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The 2016 U.S. Environmental Protection Agency (EPA) Integrated Risk Information System (IRIS) assessment for ethylene oxide (EO) estimated a 10 -6 increased inhalation cancer risk of 0.1 parts per trillion, based on National Institute of Occupational Safety and Health (NIOSH) epidemiology studies of sterilization facility workers exposed to EO between 1938 and 1986. The worker exposure estimates were based on a NIOSH statistical regression (NSR) model "validated" with EO levels measured after 1978. Between 1938 and 1978, when EO data was unavailable, the NSR model predicts exposures lowest in 1938 increasing to peak levels in 1978. That increasing EO concentration trend arose, in part, because engineering/industrial-hygiene (E/IH) factors associated with evolving EO-sterilization equipment and operations before 1978 were not properly considered in the NSR model. To test the NSR model trend prediction, a new E/IH-based model was developed using historical data on EO kill concentrations, EO residue levels in sterilized materials, post-wash EO concentrations in a sterilization chamber, and information on facility characteristics and sterilizer operator practices from operators familiar with pre-1978 industry conditions. The E/IH 90th percentile of 8 h time-weighted average EO exposures (C 90 ) for highly exposed sterilizer operators was calibrated to match 1978 C 90 values from the NSR model. E/IH model C 90 exposures were estimated to decrease over time from levels 16 and were four-fold greater than NSR-estimated exposures for workers during 1938-1954 and 1955-1964. This E/IH modeled trend is opposite to that of NSR model predictions of exposures before 1978, suggesting that EPA's exclusive reliance on the NIOSH cohort to estimate EO cancer risk should be re-examined.

Swimming pools are disinfected to protect against the risk of microbial disease, however, the formation of disinfection by-products (DBPs) is an unwanted consequence. While many studies have reported the occurrence of commonly investigated DBPs (trihalomethanes and haloacetic acids) in pools, few studies have investigated emerging DBP classes, such as the haloketones or haloacetaldehydes, and the nitrogenous haloacetamides, halonitromethanes, haloacetonitriles and N-nitrosamines. This study investigated the occurrence of sixty four DBPs from the eight aforementioned DBP classes in pools employing different treatment methods. Approximately 70% of the DBPs were detected in at least one of the pools, with most concentrations being equal to or greater than those previously reported. Chloral hydrate (trichloroacetaldehyde) was one of many DBPs detected in all chlorinated waters (202 to 1313 μg/L), and, on a molar basis, was the predominant DBP. Several other DBPs, namely chloroacetic acid, dichloroacetic acid, trichloroacetic acid, dichloroacetamide, dibromoacetamide, dibromochloroacetamide and trichloroacetamide, and many of the N-nitrosamines, were measured at concentrations greater than previously reported: up to 200 to 479 μg/L for the haloacetic acids, 56 to 736 μg/L for the haloacetamides and up to 1093 ng/L for some N-nitrosamines. The higher disinfectant residuals required to be employed in Australian pools, and poor pool management (e.g. of chlorine residual and pH) are likely factors contributing to these relatively high DBP concentrations. Where possible, the cytotoxicity values of the investigated DBPs were evaluated, with chloral hydrate representing over 90% of the total chronic cytotoxicity despite only representing up to 64% of the total molar DBP concentration. This study is the first report of bromodichloroacetaldehyde and bromochloroacetaldehyde in pools and is the first investigation of N-nitrosamines in a brominated pool. Furthermore, this work aids in understanding DBPs in both chlorine and bromine treated pools, the latter being the subject of only limited previous studies., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Certain volatile disinfection by-products (DBPs) off-gassing from pool water can cause eye and skin irritations, respiratory problems, and even cancer. No guidelines or recommendations concerning DBPs in the air exist in Norway. Traditionally, ventilation strategies in indoor swimming pools are based on reducing condensation on the windows rather than ensuring proper air quality in the users' breathing zone. A total of 93 air samples of airborne concentrations of trihalomethanes (THMs) were collected via stationary sampling. We investigated the distribution of total THM (tTHM) 0.05 m and 0.60 m above the water surface at six different locations in the poolroom and the covariation between the water and air quality parameters. Based on a linear mixed effects model, the most important determinants in terms of predicting the air concentration of CHCl 3 were height above water surface, air changes of fresh air per hour, concentration of combined chlorine in the water, relative humidity (RH) and day of the week. Approximately 36% of the total variability could be attributed to these variables; hence, to reduce the average exposure in the poolroom, hazard control should focus on these variables. Based on the identified predictor variables, the supplied air should be controlled based on water quality in addition to the traditional control censors for RH and air temperature used in the ventilation system of Norwegian swimming facilities., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Formation of iodinated disinfection byproducts (I-DBPs) in drinking water has become an emerging concern. Compared to chlorine- and bromine-containing DBPs, I-DBPs are more toxic, have different precursors and formation mechanisms, and are unregulated. In this Account, we focus on recent research in the formation of known and unknown I-DBPs in drinking water. We present the state-of-the-art understanding of known I-DBPs for the six groups reported to date, including iodinated methanes, acids, acetamides, acetonitriles, acetaldehyde, and phenols. I-DBP concentrations in drinking water generally range from ng L -1 to low-μg L -1 . The toxicological effects of I-DBPs are summarized and compared with those of chlorinated and brominated DBPs. I-DBPs are almost always more cytotoxic and genotoxic than their chlorinated and brominated analogues. Iodoacetic acid is the most genotoxic of all DBPs studied to date, and diiodoacetamide and iodoacetamide are the most cytotoxic. We discuss I-DBP formation mechanisms during oxidation, disinfection, and distribution of drinking water, focusing on inorganic and organic iodine sources, oxidation kinetics of iodide, and formation pathways. Naturally occurring iodide, iodate, and iodinated organic compounds are regarded as important sources of I-DBPs. The apparent second-order rate constant and half-lives for oxidation of iodide or hypoiodous acid by various oxidants are highly variable, which is a key factor governing the iodine fate during drinking water treatment. In distribution systems, residual iodide and disinfectants can participate in reactions involving heterogeneous chemical oxidation, reduction, adsorption, and catalysis, which may eventually affect I-DBP levels in finished drinking water. The identification of unknown I-DBPs and total organic iodine analysis is also summarized in this Account, which provides a more complete picture of I-DBP formation in drinking water. As organic DBP precursors are difficult to completely remove during the drinking water treatment process, the removal of iodide provides a cost-effective solution for the control of I-DBP formation. This Account not only serves as a reference for future epidemiological studies to better assess human health risks due to exposure to I-DBPs in drinking water but also helps drinking water utilities, researchers, regulators, and the general public understand the formed species, levels, and formation mechanisms of I-DBPs in drinking water.

Steroid hormones and biocides are regarded as emerging contaminants in rural wastewater in China, owing to their widespread occurrence and adverse effects on both aquatic organisms and humans. Constructed wetlands (CWs) are an alternative technology for cost-effective and efficient decentralized rural sewage treatment. In this study, an integrated constructed wetland (ICW) system was built and used to treat a typical rural wastewater mixture composed of domestic sewage and livestock wastewater from a small village. As expected, five steroid hormones (ADD, AED, 19-NTD, T, and P) and four biocides (DEET, TCS, CBD, and MP) were detected in the influent in concentrations ranging from 30.5 ± 1.25 ng/L to 105 ± 5.14 ng/L and from 63.4 ± 2.85 ng/L to 515 ± 19.7 ng/L, respectively. The ICW system effectively removed the detected steroid hormones (97.4 ± 0.09%) and biocides (92.4 ± 0.54%). Based on the measured concentrations, the total pollution loadings of the detected steroid hormones and biocides in the influent were calculated to be 2330 ± 26.5 μg/day and 5710 ± 196 μg/day, which decreased to 60.8 ± 1.44 μg/day and 433 ± 25.6 μg/day in the final effluent. The risk quotients for these steroid hormones and biocides in the effluent from the ICW system were lower than those from reported wastewater treatment plants, indicating that CWs are a promising technology for removing contaminants including steroid hormones and biocides in rural wastewater, although additional efforts are required to optimize and improve the design of CWs before the steroid hormones and biocides present in the effluent can be safely and directly discharged into the environment., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Trial-and-error chlorination as a conventional practice for swimming pool water disinfection may fail to consistently maintain the pool's residual chlorine within regulatory limits. This study explored the variability of residual chlorine and other common water quality parameters of two sample swimming pools and examined the potential of using a mass balance model for proactive determination of chlorine consumption to better secure the hygienic safety of bathers. A lightly loaded Pool 1 with a normalized bather load of 0.038 bather/m 3 /day and a heavily loaded Pool 2 with a normalized bather load of 0.36 bather/m 3 /day showed great variances in residual free and combined chlorine control by trial-and-error methods due to dynamic pool uses. A mass balance model based on chemical and physical chlorine consumption mechanisms was found to be statistically valid using field data obtained from Pool 1. The chlorine consumption per capita coefficient was determined to be 4120 mg/bather. The predictive method based on chlorine demand has a potential to be used as a complementary approach to the existing trial-and-error chlorination practices for swimming pool water disinfection. The research is useful for pool maintenance to proactively determine the required chlorine dosage for compliance of pool regulations.

