected from five DWDSs. Total nucleic acids were extracted, and RNA was further purified and transcribed into its cDNA from a total of 181 water and biofilm samples originating from the DWDS of two surface water supplies (disinfected with UV and chlorine), two artificially recharged groundwater supplies (non-disinfected), and a groundwater supply (disinfected with UV and chlorine). In chlorinated DWDSs, concentrations of <0.02-0.97 mg/l free chlorine were measured. Bacterial communities in the RNA and DNA fractions were analysed using Illumina MiSeq sequencing with primer pair 341F-785R targeted to the 16S rRNA gene. The sequence libraries were analysed using QIIME pipeline, Program R, and MicrobiomeAnalyst. Not all bacterial cells were active based on their 16S rRNA content, and species richness was lower in the RNA fraction (Chao1 mean value 490) than in the DNA fraction (710). Species richness was higher in the two DWDSs distributing non-disinfected artificial groundwater (Chao1 mean values of 990 and 1 000) as compared to the two disinfected DWDSs using surface water (Chao1 mean values 190 and 460) and disinfected DWDS using ground water as source water (170). The difference in community structures between non-disinfected and disinfected water was clear in the beta-diversity analysis. Distance from the waterworks also affected the beta diversity of community structures, especially in disinfected distribution systems. The two most abundant bacteria in the active part of the community (RNA) and total bacterial community (DNA) belonged to the classes Alphaproteobacteria (RNA 28 %, DNA 44 %) and Gammaproteobacteria (RNA 32 %, DNA 30 %). The third most abundant and active bacteria class was Vampirovibrionia (RNA 15 %), whereas in the total community it was Paceibacteria (DNA 11 %). Class Nitrospiria was more abundant and active in both cold and hot water in DWDS that used chloramine disinfection compared to non-chlorinated or chlorine-using DWDSs. Thirty-eight operational taxonomic units (OTU) of Legionella, 30 of Mycobacterium, and 10 of Pseudomonas were detected among the sequences. The (RT)-qPCR confirmed the presence of opportunistic pathogens in the DWDSs studied as Legionella spp. was detected in 85 % (mean value 4.5 × 104 gene copies/100 ml), Mycobacterium spp. in 95 % (mean value 8.3 × 106 gene copies/100 ml), and Pseudomonas spp. in 78 % (mean value 1.6 × 105 gene copies/100 ml) of the water and biofilm samples. Sampling point inside the system (distance from the waterworks and cold/hot system) affected the active bacterial community composition. Chloramine as a chlorination method resulted in a recognizable community composition, with high abundance of bacteria that benefit from the excess presence of nitrogen. The results presented here confirm that each DWDS is unique and that opportunistic pathogens are present even in conditions when water quality is considered excellent.

Acid treatment for enhancing Hg0 removal efficiency of chlorine-loaded biochar: mechanism and kinetic analysis.

Adsorbents modified solely with chlorine have limited effectiveness in removing mercury at high temperatures. This study aims to investigate the influence of various acid (HNO3, H2SO4, and H2O2) loadings on the removal efficiency of mercury from NH4Cl-modified adsorbents. The objective is to develop rice straw carbon adsorbents that are both more efficient and cost-effective. The experiments were conducted on a fixed bed experimental platform, with SEM and BET to observe the physical property changes of the modified char samples. XPS analysis was employed to analyze the effects of oxygen, chlorine, and sulfur functional groups. Additionally, a kinetic model was used to investigate the interaction mechanism between the adsorbent and mercury. The findings demonstrate that co-modification surpasses the use of NH4Cl alone, with the combination of NH4Cl and HNO3 yielding the best results. Co-modification enhances the development of a more refined and compact pore structure on the char surface, promoting the physical adsorption of mercury. Moreover, an increased presence of chlorine and oxygen functional groups is observed on the char surface, particularly in the NH4Cl and HNO3 co-modified samples, further enhancing the chemical adsorption capacity of the char. The results from the kinetic analysis support this conclusion. Furthermore, the adsorption process of Hg0 relies on both external mass transfer and chemical adsorption, with the chemical adsorption process playing a more significant role as the controlling factor.

Comprehensive Assessment of Reactive Bromine Species in Advanced Oxidation Processes: Differential Roles in Micropollutant Abatement in Bromide-Containing Water.

