Sunlight enhanced the formation of tribromomethane from benzotriazole degradation during the sunlight/free chlorine treatment in the presence of bromide.

The coexistence of free chlorine and bromide under sunlight irradiation (sunlight/FC with Br-) is unavoidable in outdoor seawater swimming pools, and the formation of brominated disinfection byproducts could act more harmful than chlorinated disinfection byproducts. In this study, benzotriazole was selected as a model compound to investigate the degradation rate and the subsequent formation of disinfection byproducts via sunlight/FC with Br- process. The rate constants for the degradation of benzotriazole under pseudo first order conditions in sunlight/FC with Br- and sunlight/FC are 2.3 ± 0.07 × 10-1 min-1 and 6.0 ± 0.7 × 10-2 min-1, respectively. The enhanced degradation of benzotriazole can be ascribed to the generation of HO•, bromine species, and reactive halogen species (RHS) during sunlight/FC with Br-. Despite the fact that sunlight/FC with Br- process enhanced benzotriazole degradation, the reaction results in increasing tribromomethane (TBM) formation. A high concentration (37.8 µg/L) of TBM was detected in the sunlight/FC with Br-, which was due to the reaction of RHS. The degradation of benzotriazole was notably influenced by the pH value (pH 4 - 11), the concentration of bromide (0 - 2 mM), and free chlorine (1 - 6 mg/L). Furthermore, the concentration of TBM increased when the free chlorine concentrations increased, implying the formation potential of harmful TBM in chlorinated seawater swimming pools.

Analytical methods for conventional and emerging disinfection by-products in fresh-cut produce.

The formation of toxic disinfection by-products (DBPs) is among the main concerns in the use of chlorine sanitizers for washing fresh and fresh-cut produce to minimize microbial cross-contamination. Even so, robust analytical methods for measuring various DBPs in produce have been lacking. This study has established two liquid-liquid extraction methods, followed by gas chromatography with electron capture detection, to measure 32 conventional and emerging DBPs in different produce types including lettuce, cabbage and strawberry. Good recoveries (50-130%) were achieved for most DBPs in the different produce. The method detection limits were in the range of 0.3-10 ng/g for trihalomethanes, haloacetic acids, nitrogenous DBPs, and other carbonaceous DBPs. Preliminary screening analysis indicated one-third of the target DBPs were found in unwashed produce, and washing with chlorine significantly promoted DBPs' formation and concentrations in the produce. The developed analytical methods will be useful tools for future research on food DBPs.

Removal of pharmaceuticals and personal care products by two-stage biofiltration for drinking water treatment.

Contamination of drinking water with pharmaceuticals and personal care products (PPCPs) is an issue of health concerns. To effectively control the level of PPCPs in drinking water, a pilot study employing two parallel trains of two-stage biofiltration, i.e., a sand/anthracite (SA) biofilter coupled with a biologically-active granular activated carbon (GAC) post-filter contactor, was conducted as a post-treatment after coagulation in a drinking water treatment plant. Results showed the biofiltration process could effectively remove PPCPs with an average removal of 53.4%, where the GAC contactor played the dominant role to remove 48.1% of the total PPCPs. The molecular properties determined the removability of individual PPCPs, i.e., smaller molecules with simpler structure connectivity were more likely to be removed. Based on the quantitative structure-property relationships (QSPRs) analysis, a simple regression model was proposed to predict the removability of each PPCP across the biofiltration process. The drinking water equivalent level (DWEL) quotient method was developed to assess the health risks of detected PPCPs in water samples. The biofiltration process showed efficient capacity to reduce the health risks of PPCPs with an average removal of 79%, and the PPCPs in the effluents generally would not pose adverse health effects. Pearson correlation analysis explored the possible role of nitrogenous PPCPs (N-PPCPs) as the precursors of nitrogenous disinfection byproducts (N-DBPs) in drinking waters. Aromatic nitrogen in PPCPs was found to be a significant descriptor for the formation potential of trichloroacetonitrile (TCAN). In addition, it was found that pre-filter chlorination could slightly improve the biofiltration of PPCPs.

Analysis of 40 conventional and emerging disinfection by-products in fresh-cut produce wash water by modified EPA methods.

Chlorine sanitizers used in washing fresh and fresh-cut produce can lead to generation of disinfection by-products (DBPs) that are harmful to human health. Monitoring of DBPs is necessary to protect food safety but comprehensive analytical methods have been lacking. This study has optimized three U.S. Environmental Protection Agency methods for drinking water DBPs to improve their performance for produce wash water. The method development encompasses 40 conventional and emerging DBPs. Good recoveries (60-130%) were achieved for most DBPs in deionized water and in lettuce, strawberry and cabbage wash water. The method detection limits are in the range of 0.06-0.58 µg/L for most DBPs and 10-24 ng/L for nitrosamines in produce wash water. Preliminary results revealed the formation of many DBPs when produce is washed with chlorine. The optimized analytical methods by this study effectively reduce matrix interference and can serve as useful tools for future research on food DBPs.