The organic matter and two types of disinfection byproduct (DBP) precursors in micro-polluted source water were removed using an iron-carbon micro-electrolysis (ICME) combined with up-flow biological aerated filter (UBAF) process. Two pilot-scale experiments (ICME-UBAF and UBAF alone) were used to investigate the effect of the ICME system on the removal of organic matter and DBP precursors. The results showed that ICME pretreatment removed 15.6% of dissolved organic matter (DOM) and significantly improved the removal rate in the subsequent UBAF process. The ICME system removed 31% of trichloromethane (TCM) precursors and 20% of dichloroacetonitrile (DCAN) precursors. The results of measurements of the molecular weight distribution and hydrophilic fractions of DOM and DBP precursors showed that ICME pretreatment played a key role in breaking large-molecular-weight organic matter into low-molecular-weight components, and the hydrophobic fraction into hydrophilic compounds, which was favorable for subsequent biodegradation by UBAF. Three-dimensional fluorescence spectroscopy (3D-EEM) further indicated that the ICME system improved the removal of TCM and DCAN precursors. The biomass analysis indicated the presence of a larger and more diverse microbial community in the ICME-UBAF system than for the UBAF alone. The high-throughput sequencing results revealed that domination of the genera Sphingomonas, Brevundimonas and Sphingorhabdus contributed to the better removal of organic matter and two types of DBP precursors. Also, Nitrosomonas and Pseudomonas were beneficial for ammonia removal., (Copyright © 2018. Published by Elsevier B.V.)

Biocides, also referred to as 'microbicides' or 'inhibitors', are widely used in industrial processes (e.g. utility water in cooling towers) to control and/or eliminate the growth of microorganisms. Because of their inherent toxicity, their presence in various sources (e.g. river sediments, potable water) can negatively affect ecosystems. Currently available biocide detection techniques are not suitable for 'point-of-use' applications since they are tedious, complicated, and often require experienced personnel to operate. To address this concern, we sought to develop a simple-to-use toxicity bioassay based on a model microorganism (E. coli) after short (<30 min) exposure to known biocides that can be stored at room temperature (preferably) or in the fridge. Based on recent work and our expertise in polymer-based preservation of biomolecules, we leveraged this knowledge to improve E. coli preservation for biocide detection purposes. A design-of-experiments strategy was used to evaluate 16 different preservation conditions from 5 process parameters (i.e. 2 5-1 fractional factorial). It was found that pullulan, a sugar-based polymer, improved E. coli culturability by an order of magnitude after three months of storage. Also, it was found that storing E. coli in the fridge in Milli-Q water was favorable for maintaining a high level of culturability. Finally, the toxicity of three common biocides (Cetyltrimethylammonium bromide (CTAB), ProClin™ 300, and Grotan ® BK) was evaluated using a fluorescence-based assay across all 16 preservation conditions. The response of the preserved E. coli was biocide specific and at certain conditions did not vary during the entire three-month storage period., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The occurrence of disinfection by-products (DBPs) in drinking water has become an issue of concern during the past decades. The DBPs pose health risks and are suspected to cause various cancer forms, be genotoxic, and have negative developmental effects. The vast chemical diversity of DBPs makes comprehensive monitoring challenging. Only few of the DBPs are regulated and included in analytical protocols. In this study, a method for simultaneous measurement of 20 DBPs from five different structural classes (both regulated and non-regulated) was investigated and further developed for 11 DBPs using solid-phase extraction and gas chromatography coupled with a halogen-specific detector (XSD). The XSD was highly selective towards halogenated DBPs, providing chromatograms with little noise. The method allowed detection down to 0.05 μg L -1 and showed promising results for the simultaneous determination of a range of neutral DBP classes. Compounds from two classes of emerging DBPs, more cytotoxic than the "traditional" regulated DBPs, were successfully determined using this method. However, haloacetic acids (HAAs) should be analyzed separately as some HAA methyl esters may degrade giving false positives of trihalomethanes (THMs). The method was tested on real water samples from two municipal waterworks where the target DBP concentrations were found below the regulatory limits of Sweden.

Formation potential and speciation characteristics of two important groups of disinfection byproducts (DBPs), namely, trihalomethanes (THMs) and haloacetic acids (HAA S ), during Cl 2 and ClO 2 treatment of water samples collected from three different sources, namely, sea, river, and reservoir, were investigated with reference to key controlling parameters. Formation of inorganic DBPs such as chlorate and chlorite was evaluated. Dissolved organic carbon (DOC) and UV absorbance (UV 254 ) of the sea, river, and reservoir samples were 3.35 ± 0.05, 3.12 ± 0.05, and 3.23 ± 0.05 mg/L and 0.062 ± 0.01, 0.074 ± 0.01, and 0.055 ± 0.01 cm -1 , respectively. For Cl 2 and ClO 2 treatments, the respective formation potential of THMs and HAAs from the three water sources studied exhibited unidentical trend suggesting that higher THM formation was not necessarily associated with higher HAA formation. On chlorination, the concentrations of total HAAs formed were 9.8 μg/L (sea), 12.8 μg/L (river), and 20.6 μg/L (reservoir) and total THM yields were 38.3 μg/L (sea), 18.8 μg/L (river), and 21.5 μg/L (reservoir) for a Cl 2 dose of 1 mg/L and 30 min reaction time. The trend of formation of THMs and HAAs for Cl 2 treatment was similar to that for ClO 2 treatment. However, the amount of HAAs (3.5 μg/L (sea), 1.8 μg/L (river), and 1.9 μg/L (reservoir)) and THMs (not detected) formed was much lower than that formed during chlorination. Regardless of source water type, di-HAAs were the most favored HAAs, followed by tri-HAAs with a small amount of mono-HAAs formed for both Cl 2 and ClO 2 treatment. Chlorination yielded more THMs than HAAs, whereas it was reverse for chlorine dioxide treatment. Irrespective of treatment with ClO 2 or Cl 2 , seawater samples showed the highest bromine incorporation percentage (BIP) in both THMs and HAAs followed by that for river and reservoir water samples. HAAs were found to be always associated with lower amount of BIP than THMs., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Diazepam (DZP) is often found in source water and drinking water at dozens of nanograms per liter levels. The transformation of DZP in water chlorination disinfection process has aroused new concern because the toxic disinfection byproducts (DBPs) might be produced. However, the DBPs of DZP have not been fully identified, and their occurrence levels in drinking water have not been reported. In our chlorination experiment, five emerging DBPs of diazepam: (5-chloro-2-(methylamino) phenyl) (phenyl)methanone (BP-246), 6-chloro-1-methyl-4-phenylquinazolin-2(1H)-one (BP-271), N-(2-benzoyl-4,6-dichlorophenyl)formamide (BP-294), methyl-(2-benzoyl-4-chlorophenyl) (methyl)carbamate (BP-304 (1)) and 6-chloro-4-methoxy-1-methyl-4-phenyl-1,4-dihydro2H -benzo[d][1,3]oxazin-2-one (BP-304 (2)), were tentatively identified by high-resolution mass spectrometry and further characterized by nuclear magnetic resonance spectroscopy. We developed a trace analytical method for the analysis of these five DBPs in drinking water based on solid-phase extraction (SPE) followed liquid chromatography coupled with electrospray ionization tandem mass spectrometric detection. Ultrahigh sensitivities were achieved with limits of detection as low as 7 pg per liter. The recoveries at different spiking levels were all higher than 80% except for that of BP-246. Four of the DBPs and DZP were detected in real drinking water samples at concentrations ranging from several to dozens of nanograms per liter with relatively high detection frequencies. This is the first report on the existence of DZP-DBPs in drinking water. The method and results will be useful for further studies on the occurrence, toxicity, human exposure and control measures of these DBPs., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This research study aims to investigate the efficiency of synthesized porous pig bone char (PBC) for reduction of disinfection by-product (DBP) precursors from surface water. Dissolved organic matter (DOM) is commonly present in natural water and acts as a disinfection by-product precursor. Adsorption is one of the promising technologies that is commonly applied for DOM removal. Interestingly, the properties of pig bone are such that it has a surface area and pore volumes that can adsorb DOM. Pig bone was synthesized as porous bone char (PBC). The results show that synthesized PBC at 900 °C (PBC-900 °C) provides a high volume of mesoporous structure. The adsorption process was best fitted with the pseudo-second-order and Freundlich isotherm model. Thus, the mechanisms occurred on the multilayer adsorption of the surface. PBC-900 °C can remove approximately 70-80% of DOM with varying concentrations, from 0.2 g/L to 0.8 g/L. Furthermore, the results of fluorescence excitation-emission (FEEM) showed that humic acids and humic-like substances in water can be removed by using PBC at concentrations higher than 0.4 g/L. From the obtained results, it can be concluded that PBC is an alternative low-cost adsorbent which can be utilized for reduction of DBP precursors from water.