Reactive bromine species (RBS) are gaining increasing attention in natural and engineered aqueous systems containing bromide ions (Br-). However, their roles in the degradation of structurally diverse micropollutants by advanced oxidation processes (AOPs) were not differentiated. In this study, the second-order rate constants (k) of Br•, Br2•-, BrO•, and ClBr•- were collected and evaluated. Br• is the most reactive RBS toward 21 examined micropollutants with k values of 108-1010 M-1 s-1. Br2•-, ClBr•-, and BrO• are selective for electron-rich micropollutants with k values of 106-108 M-1 s-1. The specific roles of RBS in aqueous micropollutant degradation in AOPs were revealed by using simplified models via sensitivity analysis. Generally, RBS play minimal roles in the UV/H2O2 process but are significant in the UV/peroxydisulfate (PDS) and UV/chlorine processes in the presence of trace Br-. In UV/PDS with ≥1 µM Br-, Br• emerges as the major RBS for removing electron-rich micropollutants. In UV/chlorine, BrO• contributes to the degradation of specific electron-rich micropollutants with removal percentages of ≥20% at 1 µM Br-, while the contributions of BrO• and Br• are comparable to those of reactive chlorine species as Br- concentration increases to several µM. In all AOPs, Br2•- and ClBr•- play minor roles at 1-10 µM Br-. Water matrix components such as HCO3-, Cl-, and natural organic matter (NOM) significantly inhibit Br•, while BrO• is less affected, only slightly scavenged by NOM with a k value of 2.1 (mgC/L)-1 s-1. This study sheds light on the differential roles of multiple RBS in micropollutant abatement by AOPs in Br--containing water.

Diversity and negative effect of PM0.3-10.0 adsorbed by needles of urban trees in Irkutsk, Russia.

The study was performed in natural forests preserved within the Boreal zone city, Irkutsk, Russia. Test sites were selected in the forests in different districts of the city, where samples of Scots pine (Pinus sylvestris L.) and Siberian larch (Larix sibirica Ledeb.) needles were taken to study the adsorption on their surface of aerosol particles of different sizes, in microns: PM0.3, PM0.5, PM1, PM2.5, PM5, PM10. Scanning electron microscopy was used to obtain high-resolution photographs (magnification 800- × 2000, × 16,000) and aerosol particles (particulate matter-PM) were shown to be intensively adsorbed by the surface of needles, with both size and shape of the particles characterized by a wide variety. Pine needles can be covered with particles of solid aerosol by 50-75%, stomata are often completely blocked. Larch needles often show areas, which are completely covered with aerosol particles, there are often found stomata deformed by the penetration of PMx. X-ray spectral microanalysis showed differences in the chemical composition of adsorbed PMx, the particles can be metallic if metals predominate in their composition, carbonaceous-in case of carbon predominance-or polyelemental if the composition is complex and includes significant quantities of other elements besides metals and carbon (calcium, magnesium, potassium, sodium, sulfur, chlorine, fluorine). Since the particles contain a large proportion of technogenic pollutants, accumulation by the needles of some widespread pollutants was investigated. A direct correlation of a highly significant level between the concentration of PMx in the air and the accumulation of many heavy metals in pine and larch needles, as well as sulfur, fluorine, and chlorine, has been revealed, which indicates a high cleaning capacity of urban forests. At the same time, the negative impact of PMx particles on the vital status of trees is great, which shows in intense disturbance of the parameters of photosynthesis and transpiration, leading to a significant decrease in the growth characteristics of trees and reduction in the photosynthetic volume of the crowns. We consider that the results obtained are instrumental in developing an approach to improvement of urban forests status and creating a comfortable urban environment for the population.

Interlaboratory trial of short-chain chlorinated paraffin: comparison of mass fractions and homolog profiles in a simulation environmental sample.

Short-chain chlorinated paraffins (SCCPs) are listed in the Stockholm Convention. Therefore, selecting suitable methods for their accurate quantification is essential. Nowadays, the quality of commercial reagents employed as quantification standards is not guaranteed. As a solution, we adopted an SCCP formulation reference material with known homolog composition ratios as the quantification standard to evaluate the appropriateness of the methods. By mixing the SCCP formulation and interferences, an analytical sample was independently prepared and used as the simulation environmental sample. The homolog compositional profiles of the SCCPs resembled those of the quantification standard and the analytical sample. The mass fractions and the homolog profiles, including the carbon chain length and chlorine homolog profiles, of the SCCPs were reported by 14 different laboratories. For the mass fraction, the results reported by participants were consistent, except for the participants that employed low-resolution gas chromatography (GC). The results generated from liquid chromatography (LC) and GC were slightly different, despite of the similar homolog composition ratios between the quantification standard and the analytical sample. Although there were discreet discrepancies in the overall chlorine homolog profiles, the carbon chain length profiles acquired from GC and LC were similar. The differences depended on the method employed. Additionally, compared with the low-resolution data, the high-resolution data displayed less fluctuation since the effect of the interferences on the analytical sample was reduced because of the mass accuracy of high-resolution instruments. Accordingly, the interlaboratory trial employing the similar homolog compositional profiles of the quantification standard and the analytical sample proved valuable in elucidating the differences among methods, considering equipment, resolution specification, and ionization.