Sources of pharmaceuticals and personal care products in swimming pools.

Pharmaceuticals and personal care products (PPCPs) in swimming pool water are hypothesized to originate from fill water and anthropogenic sources like urine, sweat, swimwear and body surfaces. However, research exploring PPCP origins in pools is lacking. This research investigates PPCP sources at 31 swimming pools. Pool water was analyzed for 24 representative PPCPs using advanced liquid chromatography-mass spectrometry techniques. Fill water was analyzed as a contamination source and to determine if swimmers introduce PPCPs to pools. Results show every PPCP in fill water was present in pools except one, suggesting fill water is a PPCP source at pools. The presence of the antidepressant fluoxetine in 26% of pools and 0% of fill water indicates swimmers introduce pharmaceuticals. The flame retardant (tris(2-carboxyethyl)phosphine (TCEP)) was present 48% more frequently in pool than fill water, suggesting TCEP is introduced by body surfaces or swimwear. Enforcing showering and bathroom breaks is recommended to reduce PPCP contamination from swimmers.

Removal of disinfection byproduct (DBP) precursors in water by two-stage biofiltration treatment.

The removal of precursors of 36 disinfection byproducts (DBPs) in effluents from flocculation/sedimentation process was evaluated across a pilot-scale two-stage biofiltration process, i.e., a sand/anthracite (SA) biofilter (empty bed contact time (EBCT) of 7.5 min) coupled with a biologically-active granular activated carbon (GAC) contactor (EBCT of 15 min). The biofiltration process exhibited a good capacity for removal of the total DBP formation potential (DBPFP) (by 25.90 ± 2.63%), and GAC contactors contributed most to the DBPFP removal (accounting for 60.63 ± 16.64% of the total removal). The removal percentage of DBPFPs of different structure types was in the following order: halonitroalkanes (58.50%) > haloaldehydes (33.62%) > haloacetic acids (HAAs, 28.13%) > haloalkanes (20.46%) > haloketones (13.46%) > nitrosamines (10.23%) > halonitriles (-8.82%) > haloalkenes (-9.84%). The precursors of bromo-DBPs (containing only bromine atoms) and maximal halogenated DBPs (containing 3 & 4 halo atoms) were removed largely compared to other DBPs. Among the total DBPFP, trihalomethanes (THMs), HAAs, and chloral hydrate were the dominant DBPs, and they accounted for >92% of the total targeted DBPs by weight. Pearson correlation analysis (CA) and principal components analysis (PCA) indicated a significant association among these dominant DBPs. Canonical correspondence analysis (CCA) revealed specific ultraviolet absorbance (SUVA254) could serve as a good surrogate parameter for DBPFP. Pre-chlorination upstream of the biofilters may not greatly impact the overall removal of DBPFP by SA/GAC biofiltration. In addition, results showed that SA/GAC biofiltration was a useful procedure to remove the inorganic DBP chlorite.

Pilot investigation of two-stage biofiltration for removal of natural organic matter in drinking water treatment.

A pilot study employing two parallel trains of two-stage biofiltration, i.e., a sand/anthracite (SA) biofilter followed by a biologically-active granular activated carbon (GAC) contactor, was conducted to test the efficiency, feasibility and stability of biofiltration for removing natural organic matter (NOM) after coagulation in a drinking water treatment plant. Results showed the biofiltration process could effectively remove turbidity (<0.1 NTU in all effluents) and NOM (>24% of dissolved organic carbon (DOC), >57% of UV254, and >44% of SUVA254), where the SA biofilters showed a strong capacity for turbidity removal, while the GAC contactors played the dominant role in NOM removal. The vertical profile of water quality in the GAC contactors indicated the middle-upper portion was the critical zone for the removal of NOM, where relatively higher adsorption and enhanced biological removal were afforded. Fluorescence excitation-emission matrix (EEM) analysis of NOM showed that the GAC contactors effectively decreased the content of humic-like component, while protein-like component was refractory for the biofiltration process. Nutrients (NH4-N and PO4-P) supplementation applied upstream of one of the two-stage biofiltration trains (called engineered biofiltration) stimulated the growth of microorganisms, and showed a modest effect on promoting the biological removal of small non-aromatic compositions in NOM. Redundancy analysis (RDA) indicated influent UV254 was the most explanatory water quality parameter for GAC contactors' treatment performance, and a high load of UV254 would result in significantly reduced removals of UV254 and SUVA254.

Degradation of DEET and Caffeine under UV/Chlorine and Simulated Sunlight/Chlorine Conditions.