The scientific multistep approach described herein is a result of two years of research into a control method against microbial fouling and biodeterioration of historic building materials by phototrophs. A series of tests were conducted to select the best antifouling agent for eliminating 'green' coatings and protecting surfaces against biofouling. Of the seven active compounds, two with the best penetration abilities were subjected to a photosynthetic activity inhibition test using confocal microscopy. Of the two, a quaternary ammonium salt (QAC) - didecyldimethylammonium chloride (DDAC) - was found to be the most effective. Ten biocides containing QACs at different concentrations were then tested against 'green' coatings on wood, brick and plaster, with the best four being selected for further research in model conditions. As a result, biocides containing >14% (v v -1 ) DDAC were found to be successful antifouling agents for protecting historical materials against biodeterioration by phototrophs.

Chlorination is the most common method to control water qualities, in some case on-site outdoor measurements are required to measure easily-decaying residual chlorine concentration appropriately without delay. In this study sunlight-induced unexpected colour development (UCD) of N, N-diethyl-p-phenylenediamine (DPD) colorimetric measurement was studied under several sun exposure conditions. The colour development level was evaluated with reference to chlorine concentration (mg/L) and relationships between colour development rate (mg/L min) and intensities of solar were investigated. UCD was found to be related to both exposure intensity and time. By means of exposure experiment under specific wavelength of ultraviolet (UV), it was confirmed that both middle and short wavelength of UV radiation being responsible for such an unexpected measurement. Consequently, a simple device was designed using three commercially available anti-UV films, one of which could effectively prevent the UCD from direct sun exposure., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The heterogeneity of dissolved organic matter (DOM) in natural and human impacted waters and the variety of drinking water treatment processes employed has made a mechanistic understanding of disinfection byproduct (DBP) formation challenging. In this study, we examined the formation of the regulated DBPs (Trichloromethanes, THM, and Haloacetic acids, HAA) during full-scale water treatment operations both with prechlorination treatment (normal operations for the drinking water plant) and without (altered operations); followed by coagulation, flocculation, filtration, and chlorination. The source water DOM concentration ranged 6.4 to 7.3 mg-C/L. DOM composition was moderately humic and degraded with a mix of microbial- and terrestrial-like characteristics. Removal of raw water prechlorination caused an average reduction in total THM and HAA concentrations of 52.7% and 40.0%, respectively, with the greater reduction noted for chlorinated-DBPs rather than brominated-DBPs. Prechlorination treatment resulted in a higher relative production of Cl 3 CH and BrCl 2 CH associated with aromatic, humic, and terrestrial-like DOM. Without prechlorination, the DBP pool had higher proportions of brominated-DBPs (Br 3 CH, Br 2 ClCH, Br 2 CHCOOH, BrClCHCOOH, and BrCH 2 COOH) associated with microbial-like, processed humic-like, and protein-like DOM. These observed patterns could not be explained by chloride demand and DOM concentration, indicating that DOM composition played an important role in DBP formation., (Copyright © 2018 Elsevier B.V. All rights reserved.)

People are exposed to chlorinated by-products (CBPs) through the consumption of cold tap water (CTW) (ingestion, inhalation, dermal contact) but also through the use of hot tap water (HTW) in such activities as showering and bathing (inhalation, dermal contact). This study focuses on the impact of residential water heating on CBP levels in tap water. Trihalomethane (THM) and haloacetic acid (HAA) levels were measured in the CTW and HTW of 50 residences located in two distribution systems supplied by chlorinated surface water during summer and winter. Results show important differences between CBP levels measured in cold and hot tap water. However, the magnitude of changes differs according to the specific species of THMs and HAAs, the season, the distribution system and the location within the same distribution system. Residential water heating led to an increase in average THM levels for the two distribution systems studied, which tended to be greater in winter. Residential water heating affected the two main HAA species found in the area studied (dichloroacetic (DCAA) and trichloroacetic (TCAA) acids) differently. In fact, the average DCAA levels increased due to water residential heating while a small change in average levels was observed for TCAA. However, the water heating impact on HAAs (in terms of importance and sometimes of tendency (increase vs. decrease)) may also differed between residences. The influence of seasons on the change in the average DCAA and TCAA levels (in μg/L) from residential water heating was not statistically significant except for TCAA levels in one distribution system. Results show the importance of considering site-specific characteristics of CTW (CBP level, temperature, residual chlorine, etc.) to estimate the levels of CBPs in HTW in CBP exposure assessment studies (and not to generalize for an entire population). The reported data can thus be useful in assessing for exposure to DBPs in epidemiological studies., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Organotin contamination in marine environment has been a public concern for many years due to its adverse impacts on biota and human health. This study investigated levels, distribution and health risks of six organotin compounds: tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT), triphenyltin (TPhT), diphenyltin (DPhT) and monophenyltin (MPhT) in commercial and wild oysters in China. The total organotin in commercial oysters ranged from 251 to 1949 ng Sn g -1 dw (dry weight) >. Two endocrine disruptors TBT and TPhT were detected in these samples with the highest level of 68.1 ± 20.1 ng Sn g -1 dw and 747 ± 7.3 ng Sn g -1 dw, respectively. For wild oysters, the concentrations of total organotins varied from 33.3 to 2671 ng Sn g -1 dw. Butyltins were dominated by TBT with the mean level of 26.1 ± 30.0 ng Sn·g -1 dw and showed no significant spatial variation between the southern and northern coastal zones (p > 0.05). However, compared with the north, phenyltin levels especially TPhT were much higher in the south coastline (246-1484 ng Sn·g -1 dw) due to the wider use of TPhT-based biocides in local mariculture and agriculture. Health risk assessment indicated that a daily exposure of TPhT-contaminated oysters (including commercial and wild ones) may pose adverse threats to human particularly children as the risk quotients (RQ) were higher than 1. Organotin contamination (e.g., TPhT) still occurs in the South China's coastal zones after the TBT ban, which deserves future research and effective measures to protect the marine ecosystem and human health., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Several micropollutants show low removal efficiencies in conventional sewage treatment plants, and therefore enter the aquatic environment. To reduce the levels of micropollutants in sewage effluent, and thereby the effects on biota, a number of extra treatment steps are currently being evaluated. Two such techniques are ozonation and adsorption onto activated carbon. In this study, we investigated the efficiency of Sweden's first full-scale ozonation treatment plant at removing a number of antibiotics, antimycotics and biocides. The effect of adding granular activated carbon (GAC) on a pilot scale and pilot-scale ozonation were also evaluated. The conventional treatment (13,000 PE) with the add-on of full-scale ozonation (0.55 g O 3 /g Total organic carbon (TOC)) was able to remove most of the studied compounds (>90%), except for benzotriazoles and fluconazole (<50%). Adsorption on GAC on a pilot scale showed a higher removal efficiency than ozonation (>80% for all studied compounds). Three types of GAC were evaluated and shown to have different removal efficiencies. In particular, the GAC with the smallest particle sizes exhibited the highest removal efficiency. The results demonstrate that it is important to select an appropriate type of carbon to achieve the removal goal for specific target compounds., (Copyright © 2018 Elsevier B.V. All rights reserved.)