Temporal and spatial variations of disinfection by-products in South Taihu's drinking water, Zhejiang Province, China.

Some disinfection by-products (DBPs) in drinking water present a potential safety concern. This study focuses on the elements influencing DBPs formation. A total of 120 water samples were collected from 10 different drinking water facilities spanning 5 counties within Huzhou, Zhejiang Province, China. Concentrations of trihalomethanes (THMs) and haloacetic acids (HAAs) were observed to be 14.5 and 27.4 µg/L, respectively, constituting 34 and 64% of the total DBPs. Seasonal fluctuations demonstrated that HAAs, THMs, halonitromethanes (HNMs), and haloacetonitriles (HANs) followed a similar pattern with higher levels in summer or autumn compared to spring. Importantly, the concentrations of HAAs and THMs were markedly higher in Taihu-sourced water compared to other sources. Geographically, Nanxun exhibited the highest levels of total DBPs, HAAs, and THMs, while Deqing and Changxing demonstrated significantly lower levels. Correlation studies between water quality parameters and DBPs revealed that factors such as chloride content, temperature, and residual chlorine positively influenced DBPs formation, whereas turbidity negatively affected it. Principal component analysis suggested similar formation processes for HANs, haloketones (HKs), HNMs, and THMs. Factors such as temperature, chemical oxygen demand (COD), and residual chlorine were identified as significant contributors to the prevalence of HAAs.

High Chlorine Concentrations in an Unconventional Oil and Gas Development Region and Impacts on Atmospheric Chemistry.

Growth in unconventional oil and gas development (UOGD) in the United States has increased airborne emissions, raising environmental and human health concerns. To assess the potential impacts on air quality, we deployed instrumentation in Karnes City, Texas, a rural area in the middle of the Eagle Ford Shale. We measured several episodes of elevated Cl2 levels, reaching maximum hourly averages of 800 ppt, the highest inland Cl2 concentration reported to date. Concentrations peak during the day, suggesting a strong local source (given the short photolysis lifetime of Cl2) and/or a photoinitiated production mechanism. Well preproduction activity near the measurement site is a plausible source of these high Cl2 levels via direct emission and photoactive chemistry. ClNO2 is also observed, but it peaks overnight, consistent with well-known nocturnal formation processes. Observations of organochlorines in the gas and particle phases reflect the contribution of chlorine chemistry to the formation of secondary pollutants in the area. Box modeling results suggest that the formation of ozone at this location is influenced by chlorine chemistry. These results suggest that UOGD can be an important source of reactive chlorine in the atmosphere, impacting radical budgets and the formation of secondary pollutants in these regions.

Formation of halonitromethanes from glycine during LED-UV265/chlorine disinfection.

LED-UV265/chlorine is a promising alternative disinfection technology that emits mono-wavelength light for high germicidal efficiency. Halonitromethanes (HNMs) are highly cytotoxic and genotoxic disinfection byproducts that can be formed during LED-UV265/chlorine disinfection. Thus, this work aimed to investigate the HNMs formation from glycine (Gly) during LED-UV265/chlorine disinfection. The results indicated that the concentrations of chlorinated-HNMs (Cl-HNMs) increased first and then decreased as the reaction proceeded. Besides, the effects of operating parameters (UV intensity, free chlorine dosage, and pH) and coexisting ions (Cu2+ and Br-) on HNMs formation were investigated. It was found that the formation concentrations of Cl-HNMs increased with the increase of LED-UV265 intensity and free chlorine dosage but decreased with increased pH. The presence of Cu2+ promoted the formation of Cl-HNMs. The total concentration of HNMs (at 3 min) with adding 1.5 mg/L Cu2+ was 30.90% higher than that without Cu2+. Notably, nine species of HNMs were detected after adding Br-, and the total concentrations of HNMs were enhanced. Moreover, Cl-HNMs were gradually transformed into brominated (chlorinated)-HNMs and brominated-HNMs as Br- concentration increased. According to the findings, the possible formation mechanism of HNMs from Gly during LED-UV265/chlorine disinfection was deduced. Finally, it was demonstrated that the formation laws of HNMs from Gly in real water samples were basically consistent with those in simulated water. Insights obtained in this study help to comprehend the HNMs formation from Gly and provide strategies for controlling the production of HNMs during LED-UV265/chlorine disinfection.

