Qin L, Zhang X, Chen Y, Mo L, Zeng H, Liang Y. Predictive QSAR Models for the Toxicity of Disinfection Byproducts. Molecules 2017 Oct 9;22(10). pii: E1671. doi: 10.3390/molecules22101671
Several hundred disinfection byproducts (DBPs) in drinking water have been identified, and are known to have potentially adverse health effects. There are toxicological data gaps for most DBPs, and the predictive method may provide an effective way to address this. The development of an in-silico model of toxicology endpoints of DBPs is rarely studied. The main aim of the present study is to develop predictive quantitative structure-activity relationship (QSAR) models for the reactive toxicities of 50 DBPs in the five bioassays of X-Microtox, GSH+, GSH-, DNA+ and DNA-. All-subset regression was used to select the optimal descriptors, and multiple linear-regression models were built. The developed QSAR models for five endpoints satisfied the internal and external validation criteria: coefficient of determination (R²) > 0.7, explained variance in leave-one-out prediction (Q²LOO) and in leave-many-out prediction (Q²LMO) > 0.6, variance explained in external prediction (Q²F1, Q²F2, and Q²F3) > 0.7, and concordance correlation coefficient (CCC) > 0.85. The application domains and the meaning of the selective descriptors for the QSAR models were discussed. The obtained QSAR models can be used in predicting the toxicities of the 50 DBPs.
Wang AQ, Lin YL, Xu B, Hu CY, Zhang MS, Xia SJ, Zhang TY, Chu WH, Gao NY. Degradation of acrylamide during chlorination as a precursor of haloacetonitriles and haloacetamides. The Science of the total environment. 2017 Sep 26;615:38-46. doi: 10.1016/j.scitotenv.2017.09.141.
Acrylamide is a monomer of polyacrylamide, which is widely used in the water treatment process as a flocculant. The degradation kinetics and formation of disinfection by-products (DBPs) during acrylamide chlorination were investigated in this study. The reaction between chlorine and acrylamide followed a pseudo-first-order kinetics. A kinetic model regarding acrylamide chlorination was established and the rate constants of each predominant elementary reaction (i.e., the base-catalyzed reaction of acrylamide with ClO–as well as the reactions of acrylamide with HOCl and ClO–) were calculated as 7.89×107M-2h-1, 7.72×101M-1h-1, and 1.65×103M-1h-1, respectively. The presence of Br– in water led to the formation of HOBr and accelerated the rate of acrylamide degradation by chlorine. The reaction rate constant of acrylamide with HOBr was calculated as 1.33×103M-1h-1. The degradation pathways of acrylamide chlorination were proposed according to the intermediates identified using ultra-performance liquid chromatography and electrospray ionization-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF/MS). Five chlorinated DBPs including chloroform (CF), dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN), dichloroacetamide (DCAcAm), and trichloroacetamide (TCAcAm) were identified during acrylamide chlorination. The formation of CF, DCAN, DCAcAm, and TCAcAm kept increasing, while that of TCAN increased and then decreased with increasing reaction time. As the chlorine dosage increased from 0.75 to 4.5mM, DCAN became the dominant DBP. Large amounts of CF, DCAN, and TCAN were formed at basic pHs. The hydrolysis of DCAN and TCAN led to the formation of DCAcAm and TCAcAm, respectively. The results of this study elucidated that acrylamide can be a precursor for the formation of haloacetonitriles (HANs) and haloacetamides (HAcAms) during drinking water treatment.
Coroneo V, Carraro V, Marras B, Marrucci A, Succa S, Meloni B, Pinna A, Angioni A, Sanna A, Schintu M. PRESENCE OF TRIHALOMETHANES IN READY-TO-EAT VEGETABLES DISINFECTED WITH CHLORINE. Food additives and contaminants. Part A, Chemistry, analysis, control, exposure and risk assessment. Food Addit Contam Part A Chem Anal Control Expo Risk Assess. 2017 Sep 21. doi: 10.1080/19440049.2017.1382723.
Trihalomethanes (THMs) – CHCl3, CHCl2Br, CHClBr2 and CHBr3 – are drinking water disinfection by-products (DBPs). These compounds can also be absorbed by different types of foods, including ready-to-eat (RTE) fresh vegetables. The potential absorption of THMs during washing of RTE vegetables could pose a potential risk to consumers’ health. The concentration of THMs in the water used in the manufacturing process of these products shall not exceed the limit of 100 or 80 µgL-1 according to European Union (EU) and United States legislation respectively. By contrast, there is little information about the presence of such compounds in the final product. This study evaluated the concentration of THMs in different types of RTE vegetables (carrots, iceberg lettuce, lettuce, mixed salad, parsley, parsley and garlic, rocket salad, valerian) after washing with chlorinated water. In the 115 samples analyzed, the average value of total THMs was equal to 76.7 ng g-1. Chloroform was the THM present in the largest percentage in all the RTE vegetables. These results show that the process of washing RTE vegetables should be optimized in order to reduce the risk for consumers associated with the presence of DBPs.
Y Kimura S, Zheng W, N Hipp T, M Allen J, D Richardson S. Total organic halogen (TOX) in human urine: A halogen-specific method for human exposure studies. Journal of environmental sciences (China). 2017 Aug;58:285-295. doi: 10.1016/j.jes.2017.04.008.
