Acute toxicity formation potential of benzophenone-type UV filters in chlorination disinfection process

Benzophenones （BPs） are a class of widely used UV filters, which have been frequently detected within multiple environmental matrices. Disinfection is a necessary process in water treatment processes. The transformation behaviors and toxicity changes of 14 BP-type UV filters during chlorination disinfection treatment were investigated in this study. A new index, the acute toxicity formation potential, was proposed to evaluate the toxicity changes and potential risks of BP-type UV filters during chlorination treatment. It was found that 13 of 14 BP-type UV filters exhibited toxicity decreases in the chlorination disinfection process, more or less, while one showed a toxicity increase. The toxicity changes were dependent on substitution effects, such that 2,4-di-hydroxylated or 3-hydroxylated BPs exhibited significant toxicity decreases after chlorination treatment due to the ready cleavage of the aromatic ring. Importantly, the acute toxicity changes could be duplicated in an ambient water matrix.     

Effects of ultrasonication on the DBP formation and toxicity during chlorination of saline wastewater effluents

Chlorine disinfection of saline wastewater effluents rich in bromide and iodide forms relatively toxic brominated and iodinated disinfection byproducts (DBPs). Ultrasonication is a relatively new water treatment technology, and it is less sensitive to suspended solids in wastewaters. In this study, we examined the effects of ultrasonication (in terms of reactor type and combination mode with chlorination) on the DBP formation and toxicity in chlorinated primary and secondary saline wastewater effluents. Compared with the chlorinated wastewater effluent samples without ultrasonication, ultrasonic horn pretreatment of the wastewater effluent samples reduced the total organic halogen (TOX) levels in chlorination by ∼30%, but ultrasonic bath pretreatment of the wastewater samples did not significantly change the TOX levels in chlorination, which might be attributed to the higher energy utilization and decomposition extent of organic DBP precursors in the ultrasonic horn reactor. Moreover, the TOX levels in the chlorinated samples with ultrasonic horn pretreatment (USH–chlorination), simultaneous treatment (chlorination+USH) and subsequent treatment (chlorination–USH) were also significantly reduced, with the maximum TOX reductions occurring in the samples with ultrasonic horn pretreatment. A toxicity index was calculated by weighting and summing the levels of total organic chlorine, total organic bromine and total organic iodine in each treated sample. The calculated toxicity index values of the chlorinated wastewater effluent samples followed a descending rank order of “chlorination” > “chlorination+USH” > “chlorination–USH” > “USH–chlorination”, with the lowest toxicity occurring in the samples with ultrasonic horn pretreatment. Then, a developmental toxicity bioassay was conducted for each treated sample. The measured toxicity index values of the chlorinated wastewater samples followed the same descending rank order.     

Transformation of sulfamethazine during the chlorination disinfection process: Transformation, kinetics, and toxicology assessment

Various disinfection byproducts(DBPs) form during the process of chlorination disinfection,posing potential threats to drinking water safety and human health. Sulfamethazine(SMT),the most commonly used and frequently detected veterinary antibiotic, was investigated in detail with regard to its transformation and kinetics in reactions with free available chlorine(FAC). Using liquid chromatography coupled to quadrupole time-of-flight tandem mass spectrometry, several DBPs were identified based on different confidence levels, and a variety of reaction types, including desulfonation, S–N cleavage, hydroxylation, and chlorine substitution, were proposed. The kinetic experiments indicated that the reaction rate was FAC-and pH-dependent, and SMT exhibits low reactivity toward FAC in alkaline conditions. The DBPs exhibited a much higher acute toxicity than SMT, as estimated by quantitative structure activity relationship models. More importantly, we observed that the FAC-treated SMT reaction solution might increase the genotoxic potential due to the generation of DBPs. This investigation provides substantial new details related to the transformation of SMT in the chlorination disinfection process.     