It is necessary and important to investigate the formation of disinfection byproducts (DBPs) in water treatment systems for the management of disinfection formation risk. In the present study, the formation potential of trichloromethane (TCM) and haloacetic acids in different algal metabolites were compared, and the formation kinetics of these DBPs were investigated. The results indicated that DBP formation potential, the traditional index widely used to evaluate the disinfection formation risk, can represent neither the total precursors of DBPs nor the possible generated amounts of DBPs in drinking water systems. Kinetic analyses showed that the formation of DBPs could be well described by a classical second-order reaction kinetic model and that the actual concentrations of DBPs during chlorination were predictable with the model. The formation of DBPs in drinking water treatment systems was highly dependent on the total precursors of DBPs in water and the formation rate of DBPs with chlorine; the latter is usually underestimated in previous studies. Because of their high reactivity, TCM in hydrophilic extracellular organic matter and trichloroacetic acid in all algal metabolites should be serious considerations in the management of disinfection formation risk., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

This study focused on the presence of three biocidal products specific to healthcare facilities, i.e. chlorhexidine digluconate (CHD), bis(aminopropyl)laurylamine (BAPLA), and didecyldimethylammonium chloride (DDAC), in a hospital sewage system. Five sampling campaigns were conducted in 2016 and 2017 throughout the entire Poitiers University Hospital sewage system. DDAC concentrations ranging from 933 ± 119 to 3250 ± 482 μg/L were detected in 24-h composite samples, while lower concentrations (both within the same range) were detected for the two other compounds (i.e. 25 ± 5 to 97 ± 39 μg/L for CHD and 18 ± 3 to 142 ± 16 μg/L for BAPLA). Based on these findings, a mass balance was determined for these discharged compounds to compare the quantities detected in discharges to the amounts used for healthcare in the hospital. Hence, 60-90% of the quantities of DDAC used were found to be present at the hospital sewage outfall. Higher percentages of CHD (100-242%) were noted because of the high presumably quantities used for antiseptic applications, which were not considered in mass balance calculation. Finally, only 10-30% of BAPLA quantities used were detected at the site outfall. Analysis of the results for the different sampling points revealed the nature of the emission sources. For surface applications of DDAC and BAPLA, management of hospital linen is thus a major source of discharged biocidal products, probably following the washing of biocide-soaked textiles used for hospital facility maintenance. Moreover, discharge of biocidal products from a healthcare establishment depends especially on biocide handling practices in the emitting establishment. For BAPLA, compliance with hospital recommended dosages and practices whereby operators are required to prepare tailored quantities of detergents and disinfectants for each specific task could largely explain the limited release of this compound.

Desalinated seawater is the major source of drinking water in many countries. During desalination, several activities including pretreatment, desalination, stabilization, mixing, storage and distribution are performed. Few disinfectants are used during these activities to control the biofouling agents and microbiological regrowth. The reactions between the disinfectants and natural organic matter (NOM), bromide and iodide form disinfection by-products (DBPs) in product water. The product water is stabilized and mixed with treated freshwater (e.g., groundwater) to meet the domestic water demands. The DBPs in desalinated and blend water are an issue due to their possible cancer and non-cancer risks to humans. In this paper, formation and distribution of DBPs in different steps of desalination and water distribution systems prior to reaching the consumer tap were reviewed. The variability of DBPs among different sources and desalination processes was explained. The toxicities of DBPs were compared and the strategies to control DBPs in desalinated water were proposed. Several research directions were identified to achieve comprehensive control on DBPs in desalinated water, which are likely to protect humans from the adverse consequences of DBPs.

Personnel in swimming pool facilities typically experience ocular, nasal, and respiratory symptoms due to water chlorination and consequent exposure to disinfection by-products in the air. The aim of the study was to investigate exposure to trichloramine and trihalomethanes (chloroform, bromodichloromethane, dibromochloromethane, and bromoform) from the perspective of adverse health effects on the personnel at Swedish habilitation and rehabilitation swimming pools. The study included 10 habilitation and rehabilitation swimming pool facilities in nine Swedish cities. The study population comprised 24 exposed swimming pool workers and 50 unexposed office workers. Personal and stationary measurements of trichloramine and trihalomethanes in air were performed at all the facilities. Questionnaires were distributed to exposed workers and referents. Spirometry, fraction of exhaled nitric oxide (FE NO ), and peak expiratory flow (PEF) were measured. Personal and stationary measurements yielded trichloramine levels of 1-76 µg/m 3 (average: 19 µg/m 3 ) and 1-140 µg/m 3 (average: 23 µg/m 3 ), respectively. A slightly higher, but not significant, prevalence of reported eye- and throat-related symptoms occurred among the exposed workers than among the referents. A significantly increased risk of at least one ocular symptom was attributed to trichloramine exposure above the median (20 µg/m 3 ). Lung function (FVC and FEV1) was in the normal range according to the Swedish reference materials, and no significant change in lung function before and after shift could be established between the groups. Average FE NO values were in the normal range in both groups, but the difference in the values between the exposed workers and referents showed a significant increase after shift. Hourly registered PEF values during the day of the investigation did not show any unusual individual variability. In conclusion, the increased risk of developing at least one ocular symptom at personal trichloramine concentrations over 20 µg/m 3 combined with an increase in the difference in FE NO during the work shift of the exposed workers should not be neglected as an increased risk of respiratory inflammation in the habilitation and rehabilitation swimming pool environment.

Pollution has been less investigated in marine and coastal environments than in inland waters. The low levels at which pollutants are expected to be present in seawater calls for the use of reliable and high sensitivity analytical methodologies. In this context, this work presents the optimization and validation of an analytical method to determine 26 medium to highly polar pesticides in seawater based on solid phase extraction and liquid chromatography-tandem mass spectrometry detection. The developed methodology was linear, accurate (relative recoveries within 80-120% for most analytes), repeatable (relative standard deviations <18% for most analytes), and sensitive (limits of determination <1 ng/L for 89% of the compounds). The use of isotopically labeled compounds as surrogate standards compensated for low analyte recoveries and matrix effects. The method was applied to the analysis of seawater samples collected along the coastline of Catalonia (NE Spain). Overall, total pesticide loads were higher inside the marinas than outside. The booster biocides diuron and irgarol used in antifouling paintings and different triazine pesticides were the most abundant compounds. Irgarol was present above the maximum allowable concentration set in European regulations in 70% of the samples collected inside the marinas. A different pesticide pollution pattern, with MCPA and bentazone presenting the highest concentrations, was observed at the Ebro Delta area due to the impact of the agricultural activities carried out there. To the authors' knowledge, 4 out of the 26 target pesticides, namely, chlorfenvinphos, fenthion oxon, fenthion sulfone, and fenthion sulfoxide, have not been previously investigated in seawater., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Raw water (RW) from the Bangkok and Sing Buri water treatment plants located on the Chao Phraya River, river water, domestic wastewater (WW), and treated wastewater (TWW) from two wastewater treatment plants in Thailand were collected three times to investigate disinfection by-products' (DBPs) formation potential (FP) including trihalomethane FP (THMFP), iodo-THMFP (I-THMFP), haloacetonitriles FP (HANFP), and trichloronitromethane FP (TCNMFP). High THMFP levels were observed in river water, WW, and TWW. Considering average value, the THMFP of TWW was about two times higher than that of RW. Relatively high levels of I-THMFP were found in WW and TWW. The I-THMFP of TWW was three to seven times higher than that of RW. The HANFP of TWW was one to three times higher than that of RW. High levels of TCNMFP were found in WW and TWW. TCNMFP of TWW was six to thirteen times higher than that of RW. The discharge of TWW to RW must be prevented and controlled. The moderately positive linear relationship was obtained between dissolved organic carbon and TCNMFP in TWW. Considering measured weight concentration, THMFP was found as the highest DBPs. The highest lethal concentration 50-weighted and lowest cytotoxicity-weighted concentrations of DBPs were determined for HANFP.