Photo-transformation of wastewater effluent organic matter reduces the formation potential and toxicity of chlorinated disinfection byproducts.

Sunlight exposure can degrade and transform discharged wastewater effluent organic matter (EfOM) in aquatic systems, potentially enhancing the feasibility of reusing wastewater for drinking purposes. However, there remains a lack of comprehensive understanding regarding the sunlight-induced changes in the molecular-level composition, characteristics, and chlorine reactivity of EfOM. Herein, we investigated the impact of sunlight on the optical properties, chemical composition, and formation of disinfection byproducts of EfOM using multiple spectroscopic analyses, high-resolution mass spectrometry, chlorination experiments, and in vitro bioassays. Upon natural sunlight exposure, we observed significant decreases in ultraviolet-visible absorbance and fluorescence intensity of EfOM, indicating the destruction of chromophores and fluorophores. Photolysis generally yields products with lower molecular weight and aromaticity, and with higher saturation and oxidation levels. Moreover, a shift within the EfOM from condensed aromatic-like compounds to tannin-like components was observed. Furthermore, sunlight exposure reduced the reactivity of EfOM toward the formation of trihalomethanes and haloacetonitriles during chlorination, while there was a slight increase in the specific formation potential of haloketones. Importantly, the disinfection byproducts resulting from chlorination of the irradiated EfOM exhibited reduced microtoxicity. Overall, this study provides new insights into alterations in EfOM under sunlight exposure and aids in predicting the health risks of effluent discharge in water environments.

Machine-learning-assisted prediction and optimized kinetic modelling of residual chlorine decay for enhanced water quality management.

The quality of water changes from source to tap, presenting challenges in maintaining consistent water quality across the system. Predicting water quality in distribution systems, including disinfectant residual loss and by-product formation, has been the subject of research since the early 1990s. Although numerous models have been proposed to predict residual chlorine decay, disputes exist among researchers and experts over the superiority of certain models. Accordingly, this study modified the existing process-based bulk decay models by replacing the initial Total Residual Chlorine (TRC) concentration parameter with TRC demand, leading to an improvement in the models' performance. The modification resulted in a 38.03%, 28.02%, 23.11%, and 33.29% average improvement in Mean Squared Error (MSE) values for the First Order Model (FOM), Parallel First Order Model (PFOM), Second Order Model (SOM), and Parallel Second Order Model (PSOM), respectively. The study also introduced an online predictive method based on a Machine Learning (ML) algorithm that predicts the first-order TRC bulk decay rate by using water quality parameters as inputs. A Gaussian Process Regression (GPR) model was used to predict the kinetic parameters in FOM, which accurately predicted the test sets for most of the cases. In addition, a new methodology was proposed in this study for predicting TRC in water distribution systems that incorporates the variability of source natural organic matter, operational actions, and water demands. This method seeks to develop high-fidelity and robust water quality predictions that provide operational decision support for optimized distribution system management. In conclusion, this study emphasizes the importance of understanding water quality changes from source to tap and the challenges of maintaining consistent water quality across the system. The study suggests modifying existing models and introducing a novel methodology for predicting residual chlorine in water distribution systems that can improve water quality management and, ultimately, better public health outcomes.

Factors affecting the leaching of micro and nanoplastics in the water distribution system.

The role of the water distribution system (WDS) requires that it supply water of sufficient quality to households. Unregulated leaching of micro and nanoplastics from plastic pipes of the distribution system is therefore a cause for concern, particularly with the rise in research associating these plastic particles to adverse health impacts in living organisms. Within this study, four parameters (pH, free chlorine concentration, pipe material, and time) were varied in a pipe loop network to observe their effect on microplastic (MP) and nanoplastic (NP) leaching into the simulated distribution network. Results indicated an abundance of MPs/NPs in different shapes and sizes throughout the samples. Graphical trends illustrated that basic pH values contributed to a higher number of particles. Statistical analysis via analysis of variance (ANOVA) confirmed this observation and further showed interaction of chlorine dose and pH concentration (p-value = 0.000), and chlorine dose and pipe material (p-value = 0.038) was also significant to leaching. Numerically, polyethylene (PE) particles were the most abundant with a total of 15194 particles, followed by 12920 polypropylene random copolymer (PPR) particles and 12317 polyvinyl chloride (PVC) particles. It was also noticed that the number of particles decreased with time.© 2023 Elsevier Inc. All rights reserved.