Formation pathways of brominated products from benzophenone-4 chlorination in the presence of bromide ions

The brominated products, formed in chlorination treatment of benzophenone-4 in the presence of bromide ions, were identified, and the formation pathways were proposed.Under disinfection conditions, benzophenone-4 would undertake electrophilic substitution generating mono- or di-halogenated products, which would be oxidized to esters and further hydrolyzed to phenol derivatives. The generated catechol intermediate would be transformed into furan-like heterocyclic product. The product species were p H-dependent,while benzophenone-4 elimination was chlorine dose-dependent. When the chlorination treatment was performed on ambient water spiked with benzophenone-4 and bromide ions, most of brominated byproducts could be detected, and the acute toxicity significantly increased as well.     

Degradation of sulfonamides and formation of trihalomethanes by chlorination after pre-oxidation with Fe(Ⅵ)

Sulfonamides are used in human therapy,animal husbandry and agriculture but are not easily biodegradable,and are often detected in surface water.Sulfamethazine(SMZ) and sulfadiazine(SDZ) are two widely used sulfonamide antibiotics that are used heavily in agriculture.In this study,they were degraded in an aqueous system by chlorination after pre-oxidation with ferrate(VI)(FeVIO42-,Fe(VI)),an environmentally friendly oxidation technique that has been shown to be effective in degrading various organics.The kinetics of the degradation were determined as a function of Fe(VI)(0–1.5 mg/L),free chlorine(0–1.8 mg/L) and temperature(15–35°C).According to the experimental results,SMZ chlorination followed second-order kinetics with increasing Fe(VI) dosage,and the effect of the initial free chlorine concentration on the reaction kinetics with pre-oxidation by Fe(VI) fitted a pseudo-first order model.The rate constants of SDZ and SMZ chlorination at different temperatures were related to the Arrhenius equation.Fe(VI) could reduce the levels of THMs formed and the toxicity of the sulfonamide degradation systems with Fe(VI) doses of 0.5–1.5 mg/L,which provides a reference for ensuring water quality in drinking water systems.     

Formation of THMs and HANs during bromination of Microcystis aeruginosa

Bromine-contained disinfectants and biocides are widely used in swimming pools, recreational waters and cooling towers. The objective of this study was to evaluate the formation of thrihalomethanes (THMs) and haloacetonitriles (HANs) and their cytotoxicity in algae solutions during free bromine disinfection. Disinfection by-products formation potential experiments were conducted using model solutions containing 7 mg/L (as total organic carbon) Microcystis aeruginosa cells. Effects of free bromine dosage, pH and ammonia were investigated. The results showed that brominated disinfection by-products were the major products when free bromine was applied. The total THMs formed during bromination was much as that formed during chlorination, whereas HANs were elevated by using bromination instead of chlorination. Dibromoacetonitrice (C2H2NBr2 ) and bromoform (CHBr3 ) were the only detected species during free bromine disinfection. The production of C2H2NBr2 and CHBr 3 increased with disinfectant dosage but decreased with dosing ammonia. CHBr3 increased with the pH changing from 5 to 9. However, C2H2NBr2 achieved the highest production at neutral pH, which was due to a joint effect of variation in hydrolysis rate and free bromine reactivity. The hydrolysis of C2H2NBr2 was base-catalytic and nearly unaffected by disinfectant. Finally, estimation of cytotoxicity of the disinfected algae solutions showed that HANs formation was responsible for the majority of toxicity. Considering its highest toxicity among the measured disinfection by-products, the elevated C2H2NBr2 should be considered when using bromine-related algaecide.     

Variation in assimilable organic carbon formation during chlorination of Microcystis aeruginosa extracellular organic matter solutions

This study investigated the chlorination of Microcystis aeruginosa extracellular organic matter(EOM) solutions under different conditions, to determine how the metabolites produced by these organisms affect water safety and the formation of assimilable organic carbon(AOC). The effects of chlorine dosages, coagulant dosage, reaction time and temperature on the formation of AOC were investigated during the disinfection of M.aeruginosa metabolite solutions. The concentration of AOC followed a decreasing and then increasing pattern with increasing temperature and reaction time. The concentration of AOC decreased and then increased with increasing chlorination dosage, followed by a slight decrease at the highest level of chlorination. However, the concentration of AOC decreased continuously with increasing coagulant dosage. The formation of AOC can be suppressed under appropriate conditions. In this study, chlorination at 4 mg/L, combined with a coagulant dose of 40 mg/L at 20°C over a reaction time of 12 hr, produced the minimum AOC.     