An analytical method employing solid phase extraction (SPE) and gas chromatography-tandem mass spectrometry (GC-MS/MS) has been developed for quantitative determination of twenty-six organohalogen disinfectant by-products (OXBPs) in water samples. Target analytes include four trihalomethanes (THMs), four iodohalomethanes (I-HMs), one haloacetaldehyde (HAL), six haloketones (HKs), four halonitromethanes (HNMs), and seven haloacetonitriles (HANs). The sample preparation procedure includes pretreatment with ascorbic acid to quench residual oxidants, followed by analyte enrichment using solid-phase extraction. Five SPE sorbents were tested. The best results for the majority of target analytes were obtained using a styrene-divinylbenzene copolymer phase and methyl tert-butyl ether (MTBE) as the elution agent. GC-MS analysis was performed using electron ionization (EI) and selected reaction monitoring (SRM) for analyte detection. The performance of the method was assessed according to the French standard NF T90-210. The method showed LOQs ranging from 3 to 3000 ng L -1 . The applicability of the method has been demonstrated by analyzing both river water and tap water samples. The OXBPs detected most often in the tap water were dibromochloromethane (in 100% of the samples, 4.3-4.7 μg L -1 ), bromodichloromethane (100%, 1.3-1.7 μg L -1 ), tribromomethane (100%, 0.8-4.4 μg L -1 ), trichloromethane (100%, 0.6-0.7 μg L -1 ), dibromoacetonitrile (75%, 0.5-0.9 μg L -1 ), with dichloroacetonitrile and 1,1,1-trichloro-2-propanone detected at concentrations around the LOQ levels. In the treated river water samples, the only OXBPs measured at levels above the limit of quantification were trichloromethane and 1,1,1-trichloro-2-propanone. To the best of our knowledge, this is the first SPE-GC-MS/MS method enabling the analysis of an extensive list of OXBPs., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper investigates disinfection by-products (DBPs) formation and their relationship with governing factors in chlorinated swimming pools. The study compares concentrations of DBPs with WHO guidelines for drinking water quality recommended to screen swimming pool water quality. The statistical analysis is based on a global database of 188 swimming pools accumulated from 42 peer-reviewed journal publications from 16 countries. The mean and standard deviation of dichloroacetic acid and trichloroacetic acid were estimated as 282 ± 437 and 326 ± 517 μg L -1 , respectively, which most often surpassed the WHO guidelines. Similarly, more than half of the examined pools had higher values of chloral hydrate (102 ± 128 μg L -1 ). The concentration of total chloramines (650 ± 490 μg L -1 ) was well above the WHO guidelines in all reported cases. Nevertheless, the reported values remained below the guidelines for most of the studied pools in the case of total trihalomethanes (134 ± 160 μg L -1 ), dichloroacetonitrile (12 ± 12 μg L -1 ) and dibromoacetonitrile (8 ± 11 μg L -1 ). Total organic carbon, free residual chlorine, temperature, pH, total nitrogen and bromide ions play a pivotal role in DBPs formation processes. Therefore, proper management of these governing factors could significantly reduce DBPs formation, thereby, contributing towards a healthy swimming pool environment.

Routine flexible nasoendoscopy in otolaryngology clinics is well established, the rate-limiting step of which being the speed of the nasoendoscopes reprocessing method used. Non-lumened flexible nasoendoscopes are expensive, heat-sensitive, delicate instruments that cannot be sterilized in an autoclave but must be disinfected by means of high level disinfection (HLD). In one of the public hospitals in Singapore, the method of disinfection was recently changed to the use of commercial impregnated wipes which generates less than 1% chlorine dioxide upon activation. An exposure assessment was performed to assess the potential exposure of healthcare workers (HCWs) to airborne chlorine dioxide during nasoendoscope disinfection. A total of 14 long-term personal samples, four short-term personal samples and 16 long-term area samples were collected over 8 days in midget impingers containing 0.02% potassium iodide in sodium carbonate/sodium bicarbonate buffer during the nasoendoscope disinfection. The samples were then analyzed by ion-chromatograph. The chlorine dioxide concentrations and upper confidence limit at 95% confidence level (UCL 95% ) for personal and area samples collected were all below the occupational exposure limits (OEL) for chlorine dioxide (Singapore Workplace Safety and Health PELs, ACGIH TLVs, U.S. OSHA PELs). The study presented evidence that the exposure of HCWs to chlorine dioxide during high-level disinfection of flexible nasoendoscopes were deemed insignificant.

While disinfection of swimming pools is indispensable for microbiological safety, it may lead to the formation of disinfection by-products. Most studies agree that inhalation exposure is the predominant pathway of the associated health risks, but assumptions are based on concentrations measured in water and evaporation models. Pool water and air were sampled in 19 swimming pools. Trihalomethanes were detected in all sites; chloroform being the most abundant species. Concentrations ranged between 12.8-71.2 μg/L and 11.1-102.2 μg/m 3 in pool water and air, respectively. The individual lifetime carcinogenic risk associated with chloroform in swimming pools exceeded 10 -6 in all age groups for recreational swimmers and 10 -5 for elite swimmers and staff, even if the pool complied with the national standards. Inhalation exposure was estimated and found to be the most relevant, however, different mass transfer models from water measurements significantly under- or overestimated the health burden compared to direct calculation from the concentration in air. The observed health risks call for defining regulatory values and monitoring requirement of indoor air quality in swimming pools.

Monochloramine (NH 2 Cl), as the dominant disinfectant in drinking water chloramination, can provide long-term disinfection in distribution systems. However, NH 2 Cl can also be discharged into storm sewer systems and cause stormwater contamination through outdoor tap water uses. In storm sewer systems, NH 2 Cl dissipation can occur by three pathways: (i) auto-decomposition, (ii) chemical reaction with stormwater components, and (iii) biological dissipation. In this research, a field NH 2 Cl dissipation test was conducted with continuous tap water discharge into a storm sewer. The results showed a fast decrease of NH 2 Cl concentration from the discharge point to the sampling point at the beginning of the discharge period, while the rate of decrease decreased as time passed. Based on the various pathways involved in NH 2 Cl decay and the field testing results, a kinetic model was developed. To describe the variation of the NH 2 Cl dissipation rates during the field testing, a time coefficient f T was introduced, and the relationship between f T and time was determined. After calibration through the f T coefficient, the kinetic model described the field NH 2 Cl dissipation process well. The model developed in this research can assist in the regulation of tap water outdoor discharge and contribute to the protection of the aquatic environment.

The fates of the antibiotic sulfamethoxazole (SMX) in the chlorination of fresh water, simulated brackish marine culture water, and marine water were investigated. SMX was oxidized by sodium hypochlorite (NaClO) at different reaction rates in the different samples. The oxidation of SMX followed pseudo-first-order kinetics, and the rate constant was the largest in marine water (3.44 min -1 ), as Br - ions promote the oxidation reaction. Moreover, the kinds of disinfection byproducts (DBPs) were also affected by Br - ions. Br-DBPs were found in the simulated brackish marine culture water and marine water disinfection systems. The structures of the DBPs indicated that S-C cleavage, polymerization, S-N hydrolysis, chlorine/bromine substitution, and desulfonation reactions occurred on SMX during the disinfection process. EPI (Estimation Programs Interface) Suite™ and absorbable organic halogen (AOX) analysis were used to evaluate the toxicity of the DBPs. The results suggested that DBPs in the simulated brackish marine culture water and marine water systems were more toxic than those in the fresh water system.