Photoactivation of aqueous chlorine could promote degradation of chlorine-resistant and photochemically stable chemicals accumulated in swimming pools. This study investigated the degradation of two such chemicals, N,N-diethyl-3-methylbenzamide (DEET) and caffeine, by low pressure ultraviolet (UV) light and simulated sunlight (SS) activated free chlorine (FC) in different water matrices. Both DEET and caffeine were rapidly degraded by UV/FC and SS/FC but exhibited different kinetic behaviors. The degradation of DEET followed pseudo-first-order kinetics, whereas the degradation of caffeine accelerated with reaction. Mechanistic study revealed that, under UV/FC, ·OH and Cl· were responsible for degradation of DEET, whereas ClO· related reactive species (ClOrrs), generated by the reaction between FC and ·OH/Cl·, played a major role in addition to ·OH and Cl· in degrading caffeine. Reaction rate constants of DEET and caffeine with the respective radical species were estimated. The imidazole moiety of caffeine was critical for the special reactivity with ClOrrs. Water matrix such as pH had a stronger impact on the UV/FC process than the SS/FC process. In saltwater matrix under UV/FC and SS/FC, the degradation of DEET was significantly inhibited, but the degradation of caffeine was much faster than that in nonsalty solutions. The interaction between Br- and Cl- may play an important role in the degradation of caffeine by UV/FC in saltwater. Reaction product analysis showed similar product patterns by UV/FC and SS/FC and minimal formation of chlorinated intermediates and disinfection byproducts.

Ketamine and the metabolite norketamine: persistence and phototransformation toxicity in hospital wastewater and surface water.

Ketamine has been increasingly used both recreationally and medicinally around the world. Although the metabolic pathways to form its metabolite norketamine have been carefully investigated in humans and animals, knowledge of their environmental occurrence and fate is limited. In this study, we investigated the occurrence of ketamine and norketamine in 20 natural bodies of water, effluents from 13 hospitals, two wastewater treatment plants and one water supply plant. Ketamine was found at concentrations as high as 10 µg/L. Ketamine and norketamine were consistently found in similar concentrations (ketamine/norketamine ratio: 0.3-4.6) in the collected water samples, and this ratio similar to that found in urine samples. Dark incubation experiments have shown that ketamine is not susceptible to microbial degradation or hydrolysis. Phototransformation was demonstrated to significantly reduce the concentration of ketamine and norketamine in river waters (t(1/2) = 12.6 ± 0.4 and 10.1 ± 0.4 h, respectively) and resulted in byproducts that are similar to human metabolites. Both direct and indirect photolysis led to the N-demethylation of ketamine to form norketamine and other byproducts, including hydroxy-norketamine (HNK), dehydronorketamine (DNK), hydroxy-ketamine (HK) and isomer forms of ketamine and norketamine. Irradiated solutions exhibited higher toxicity (via the Microtox test). Although a final risk assessment could not be made due to a lack of studies on the chronic effects on aquatic organisms, the high and persistent environmental occurrences of ketamine and norketamine as well as the increasingly acute toxicity of the photo byproducts demonstrate the importance of including metabolites in evaluation of the overall risk of ketamine.

Prevalence and sunlight photolysis of controlled and chemotherapeutic drugs in aqueous environments.

This study addresses the occurrences and natural fates of chemotherapeutics and controlled drugs when found together in hospital effluents and surface waters. The results revealed the presence of 11 out of 16 drugs in hospital effluents, and the maximum detected concentrations were at the µg L(-1) level in the hospital effluents and the ng L(-1) level in surface waters. The highest concentrations corresponded to meperidine, morphine, 5-fluorouracil and cyclophosphamide. The sunlight photolysis of the target compounds was investigated, and the results indicated that morphine and codeine can be significantly attenuated, with half-lives of 0.27 and 2.5 h, respectively, in natural waters. Photolysis can lower the detected environmental concentrations, also lowering the estimated environmental risks of the target drugs to human health. Nevertheless, 5-fluorouracil and codeine were found to have a high risk quotient (RQ), demonstrating the high risks of directly releasing hospital wastewater into the environment.

Phototransformation determines the fate of 5-fluorouracil and cyclophosphamide in natural surface waters.

The use of cytotoxic substances, such as 5-fluorouracil and cyclophosphamide, is carefully controlled; however, these medications may still enter bodies of water through wastewater discharge. These substances may pose risks to stream and river life, as well as to humans via drinking water. In this study, the photochemical fate of 5-fluorouracil and cyclophosphamide was investigated in synthetic waters and four river waters and was found to be the most important attenuation process for each entity in natural surface waters. Bicarbonate alone was found to react with the excited states of 5-fluorouracil, thus enhancing direct photolysis rates. In the presence of nitrate and significant amounts of bicarbonate (close to 2 mM), 5-fluorouracil was rapidly removed (within 1 day) through indirect photolysis. In contrast, natural attenuation was of low importance for cyclophosphamide in most surface waters studied. A long, shallow river or lake with a long residence time (>7 days), very low alkalinity, and significant nitrate levels (>5 mg-N L(-1)) may be an exception. The phototransformation product of 5-fluorouracil was also identified. However, the total organic carbon experiments yielded important results: photolysis resulted in quick transformation of 5-fluorouracil but minimal mineralization. Additional studies of the toxicity of photobyproducts of 5-fluorouracil are needed to determine the true risk to human health of 5-fluorouracil contamination of surface water, given its near-total photodegradation and resultant, deceptively low detection rate in surface waters.