DBP formation from degradation of DEET and ibuprofen by UV/chlorine process and subsequent post-chlorination

The formation of disinfection by-products(DBPs) from the degradation of N,N-diethyl-3-methyl benzoyl amide(DEET) and ibuprofen(IBP) by the ultraviolet irradiation(UV)/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H_2O_2 process.The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H_2O_2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species U(RCS) and hydroxyl radicals(HO) in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50%after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine(TOCl), respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H_2O_2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%–63% higher,Ulikely due to the generation of more DBP precursors from the attack of RCS, in addition to HO.     

Evaluation of the infectivity, gene and antigenicity persistence of rotaviruses by free chlorine disinfection

The effects of free chlorine disinfection of tap water and wastewater effluents on the infectivity, gene integrity and surface antigens of rotaviruses were evaluated by a bench-scale chlorine disinfection experiments. Plaque assays, integrated cell culture-quantitative RT-PCR (ICC-RT-qPCR), RT-qPCR, and enzyme-linked immunosorbent assays (ELISA), respectively, were used to assess the influence of the disinfectant on virus infectivity as well as genetic and antigenic integrity of simian rotavirus SA11 as a surrogate for human rotaviruses. The ICC-RT-qPCR was able to detect rotaviruses survival from chlorine disinfection at chlorine dose up to 20 mg/L (60 min contact), which suggested a required chlorine dose of 5 folds (from 1 to 5 mg/L) higher than that indicated by the plaque assay to achieve 1.8 log₁₀ reductions in tap water with 60 min exposing. The VP7 gene was more resistant than the infectivity and existed at chlorine dose up to 20 mg/L (60 min contact), while the antigencity was undetectable with chlorine dose more than 5 mg/L (60 min contact). The water quality also impacted the inactivation efficiencies, and rotaviruses have a relatively higher resistant in secondary effluents than in the tap water under the same chlorine disinfection treatments. This study indicated that rotaviruses have a higher infectivity, gene and antigencity resistance to chlorine than that previously indicated by plaque assay only, which seemed to underestimate the resistance of rotaviruses to chlorine and the risk of rotaviruses in environments. Present results also suggested that re-evaluation of resistance of other waterborne viruses after disinfections by more sensitive infectivity detection method (such as ICC-RT-qPCR) may be necessary, to determine the adequate disinfectant doses required for the inactivation of waterborne viruses.     

Inactivation, reactivation and regrowth of indigenous bacteria in reclaimed water after chlorine disinfection of a municipal wastewater treatment plant

Disinfection of reclaimed water prior to reuse is important to prevent the transmission of pathogens. Chlorine is a widely utilized disinfectant and as such is a leading contender for disinfection of reclaimed water. To understand the risks of chlorination resulting from the potential selection of pathogenic bacteria, the inactivation, reactivation and regrowth rates of indigenous bacteria were investigated in reclaimed water after chlorine disinfection. Inactivation of total coliforms, Enterococcus and Salmonella showed linear correlations, with constants of 0.1384, 0.1624 and 0.057 L/(mg·min) and R² of 0.7617, 0.8316 and 0.845, respectively. However, inactivation of total viable cells by measurement of metabolic activity typically showed a linear correlation at lower chlorine dose (0-22 (mg·min)/L), and a trailing region with chlorine dose increasing from 22 to 69 (mg·min)/L. Reactivation and regrowth of bacteria were most likely to occur after exposure to lower chlorine doses, and extents of reactivation decreased gradually with increasing chlorine dose. In contrast to total coliforms and Enterococcus, Salmonella had a high level of regrowth and reactivation, and still had 2% regrowth even after chlorination of 69 (mg·min)/L and 24 hr storage. The bacterial compositions were also significantly altered by chlorination and storage of reclaimed water, and the ratio of Salmonella was significantly increased from 0.001% to 0.045% after chlorination of 69 (mg·min)/L and 24 hr storage. These trends indicated that chlorination contributes to the selection of chlorine-resistant pathogenic bacteria, and regrowth of pathogenic bacteria after chlorination in reclaimed water with a long retention time could threaten public health security during wastewater reuse.     