This is the first time that correlations between the spectroscopic properties of algal organic matter (AOM) and cyanobacteria-related C- and N-disinfection byproduct (DBP) formation have been presented. Three types of coagulants, aluminium chloride (AC), chitosan (CTS) and a composite chitosan-aluminium chloride (CTSAC), were selected to assess and compare the performance of coagulation to control DBPs formation in dewatering water (DW). Fluorescence excitation-emission matrices (EEMs) coupled with parallel factor analysis (PARAFAC) indicated that four components dominated the EEM of the DW samples. Examination of C-, N-DPBs formation and attendant changes in the AOM parameters allows the establishment of strong linear relationships between yields of the trihalomethanes, haloacetonitriles and trichloronitromethane and the relative changes in the fluorescence compounds. Stronger linear correlations were found between trihalomethanes and tryptophan-like substance C1 (r = 0.918), between haloacetonitriles and C1 (r = 0.934), and between trichloronitromethane and amino acid-like substance C2 (r = 0.915) than other AOM parameters, suggesting that tryptophan-like substance and amino acid-like substance in AOM play major roles in generating cyanobacteria-related DBPs upon chlorination. Furthermore, because the CTSAC composite was effective in removing fluorophores and caused little cell lysis during the first 4 days of sludge storage, the production of C-, N-DBPs in the DW was lower than those in the AC or CTS systems for the same storage period. This indicates the feasibility of surrogate monitoring of the production of cyanobacteria-related C-, N-DBPs via online measurements of water EEM fluorescence. CTSAC composite coagulant is thus recommended, and the sludge should be disposed of within 4 days to obtain DW with lower DBPs formation potentials., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Biocides are, inter alia, applied as preservatives on facades to prevent the growth of microorganisms. Their incomplete mineralization results in new compounds, so-called transformation products (TPs). Rain causes that both applied biocides and their TPs leach from facades with stormwater into the urban aquatic environment. This study is the first to investigate the introduction of the biocides Diuron, Terbutryn, and Octylisothiazolinone (OIT) and their TPs into the groundwater via urban stormwater infiltration systems. In this study, the TPs of these biocides were created by laboratory photolysis and elucidated using LC-HRMS. The results were then used to analyze TPs by LC-MS/MS in stormwater and groundwater samples, which were taken from an urban swale-trench system and from groundwater wells upgradient and downgradient of the infiltration system. A sprinkling experiment was conducted to evaluate facades as a contamination source. Biodegradation tests were conducted to determine bio-persistence of biocides and their TPs. Fourteen TPs were identified under laboratory photolysis. TP-186, TP-210, and TP-256 of Terbutryn were hitherto unknown. Nine TPs were qualitatively detected in environmental water samples. Parent compounds, TP-219 of Diuron and TP-212, TP-214, and TP-226 of Terbutryn were detected at a maximum concentration of 140 ng L -1 during stormwater events. Concentrations in groundwater were considerably below German drinking water limits, but were higher in groundwater samples downgradient from the investigated swale-trench system than in those collected upgradient. Neither the biocides nor most of their TPs were readily biodegradable under simulated surface water conditions. The results show that entry of biocides and their TPs into groundwater is caused by infiltration of urban stormwater., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Disinfection is essential to preventing infection caused by microbial pathogens in swimming pool water. The most commonly used disinfection methods are chlorine disinfectant, including sodium hypochlorite (NaOCl) and sodium dichloroisocyanurate (SDIC, C 3 O 3 N 3 Cl 2 Na) with characteristics of available chlorine formation and stability. In this study, we estimate the formation of trihalomethanes (THM 4 ) in indoor swimming pools filled with seawater that adopt these disinfection methods, and we investigated the factors influencing the formation of THM 4 . Formation of THM 4 by free chlorine (FC) and SDIC respectively is 327.8 μg L -1 and 307.6 μg L -1 ; Br-THMs is 226.7 μg L -1 for FC, 198 μg L -1 for SDIC. SDIC has less THM 4 formation than FC in the same molar Br - dosage (10 μM) and total chlorine dosage (20 μM), and bromoform is the main Br-THMs species. The occurrence of THM 4 is inhibited at high dosages of natural organic matter and Br - . The total Br-THMs increase from 75 μg L -1 to 189.7 μg L -1 and from 64.6 μg L -1 to 190 μg L -1 by FC and SDIC at pH 5.0-9.0, both of which are highly dependent on pH. In real water, similar results were found in Br - -containing water (1 mg-Br - L -1 ).

Antimicrobial compounds, such as biocides and antibiotics, are widely used in society with significant quantities of these chemicals ending up in sewage treatment plants (STPs). In this study, mass flows and removal efficiency in different treatment steps at three Swedish STPs were evaluated for eleven different biocides and antibiotics. Mass flows were calculated at eight different locations (incoming wastewater, water after the first sedimentation step, treated effluent, primary sludge, surplus sludge, digested sludge, dewatered digested sludge and reject water). Samples were collected for a total of nine days over three weeks. The STPs were able to remove 53->99% of the antimicrobial compounds and 0-64% were biodegraded on average in the three STPs. Quaternary ammonium compounds were removed from the wastewater >99%, partly through biodegradation, but 38-96% remained in the digested sludge. Chlorhexidine was not biodegraded but was efficiently removed from the wastewater to the sludge. The biological treatment step was the most important step for the degradation of the studied compounds, but also removed several compounds through the surplus sludge. Compounds that were inefficiently removed included benzotriazoles, trimethoprim and fluconazole. The study provides mass flows and removal efficiencies for several compounds that have been seldom studied., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Parallel factor (PARAFAC) analysis of fluorescence excitation-emission matrices (EEMs) was used to investigate the organic matter and DBP formation characteristics of untreated, primary treated (enhanced coagulation; EC) and secondary treated synthetic waters prepared using a Suwannee River natural organic matter (SR-NOM) isolate. The organic matter was characterised by four different fluorescence components; two humic acid-like (C1 and C2) and two protein-like (C3 and C4). Secondary treatment methods tested, following EC treatment, were; powdered activated carbon (PAC), granular activated carbon (GAC), 0.1% silver-impregnated activated carbon (SIAC), and MIEX® resin. Secondary treatments were more effective at removing natural organic matter (NOM) and fluorescent DBP-precursor components than EC alone. The formation of a suite of 17 DBPs including chlorinated, brominated and iodinated trihalomethanes (THMs), dihaloacetonitriles (DHANs), chloropropanones (CPs), chloral hydrate (CH) and trichloronitromethane (TCNM) was determined after chlorinating water sampled before and after each treatment step. Regression analysis was used to investigate the relationship between peak component fluorescence intensity (F MAX ), DBP concentration and speciation, and more commonly used aggregate parameters such as DOC, UV 254 and SUVA 254 . PARAFAC component 1 (C1) was in general a better predictor of DBP formation than other aggregate parameters, and was well correlated (R ≥ 0.80) with all detected DBPs except dibromochloromethane (DBCM) and dibromoacetonitrile (DBAN). These results indicate that the fluorescence-PARAFAC approach could provide a robust analytical tool for predicting DBP formation, and for evaluating the removal of NOM fractions relevant to DBP formation during water treatment., (Copyright © 2018. Published by Elsevier B.V.)