Disinfection by-products (DBPs) are a complex mixture of compounds unintentionally formed as a result of disinfection processes used to treat drinking water. Effects of long-term exposure to DBPs are mostly unknown and were the subject of recent epidemiological studies. However, most bioanalytical methods focus on a select few DBPs. In this study, a new comprehensive bioanalytical method has been developed that can quantify mixtures of organic halogenated compounds, including DBPs, in human urine as total organic chlorine (TOCl), total organic bromine (TOBr), and total organic iodine (TOI). The optimized method consists of urine dilution, adsorption to activated carbon, pyrolysis of activated carbon, absorption of gases in an aqueous solution, and halide analysis with ion chromatography and inductively coupled plasma-mass spectrometry. Spike recoveries for TOCl, TOBr, and TOI measurements ranged between 78% and 99%. Average TOCl, TOBr, and TOI concentrations in five urine samples from volunteers who consumed tap water were 1850, 82, and 21.0μg/L as X–, respectively. Volunteers who consumed spring water (control) had TOCl, TOBr, and TOI average concentrations in urine of 1090, 88, and 10.3μg/L as X–, respectively. TOCl and TOI in the urine samples from tap water consumers were higher than the control. However, TOBr was slightly lower in tap water urine samples compared to mineral water urine samples, indicating other sources of environmental exposure other than drinking water. A larger sample population that consumes tap water from different cities and mineral water is needed to determine TOCl, TOBr, and TOI exposure from drinking water.
Zhang Y, Chu W, Yao D, Yin D. Control of aliphatic halogenated DBP precursors with multiple drinking water treatment processes: Formation potential and integrated toxicity. J Environ Sci (China). 2017 Aug;58:322-330. doi: 10.1016/j.jes.2017.03.028.
The comprehensive control efficiency for the formation potentials (FPs) of a range of regulated and unregulated halogenated disinfection by-products (DBPs) (including carbonaceous DBPs (C-DBPs), nitrogenous DBPs (N-DBPs), and iodinated DBPs (I-DBPs)) with the multiple drinking water treatment processes, including pre-ozonation, conventional treatment (coagulation-sedimentation, pre-sand filtration), ozone-biological activated carbon (O3-BAC) advanced treatment, and post-sand filtration, was investigated. The potential toxic risks of DBPs by combing their FPs and toxicity values were also evaluated. The results showed that the multiple drinking water treatment processes had superior performance in removing organic/inorganic precursors and reducing the formation of a range of halogenated DBPs. Therein, ozonation significantly removed bromide and iodide, and thus reduced the formation of brominated and iodinated DBPs. The removal of organic carbon and nitrogen precursors by the conventional treatment processes was substantially improved by O3-BAC advanced treatment, and thus prevented the formation of chlorinated C-DBPs and N-DBPs. However, BAC filtration leads to the increased formation of brominated C-DBPs and N-DBPs due to the increase of bromide/DOC and bromide/DON. After the whole multiple treatment processes, the rank order for integrated toxic risk values caused by these halogenated DBPs was haloacetonitriles (HANs)≫haloacetamides (HAMs)>haloacetic acids (HAAs)>trihalomethanes (THMs)>halonitromethanes (HNMs)≫I-DBPs (I-HAMs and I-THMs). I-DBPs failed to cause high integrated toxic risk because of their very low FPs. The significant higher integrated toxic risk value caused by HANs than other halogenated DBPs cannot be ignored.
Allen JM, Cuthbertson AA, Liberatore HK, Kimura SY, Mantha A, Edwards MA, Richardson SD. Showering in Flint, MI: Is there a DBP problem? J Environ Sci (China). 2017 Aug;58:271-284. doi: 10.1016/j.jes.2017.06.009.
Lead contamination in the City of Flint, MI has been well documented over the past two years, with lead levels above the EPA Action Level until summer 2016. This resulted from an ill-fated decision to switch from Detroit water (Lake Huron) with corrosion control, to Flint River water without corrosion control. Although lead levels are now closer to normal, reports of skin rashes have sparked questions surrounding tap water in some Flint homes. This study investigated the presence of contaminants, including disinfection by-products (DBPs), in the hot tap water used for showering in the homes of residents in Flint. Extensive quantitative analysis of 61 regulated and priority unregulated DBPs was conducted in Flint hot and cold tap water, along with the analysis of 50 volatile organic compounds and a nontarget comprehensive, broadscreen analysis, to identify a possible source for the reported skin rashes. For comparison, chlorinated hot and cold waters from three other cities were also sampled, including Detroit, which also uses Lake Huron as its source water. Results showed that hot water samples generally contained elevated levels of regulated and priority unregulated DBPs compared to cold water samples, but trihalomethanes were still within regulatory limits. Overall, hot shower water from Flint was similar to waters sampled from the three other cities and did not have unusually high levels of DBPs or other organic chemicals that could be responsible for the skin rashes observed by residents. It is possible that an inorganic chemical or microbial contaminant may be responsible.
Nie X, Liu W, Zhang L, Liu Q. Genotoxicity of drinking water treated with different disinfectants and effects of disinfection conditions detected by umu-test. Journal of environmental sciences (China). 2017 Jun;56:36-44. doi: 10.1016/j.jes.2016.07.016.
The genotoxicity of drinking water treated with 6 disinfection methods and the effects of disinfection conditions were investigated using the umu-test. The pretreatment procedure of samples for the umu-test was optimized for drinking water analysis. The results of the umu-test were in good correlation with those of the Ames-test. The genotoxicity and production of haloacetic acids (HAAs) were the highest for chlorinated samples. UV+chloramination is the safest disinfection method from the aspects of genotoxicity, HAA production and inactivation effects. For chloramination, the effects of the mass ratio of Cl2 to N of chloramine on genotoxicity were also studied. The changes of genotoxicity were different from those of HAA production, which implied that HAA production cannot represent the genotoxic potential of water. The genotoxicity per chlorine decay of chlorination and chloramination had similar trends, indicating that the reaction of organic matters and chlorine made a great contribution to the genotoxicity. The results of this study are of engineering significance for optimizing the operation of waterworks.