Method to assess component contribution to toxicity of complex mixtures: Assessment of puberty acquisition in rats exposed to disinfection byproducts

A method based on regression modeling was developed to discern the contribution of component chemicals to the toxicity of highly complex, environmentally realistic mixtures of disinfection byproducts(DBPs). Chemical disinfection of drinking water forms DBP mixtures.Because of concerns about possible reproductive and developmental toxicity, a whole mixture(WM) of DBPs produced by chlorination of a water concentrate was administered as drinking water to Sprague–Dawley(S–D) rats in a multigenerational study. Age of puberty acquisition,i.e., preputial separation(PPS) and vaginal opening(VO), was examined in male and female offspring, respectively. When compared to controls, a slight, but statistically significant delay in puberty acquisition was observed in females but not in males. WM-induced differences in the age at puberty acquisition were compared to those reported in S–D rats administered either a defined mixture(DM) of nine regulated DBPs or individual DBPs. Regression models were developed using individual animal data on age at PPS or VO from the DM study. Puberty acquisition data reported in the WM and individual DBP studies were then compared with the DM models. The delay in puberty acquisition observed in the WM-treated female rats could not be distinguished from delays predicted by the DM regression model, suggesting that the nine regulated DBPs in the DM might account for much of the delay observed in the WM. This method is applicable to mixtures of other types of chemicals and other endpoints.     

Degradation of sulfonamides and formation of trihalomethanes by chlorination after pre-oxidation with Fe(VI)

Sulfonamides are used in human therapy, animal husbandry and agriculture but are not easily biodegradable, and are often detected in surface water. Sulfamethazine (SMZ) and sulfadiazine (SDZ) are two widely used sulfonamide antibiotics that are used heavily in agriculture. In this study, they were degraded in an aqueous system by chlorination after pre-oxidation with ferrate(VI) (Fe^VIO₄^2 ?, Fe(VI)), an environmentally friendly oxidation technique that has been shown to be effective in degrading various organics. The kinetics of the degradation were determined as a function of Fe(VI) (0–1.5 mg/L), free chlorine (0–1.8 mg/L) and temperature (15–35°C). According to the experimental results, SMZ chlorination followed second-order kinetics with increasing Fe(VI) dosage, and the effect of the initial free chlorine concentration on the reaction kinetics with pre-oxidation by Fe(VI) fitted a pseudo-first order model. The rate constants of SDZ and SMZ chlorination at different temperatures were related to the Arrhenius equation. Fe(VI) could reduce the levels of THMs formed and the toxicity of the sulfonamide degradation systems with Fe(VI) doses of 0.5–1.5 mg/L, which provides a reference for ensuring water quality in drinking water systems.     

Formation and control of nitrogenous DBPs from Western Australian source waters: Investigating the impacts of high nitrogen and bromide concentrations

We studied the formation of four nitrogenous DBPs(N-DBPs) classes(haloacetonitriles,halonitromethanes, haloacetamides, and N-nitrosamines), as well as trihalomethanes and total organic halogen(TOX), after chlorination or chloramination of source waters. We also evaluated the relative and additive toxicity of N-DBPs and water treatment options for minimisation of N-DBPs. The formation of halonitromethanes, haloacetamides, and N-nitrosamines was higher after chloramination and positively correlated with dissolved organic nitrogen or total nitrogen. N-DBPs were major contributors to the toxicity of both chlorinated and chloraminated waters. The strong correlation between bromide concentration and the overall calculated DBP additive toxicity for both chlorinated and chloraminated source waters demonstrated that formation of brominated haloacetonitriles was the main contributor to toxicity. Ozone–biological activated carbon treatment was not effective in removing N-DBP precursors. The occurrence and formation of N-DBPs should be investigated on a case-by-case basis, especially where advanced water treatment processes are being considered to minimise their formation in drinking waters, and where chloramination is used for final disinfection.     