The aim of this study was to optimize the dispersive liquid-liquid microextraction (DLLME) parameters for simultaneous analysis through DLLME-gas chromatography-mass spectrometry (GC-MS) of six iodo-trihalomethanes, four haloacetonitriles, and one halonitromethane, which are residual disinfection products found in drinking water. Eleven disinfection by-product (DBPs) remaining in aqueous samples were extracted and concentrated using a simple, rapid, and environmentally friendly DLLME method, and then analyzed simultaneously by GC-MS. The optimized DLLME parameters were a sample volume of 5 mL, 100 μL of dichloromethane as the extraction solvent, 1 mL of methanol as the dispersion solvent, an extraction time of 60 s, and 1.5 g of sodium chloride for the salting out effect. The enrichment factor values obtained using the established DLLME-GC-MS method were 19.8-141.5, and the limit of detection and limit of quantification were 0.22-1.19 μg/L and 0.75-3.98 μg/L, respectively. The calibration curves had correlation coefficients (r 2 ) of 0.9958-0.9992 in the concentration range of 0.5-40 μg/L, and they exhibited good linearity in quantitative analysis. This new method could be useful for analyzing eleven DBPs that remain in drinking water., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Pharmaceuticals and personal care products (PPCPs) are an emerging concern because of the large amount of PPCPs that is discharged and its potential ecological effects on the aquatic environment. Chlorination has proven efficient for removing some aromatic PPCPs from wastewater, but the formation of by-products has not been thoroughly investigated partly because of analytical difficulties. This study developed a method for systematically screening and identifying the transformation products (TPs) of multiple aromatic PPCPs through high-resolution mass spectrometry (HRMS). We spiked an environmentally relevant concentration (5000 ng/L) of three anti-inflammatory drugs, four parabens, bisphenol A, oxybenzone, and triclosan in the Milli-Q water and water containing natural organic matter (NOM). Low-dose chlorination (0.2-0.7 mg/L) was performed. We compared the chemical profiles of the chlorinated and untreated water and selected the ions to be identified based on the results of t-test and the ratio of signal intensities. Compound matching and isotopic pattern comparison were applied to characterising the molecular formulae of TPs. The fragmentation of the PPCPs and TPs was used in elucidating the structures of the TPs. The confirmation of TPs was achieved by comparing the retention time and fragment patterns of TPs with the isomer standards. In the chlorinated water, the aromatic PPCPs were substantially removed, except for the anti-inflammatory drugs (removal rates -5.2%-26%). Even with moderate chlorine dosages, all of the aromatic PPCPs, except for acetylsalicylic acid, were transformed into chlorinated derivatives in the Milli-Q water, and so were some PPCPs in the NOM-added water. The results of structure elucidation and compound confirmation as well as the increases in log K ow suggested that chlorination could transform aromatic PPCPs into more persistent, bioaccumulative, and toxic TPs. The presence of these TPs in the effluents where the PPCPs are removed through chlorination may pose increased risks to aquatic organisms., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Trihalomethanes (THMs) and Haloacetic Acids (HAAs) are the main groups detected in drinking water and are consequently strictly regulated. However, the increasing quantity of data for disinfection byproducts (DBPs) produced from research projects and regulatory programs remains largely unexploited, despite a great potential for its use in optimizing drinking water quality monitoring to meet specific objectives. In this work, we developed a procedure to optimize locations and periods for DBPs monitoring based on a set of monitoring scenarios using the cluster analysis technique. The optimization procedure used a robust set of spatio-temporal monitoring results on DBPs (THMs and HAAs) generated from intensive sampling campaigns conducted in a residential sector of a water distribution system. Results shows that cluster analysis allows for the classification of water quality in different groups of THMs and HAAs according to their similarities, and the identification of locations presenting water quality concerns. By using cluster analysis with different monitoring objectives, this work provides a set of monitoring solutions and a comparison between various monitoring scenarios for decision-making purposes. Finally, it was demonstrated that the data from intensive monitoring of free chlorine residual and water temperature as DBP proxy parameters, when processed using cluster analysis, could also help identify the optimal sampling points and periods for regulatory THMs and HAAs monitoring., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Objectives: We examined stillbirths in relation to disinfection by-product (DBP) exposures including chloroform, bromodichloromethane (BDCM), dibromochloromethane, bromoform, trichloroacetic acid, dichloroacetic acid (DCAA), monobromoacetic acid and summary DBP measures (trihalomethanes (THM4), haloacetic acids (HAA5), THMBr (brominated trihalomethanes) and DBP9 (sum of THM4 and HAA5))., Methods: We randomly selected 10 controls for each of the 2460 stillbirth cases with complete quarterly 1997-2004 THM4 and HAA5 town-level drinking water data. Adjusted (aORs) were calculated based on weight-averaged second-trimester DBP exposures., Results: We detected statistically significant associations for stillbirths and the upper DCAA quartiles (aOR range: 1.50-1.71). We also found positive associations for the upper four HAA5 quintiles and different stillbirth cause of death categories that were examined including unexplained stillbirth (aOR range: 1.24-1.72), compression of umbilical cord (aOR range: 1.08-1.94), prematurity (aOR range: 1.37-2.88), placental separation and haemorrhage (aOR range: 1.44-2.01) and asphyxia/hypoxia (aOR range: 1.52-1.97). Additionally, we found positive associations between stillbirths and chloroform exposure (aOR range: 1.29 - 1.36) and unexplained stillbirths and BDCM exposure (aOR range: 1.51 - 1.78). We saw no evidence of exposure-response relationships for any categorical DBP metrics., Conclusions: Consistent with some previous studies, we found associations between stillbirths and chloroform and unexplained stillbirth and BDCM exposures. These findings strengthen existing evidence of prenatal THM exposures increasing the risk of stillbirth. Additionally, we saw statistically significant associations between DCAA and stillbirth. Future research should examine cause-specific stillbirths in relation to narrower critical windows and additional DBP exposure metrics beyond trihalomethanes and haloacetic acids., Competing Interests: Competing interests: None declared., (© Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.)

Natural organic matter (NOM) is ubiquitous in the aquatic environment and if present can cause varied drinking water quality issues, the major one being disinfection byproduct (DBP) formation. Trihalomethanes (THMs) are major classes of DBP that are formed during chlorination of NOM. The best way to remove DBPs is to target the precursors (NOM) directly. The main aim of this review is to study conventional as well as advanced ways of treating NOM, with a broad focus on NOM removal using advanced oxidation processes (AOPs) and biofiltration. The first part of the paper focuses on THM formation and removal using conventional processes and the second part focuses on the studies carried out during the years 2000-2018, specifically on NOM removal using AOPs and AOP-biofiltration. Considering the proven carcinogenic nature of THMs and their diverse health effects, it becomes important for any drinking water treatment industry to ameliorate the current water treatment practices and focus on techniques like AOP or synergy of AOP-biofiltration which showed up to 50-60% NOM reduction. The use of AOP alone provides a cost barrier which can be compensated by the use of biofiltration along with AOP with low energy inputs, making it a techno-economically feasible option for NOM removal.

A novel and reliable method to quantify residual levels of N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine in dairy products using ion-pairing reversed-phase liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed and fully validated. Sample extraction was done with salting-out technique using acetonitrile and sodium chloride. For LC-MS/MS, the analyte was detected using positive electrospray ionization (ESI+) and two multiple reaction monitoring (MRM) transitions were monitored. The method was validated in the 5-150 µg kg -1 range using total error approach. Thus, performance criteria of the method were evaluated. Relative standard deviations for trueness and precision were lower than 10%; with the exception of hard pressed cheese at 5 µg kg -1 for precision. The limit of quantification (LOQ) was around 5-7 µg kg -1 depending on the matrix of interest. The method was successfully applied to accurately quantify N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine in 146 various dairy products with a maximum contamination level of 225 µg kg -1 in cheese., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

During chlorine disinfection process, reactions between the disinfectant and 17β-estradiol (E2) lead to the formation of halogenated disinfection byproducts (DBPs) which can be a risk to both ecosystem and human health. The degradation and transformation products of E2 in sodium hypochlorite (NaClO) disinfection processes of different water samples were investigated. The reaction kinetics research showed that the degradation rates of E2 were considerably dependent on the initial pH value and the types of water samples. In fresh water, synthetic marine aquaculture water and seawater, the reaction rate constant was 0.133 min -1 , 2.067 min -1 and 2.592 min -1 , respectively. The reasons for the above phenomena may be due to the different concentrations of bromide ions (Br - ) in these three water samples which could promote the reaction between NaClO and E2. Furthermore, Br - could also cause the formation of brominated DBPs (Br-DBPs). The main DBPs, reaction centers and conceivable reaction pathways were explored. Seven halogenated DBPs have been observed including three chlorinated DBPs (Cl-DBPs) and four Br-DBPs. The active sites of E2 were found to be the pentabasic cyclic ring and the ortho position of the phenol moiety as well as C9-C10 position. The identified Cl/Br-DBPs were also confirmed in actual marine aquaculture water from a shrimp pond. The comparison of bio-concentration factors (BCF) values based on calculation of EPI-suite showed that the toxicities of the Br-DBPs were stronger than that of their chloride analogues. The absorbable organic halogens (AOX) analysis also suggested that the DBPs produced in the marine aquaculture water were more toxic than that in the fresh water system., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Disinfection is an integral component of water treatment performed daily on large volumes of water worldwide. Chemical disinfection may result in the unintended production of disinfectant by-products (DBPs) due to reactions between disinfectants and natural organic matter present in the source water. Due to their potential toxicity, levels of DBPs have been strictly regulated in drinking waters for many years. With water reuse now becoming more common around the world DBPs are increasingly becoming a concern in recycled waters, where a much larger amount and variety of compounds may be formed due to a higher abundance and diversity of organic material in the source waters. Regulation of DBPs in recycled waters is limited; generally, drinking water regulations are applied in place of specific guidelines for recycled waters. Such regulations are set for only 11, commonly observed, compounds of the 600+ that may, potentially, be found. In this review an overview of current research in this area is provided, the types of compounds that have been observed, methods for their analysis and possible regulation are also discussed. Through this review it is evident that there is a knowledge gap for the occurrence of DBPs in recycled waters, especially when comparing this information to that available for drinking waters. The concentrations of DBPs observed in recycled waters are seen to be higher than those in drinking water, though still within potable threshold limits. It is clear that there is a need for the analysis and understanding of a larger suite of compounds in recycled waters, as these will most likely be the source of future, global renewable water., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The Riverton City dump is Jamaica's largest solid waste disposal site, but it lacks engineered protection for leachate containment and treatment. Shotgun metagenomics was used to survey the microbial communities in the Riverton City dump leachate and in surface waters of the Duhaney River, an urban waterway abutting the dump. The community within the leachate pond was taxonomically distinct from that found in the surface waters of the Duhaney River. Higher microbial diversity was observed within the dump leachate, with members of the Bacteroidetes , Firmicutes , Gammaproteobacteria , Deltaproteobacteria , and Tenericutes being the most abundant, while the river community was dominated by Alphaproteobacteria , Betaproteobacteria , and Gammaproteobacteria The microbial communities exhibit similar functional potential profiles, including chemoorganoheterotrophy as the dominant metabolism, and the potential to degrade aromatic compounds. From reconstruction of metagenome-assembled genomes (MAGs), organisms within both environments are predicted to survive in the presence of multiple antibiotics, antiseptics, biocides, and metals. Strong virulence potential coincided with the most diverse multiple resistance profiles in 1 of 5 leachate MAGs and 5 of 33 river MAGs. Unexpectedly, the microbial resistance profiles were more varied and widespread in the river populations, where we had expected the chemical composition of the leachate to select and enrich for resistance characteristics. This study provides valuable insights into the total functional potential of a landfill leachate microbial community and identifies possible human health hazards within the Duhaney River and Riverton City dump, urban environments with the potential to impact human populations. IMPORTANCE Landfill leachate is a persistent contamination threat for terrestrial waters. Microbial metabolism in landfills transforms contaminants and contributes to greenhouse gas emissions. A better understanding of landfill-associated microbial communities will inform bioremediation of solid waste environments and improve pathogen monitoring. We leveraged shotgun metagenomics to investigate the microbial communities of the Riverton City dump and the adjoining Duhaney River near Kingston City, Jamaica. We identified no overlap between the microbial communities inhabiting the Riverton City dump leachate and the Duhaney River. Both communities are predicted to degrade aromatic compounds, which are ubiquitous environmental pollutants. Adversely, microbes in both environments are predicted to withstand widely used antibiotics, antiseptics, and metal contamination. The absence of evidence for microbial transfer from the leachate to the river is encouraging; however, the Duhaney River contained several organisms with predicted pathogenic lifestyles, indicating that the river represents a human health risk regardless of impact from the dump., (Copyright © 2018 Collins-Fairclough et al.)

To prevent the abuse of nucleoside-based antiviral drugs in disinfectant and anti/bacteriostatic products, a new micellar electrokinetic chromatographic (MEKC) method for the simultaneous determination of three nucleoside antiviral drugs (ganciclovir, acyclovir and penciclovir) was established. Three factors and seven levels uniform design and four factors and four levels orthogonal design were used to optimize the concentration of sodium dodecyl sulfate (SDS), sodium dihydrogen phosphate (NaH 2 PO 4 ) and sodium borate (Na 2 B 4 O 7 ) in the running buffer. The three nucleoside antiviral drugs were separated from each other in the shortest time to obtain effective separation through uniform and orthogonal designs on experimental design and optimization. The separation was performed on an uncoated fused-silica capillary with 50 μ m i. d. and a total length of 30.2 cm (effective length:20 cm). An optimized buffer solution consisting of 25 mmol/L NaH 2 PO 4 , 10 mmol/L Na 2 B 4 O 7 (pH 7.41) and 140 mmol/L dodecyl sulfate sodium was used for separation. The applied voltage was 10 kV, the injected pressure and time was at 0.003 Pa for 4 s. The wavelength of the detection was 250 nm. Under the optimum conditions, the corrected area and the concentration had good linearity. The correlation coefficients ( r ) were not less than 0.9995. The limits of detection were all 2.0 mg/kg. The limits of quantitation were all 7.0 mg/kg. The relative recoveries ranging from 85.4% to 104.1% with RSDs all lower than 8.0%. It showed that the method was suitable for the detection of ganciclovir, acyclovir and penciclovir in disinfectant and anti/bacteriostat products with simplicity and rapidity.

Chemical disinfectants effectively kill pathogenic microorganisms, eliminating routes of transmission for infectious diseases. Accurate quantification of the active ingredients can help make a more effective use of disinfectants. In this study, the active ingredients in six different types of chemical disinfectants were systematically quantified with great precision and accuracy using potentiometric titration. The coefficient of variations fell in the range of 0.04%-0.46%. The recovery rates of samples were all above 95% and the extended uncertainty was 0.32g/L. This method can be broadly applied to the analysis of disinfectants in the future., Competing Interests: The authors have declared that no competing interests exist.

Vibrio parahaemolyticus contamination causes serious foodborne illness and has become a global health problem. As a disinfectant, aqueous ozone can effectively kill a number of bacteria, viruses, parasites, and other microorganisms. In this study, three factors, namely, the aqueous ozone concentration, the exposure time, and the bacterial density, were analyzed by response surface methodology, and the aqueous ozone concentration was the most influential factor in the sterilization ratio. Under low aqueous ozone concentrations (less than 0.125 mg/l), the bacterial cell membranes remained intact, and the ozone was detoxified by intracellular antioxidant enzymes ( e.g. , superoxide dismutase and catalase). Under high aqueous ozone concentrations (more than 1 mg/l), cell membranes were damaged by the degree of peripheral electronegativity at the cell surface and the concentration of lactate dehydrogenase released into the extracellular space, and the ultrastructures of the cells were confirmed by transmission electron microscopy. Aqueous ozone penetrated the cells through leaking membranes, inactivated the enzymes, inhibited almost all the genes, and degraded the genetic materials of gDNA and total RNA, which eventually led to cell death.

Objectives: Use of cleaning and disinfecting products is associated with work-related asthma among healthcare workers, but the specific levels and factors that affect exposures remain unclear. The objective of this study was to evaluate the determinants of selected volatile organic compound (VOC) exposures in healthcare settings., Methods: Personal and mobile-area air measurements (n = 143) from 100 healthcare workers at four hospitals were used to model the determinants of ethanol, acetone, 2-propanol, d-limonene, α-pinene, and chloroform exposures. Hierarchical cluster analysis was conducted to partition workers into groups with similar cleaning task/product-use profiles. Linear mixed-effect regression models using log-transformed VOC measurements were applied to evaluate the association of individual VOCs with clusters of task/product use, industrial hygienists' grouping (IH) of tasks, grouping of product application, chemical ingredients of the cleaning products used, amount of product use, and ventilation., Results: Cluster analysis identified eight task/product-use clusters that were distributed across multiple occupations and hospital units, with the exception of clusters consisting of housekeepers and floor strippers/waxers. Results of the mixed-effect models showed significant associations between selected VOC exposures and several clusters, combinations of IH-generated task groups and chemical ingredients, and product application groups. The patient/personal cleaning task using products containing chlorine was associated with elevated levels of personal chloroform and α-pinene exposures. Tasks associated with instrument sterilizing and disinfecting were significantly associated with personal d-limonene and 2-propanol exposures. Surface and floor cleaning and stripping tasks were predominated by housekeepers and floor strippers/waxers, and use of chlorine-, alcohol-, ethanolamine-, and quaternary ammonium compounds-based products was associated with exposures to chloroform, α-pinene, acetone, 2-propanol, or d-limonene., Conclusions: Healthcare workers are exposed to a variety of chemicals that vary with tasks and ingredients of products used during cleaning and disinfecting. The combination of product ingredients with cleaning and disinfecting tasks were associated with specific VOCs. Exposure modules for questionnaires used in epidemiologic studies might benefit from seeking information on products used within a task context.

Carbendazim is a fungicide commonly used as active substance in plant protection products and biocidal products, for instance to protect facades of buildings against fungi. However, the subsequent occurrence of this fungicide and potential endocrine disruptor in the aqueous environment is a major concern. In this study, high resolution mass spectrometry shows that carbendazim can be detected with an increasing abundance from the source to the mouth of the River Rhine. Unexpectedly, the abundance of carbendazim correlates poorly with that of other fungicides used as active ingredients in plant protection products (r 2 of 0.32 for cyproconazole and r 2 of 0.57 for propiconazole) but it correlates linearly with that of pharmaceuticals (r 2 of 0.86 for carbamazepine and r 2 of 0.89 for lamotrigine). These results suggest that the occurrence of carbendazim in surface water comes mainly from the discharge of treated domestic wastewater. This hypothesis is further confirmed by the detection of carbendazim in wastewater effluents (n = 22). In fact, bench-scale leaching tests of textiles and papers revealed that these materials commonly found in households could be a source of carbendazim in domestic wastewater. Moreover, additional river samples collected nearby two paper industries indicate that the discharge of their treated process effluents is also a source of carbendazim in the environment. While characterizing paper and textile as overlooked sources of carbendazim, this study also shows the biocide as a possible ubiquitous wastewater contaminant that would require further systematic and worldwide monitoring due to its toxicological properties., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2018 Elsevier Ltd. All rights reserved.)