Mechanisms of ultraviolet disinfection and chlorination of Escherichia coli: Culturability, membrane permeability, metabolism, and genetic damage

Traditional culture methods may underestimate the tolerance of microorganisms to disinfectants because of the existence of viable but nonculturable or sublethally injured cells after disinfection.The selection of a strict method is crucial for the evaluation of disinfection performance.The actions of 2 typical disinfectants–ultraviolet(UV)and chlorine–on the fecal indicator Escherichia coli were investigated by the detection of culturability,membrane permeability,metabolic activity,deoxyribonucleic acid(DNA),and messenger ribonucleic acid(m RNA).During UV disinfection,the irreversible damages in the cell membrane and cellular adenosine triphosphate(ATP)were negligible at low UV doses(80 m J/cm~2).However,membrane permeability was damaged at low doses of chlorine(5 mg/L),leading to leakage of cellular ATP.Our study showed that a slight lesion in DNA was detected even at high doses of UV(400 m J/cm~2)and chlorine(5 mg/L)treatments.The decay of m RNA was more rapid than that of DNA.The degradation level of m RNA depended on the choice of target genes.After exposure to 50 m J/cm~2UV dose or 5 mg/L chlorine for30 min,the DNA damage repair function(Rec A m RNA)was inhibited.The m RNA involved in the DNA damage repair function can be a potential indicator of bacterial viability.     

Formation of halonitromethanes from methylamine in the presence of bromide during UV/Cl2 disinfection

The UV/Cl₂ process is commonly used to achieve a multiple-barrier disinfection and maintain residuals. The study chose methylamine as a precursor to study the formation of high-toxic halonitromethanes (HNMs) in the presence of bromide ions (Br⁻) during UV/Cl₂ disinfection. The maximum yield of HNMs increased first and then decreased with increasing concentration of Br⁻. An excessively high concentration of Br⁻ induced the maximum yield of HNMs in advance. The maximum bromine incorporation factor (BIF) increased, while the maximum bromine utilization factor (BUF) decreased with the increase of Br⁻ concentration. The maximum yield of HNMs decreased as pH value increased from 6.0 to 8.0 due to the deprotonation process. The BUF value remained relatively higher under an acidic condition, while pH value had no evident influence on the BIF value. The maximum yield of HNMs and value of BUF maximized at a Cl₂:Br⁻ ratio of 12.5, whereas the BIF value remained relatively higher at low Cl₂:Br⁻ ratios (2.5 and 5). The amino group in methylamine was first halogenated, and then released into solution as inorganic nitrogen by the rupture of C-N bond or transformed to nitro group by oxidation and elimination pathways. The maximum yield of HNMs in real waters was higher than that in pure water due to the high content of dissolved organic carbon. Two real waters were sampled to verify the law of HNMs formation. This study helps to understand the HNMs formation (especially brominated species) when the UV/Cl₂ process is adopted as a disinfection technique.     

Products of methotrexate during chlorination

Methotrexate(MTX)is a cytotoxic drug widely used in the treatment of tumors,autoimmune diseases and severe asthma. jen00883 This drug has been frequently detected in the aquatic environment with concentrations up to μg/L levels. The MTX present in environmental water might be transformed and removed during chlorination disinfection treatment. In this work,the fate of MTX during aqueous chlorination was investigated in laboratory batch experiments,and the transformation products of MTX were identified. Aqueous solutions of MTX(1 mg/L)were chlorinated by sodium hypochlorite solution at room temperature under neutral p H conditions. Chlorinated products were pre-concentrated with solid-phase extraction(SPE)cartridges and determined by liquid chromatography electrospray ionization tandem mass spectrometry(LC–ESI–MS/MS). The reaction of MTX chlorination exhibited pseudo-first-order kinetics and the half-life time of MTX degradation was calculated to be 1.65 min,when the initial chlorine concentration was 2 mg/L. Two chlorinated MTX congeners,4-amino-3-chlorinated-N10-methylpteroylglutamic(monochloro-MTX)and 4-amino-3,5-dichloro-N10-methylpteroylglutamic(dichloro-MTX)were found in the chlorinated solution. Monochloro-MTX was successfully fractionated by high performance liquid chromatography(HPLC)and its structure was further identified using ~1H nuclear magnetic resonance(NMR)analysis. The presence of the two products in real hospital wastewater was then examined and both compounds were detected. Finally,the effects of MTX and monochloro-MTX on the cell cycle progression in vitro were evaluated using zebrafish liver cell line. It was found that both compounds could inhibit the proliferation of zebrafish liver cells through S phase arrest and their effects on the cell cycle profile had no significant difference.     

Suspended particle effects on ClO2/ultraviolet light combined disinfection of effluent

The concentration of suspended solids of effluent often varies in a wide range, therefore the dose of ultraviolet light （UV） in disinfection process needs to be adjusted to meet the disinfection criterion at a high frequency, and the desired disinfection effect is difficult to be ensured. The particles size and particle-associated fecal coliform （F.C.） contribution, and their influence on UV disinfection were investigated when ClO2 and UV combined disinfection process was used. The results showed that suspended solids content had a major impact on UV disinfection efficiency, especially the large particle size fraction. Particles （D〉10μm） associated F. C. were difficult to be disinfected and were the main part of the railings of F.C. inactivation curve. Pre-ClO2 oxidation could reduce the number of particles in effluent, and make large particles decrease to small ones. Therefore, the influence of particles on UV disinfection could be reduced after pre-ClO2 oxidation, and the resistance ability to particle loadings of combined process was enhanced. Moreover, the combined process has a lot of advantages, such as low toxicity, low operational/maintenance costs; it is also convenient to be established in the existing wastewater plant or the new planned one.     

Efficacy assessment of peracetic acid in the removal of synthetic 17α-ethinyl estradiol contraceptive hormone in wastewater

Increasing concerns have been raised on endocrine disrupting chemicals like the sex hormone 17α-ethinylestradiol (EE2), the more since traditional wastewater (WW) treatments appear to be ineffective for their removal. The efficacy of the relatively novel disinfectant peracetic acid (PAA) in EE2 removal was evaluated, as well as its potential effects on WW quality parameters. The treatments tested for EE2 removal were also evaluated in terms of toxicity, through the determination of biochemical responses (antioxidant enzymes, lipid peroxidation and vitellogenin induction) using zebrafish (Danio rerio) as a biological model. PAA contact times less than 20 min appeared insufficient regardless of the PAA dose tested, but a 100% EE2 removal was attained at a PAA concentration of 15 mg/L with a contact time of 20 min. Total suspended solids, chemical oxygen demand and pH in PAA treatments remained well within levels set in European legislation for WW discharge. EE2 induced significant increased vitellogenin (VTG) levels in both female and male fish, indicating increased estrogenic activity, especially in males suggesting an endocrine disruption effect. With the addition of PAA (15 mg/L), however, VTG levels in both sexes returned to control values. Although this PAA treatment showed increased levels of the antioxidant enzyme catalase, the lipid peroxidation levels were similar or even lower than in controls. Overall the results suggest that the use of PAA appears a promising way forward as a less toxic alternative to chlorine disinfection with high efficiency in the removal of EDC like EE2.     

Assessing the capacity of biochar to stabilize copper and lead in contaminated sediments using chemical and extraction methods

Because of its high adsorption capacity, biochar has been used to stabilize metals when remediating contaminated soils; to date, however, it has seldom been used to remediate contaminated sediment. A biochar was used as a stabilization agent to remediate Cu- and Pb-contaminated sediments, collected from three locations in or close to Beijing. The sediments were mixed with a palm sawdust gasified biochar at a range of weight ratios (2.5%, 5%, and 10%) and incubated for 10, 30, or 60?days. The performance of the different treatments and the heavy metal fractions in the sediments were assessed using four extraction methods, including diffusive gradients in thin films, the porewater concentration, a sequential extraction, and the toxicity characteristic leaching procedure. The results showed that biochar could enhance the stability of heavy metals in contaminated sediments. The degree of stability increased as both the dose of biochar and the incubation time increased. The sediment pH and the morphology of the metal crystals adsorbed onto the biochar changed as the contact time increased. Our results showed that adsorption, metal crystallization, and the pH were the main controls on the stabilization of metals in contaminated sediment by biochar.