Body fluid analog chlorination: Application to the determination of disinfection byproduct formation kinetics in swimming pool water

Disinfection by-products(DBPs) are formed in swimming pools by the reactions of bather inputs with the disinfectant.Although a wide range of molecules has been identified within DBPs,only few kinetic rates have been reported.This study investigates the kinetics of chlorine consumption,chloroform formation and dichloroacetonitrile formation caused by human releases.Since the flux and main components of human inputs have been determined and formalized through Body Fluid Analogs(BFAs),it is possible to model the DBPs formation kinetics by studying a limited number of precursor molecules.For each parameter the individual contributions of BFA components have been quantified and kinetic rates have been determined,based on reaction mechanisms proposed in the literature.With a molar consumption of 4 mol Cl_2/mol,urea is confirmed as the major chlorine consumer in the BFA because of its high concentration in human releases.The higher reactivity of ammonia is however highlighted.Citric acid is responsible for most of the chloroform produced during BFA chlorination.Chloroform formation is relatively slow with a limiting rate constant determined at 5.50 × 10~(-3) L/mol/sec.L-histidine is the only precursor for dichloroacetonitrile in the BFA.This DBP is rapidly formed and its degradation by hydrolysis and by reaction with hypochlorite shortens its lifetime in the basin.Reaction rates of dichloroacetonitrile formation by L-histidine chlorination have been established based on the latest chlorination mechanisms proposed.Moreover,this study shows that the reactivity toward chlorine differs whether L-histidine is isolated or mixed with BFA components.     

Concentrations of disinfection by-products in swimming pool following modifications of the water treatment process: An exploratory study

The formation and concentration of disinfection by-products (DBPs) in pool water and the ambient air vary according to the type of water treatment process used. This exploratory study was aimed at investigating the short-term impact of modifications of the water treatment process on traditional DBP levels (e.g., trihalomethanes (THMs), chloramines) and emerging DBPs (e.g., Halonitromethanes, Haloketones, NDMA) in swimming pool water and/or air. A sampling program was carried to understand the impact of the following changes made successively to the standard water treatment process: activation of ultraviolet (UV) photoreactor, halt of air stripping with continuation of air extraction from the buffer tank, halt of air stripping and suppression of air extraction from the buffer tank, suppression of the polyaluminium silicate sulfate (PASS) coagulant. UV caused a high increase of Halonitromethanes (8.4 fold), Haloketones (2.1 fold), and THMs in the water (1.7 fold) and, of THMs in the air (1.6 fold) and contributed to reducing the level of chloramines in the air (1.6 fold) and NDMA in the water (2.1 fold). The results highlight the positive impact of air stripping in reducing volatile contaminants. The PASS did not change the presence of DBPs, except for the THMs, which decrease slightly with the use of this coagulant. This study shows that modifications affecting the water treatment process can rapidly produce important and variable impacts on DBP levels in water and air and suggests that implementation of any water treatment process to reduce DBP levels should take into account the specific context of each swimming pool.     

Assessing microbial and chemical exposure risks of Giardia in indoor swimming pool water disinfected by chlorine

Swimming pools adopt chlorination to ensure microbial safety. Giardia has attracted attention in swimming pool water because of its occurrence, pathogenicity, and chlorine resistance. To control Giardia concentrations in pool water and reduce the microbial risk, higher chlorine doses are required during disinfection. Unfortunately, this process produces carcinogenic disinfection byproducts that increase the risk of chemical exposure. Therefore, quantitatively evaluating the comparative microbial...     

Do DBPs swim in salt water pools? Comparison of 60 DBPs formed by electrochemically generated chlorine vs. conventional chlorine

Disinfectants are added to swimming pools to kill harmful pathogens. Although liquid chlorine(sodium hypochlorite) is the most commonly used disinfectant, alternative disinfection techniques like electrochemically generated mixed oxidants or electrochemically generated chlorine, often referred to as salt water pools, are growing in popularity. However, these disinfectants react with natural organic matter and anthropogenic contaminants introduced to the pool water by swimmers to form disinfectio...     

Application of a novel open-source program for measuring the effects of toxicants on the swimming behavior of large groups of unmarked fish

The aim of this study was to demonstrate a novel method for measuring the effects of toxicants on the behavior of groups of unmarked fish. Ctrax is an open source Python-based machine vision program that was originally designed to track fruit flies (Drosophila). The effects of the fish anaesthetic quinaldine sulfate on the behavior of groups of 10 unmarked Arabian killifish (Aphanias dispar) in a small arena were measured. Ctrax was able to identify and track the X-Y coordinates of the individual fish over 1 min recording periods. The data was analyzed using specifically written Matlab (The Mathworks™) toolboxes and the effects of quinaldine sulfate on absolute swimming velocity, forward swimming velocity, rate of change in orientation and distance to wall were calculated. Additionally the effects of quinaldine sulfate on path tortuosity were also measured. Ctrax has significant benefits over other available technologies for tracking the 2-dimensional coordinates of fish. In particular the software is open source and thus freely available, it is accurate, requires only simple easily available equipment and able to track potentially large groups of fish (possibly >50) while maintaining their individual identities.     

水体突发性重金属污染胁迫下斑马鱼的行为反应分析

研究了斑马鱼在不同程度突发性的Zn2＋和Cr6＋胁迫下的行为反应,采用计算机视觉技术量化研究斑马鱼游动行为数据。结果表明,在Zn2＋和Cr6＋的突发性胁迫中,斑马鱼的行为反应快速且敏感,游动行为与污染物种类、质量浓度和暴露时间直接相关,并表现出比较相似的行为变化规律;随着胁迫程度的增加,斑马鱼游动速度的变化幅度增大,反应时间缩短,且其变化曲线符合生物行为的环境压力模型。斑马鱼的行为变化远远提前于生物的病理损伤或死亡,可利用斑马鱼暴露于污染物时的行为变化实现在线水体突发性重金属污染事故的监测预警。     

Effect of treated swimming pool water on the levels of trihalomethanes in swimmer's urine

Swimming pools are considered to be the prime source for public exposure to trihalomethanes (THMs), mainly chloroform, because of their use for hygienic purposes. High doses of chlorine are easily perceptible by smell. The aim of this study was to measure simultaneously the THM levels in urine and blood of swimmers and in pool water itself (from city and university swimming pool), in order to investigate further the relationship between substances in different matrices at known environmental levels with uptake of these substances in indoor swimming pools. Volatile analytes were isolated and preconcentrated from the samples by thin layer headspace analysis (TLHS) with autogenous generation of the liquid sorbent. Chloroform, bromodichloromethane and dibromochloromethane were detected in the urine of all persons attending a swimming pool. Concentrations of THM compounds varied in the case of each swimmer. The research confirmed that approximately 10% of the volatile haloorganic compounds are excreted in urine in the unchanged form.     

Effects of two polybrominated diphenyl ethers (BDE-47, BDE-209) on the swimming behavior,population growth and reproduction of the rotifer Brachionus plicatilis

Polybrominated diphenyl ethers(PBDEs) are new kinds of persistent organic pollutants(POPs) and their potential threats to the equilibrium and sustainability of marine ecosystems have raised worldwide concerns. Here, two kinds of PBDEs, tetra-BDE(BDE-47)and deca-BDE(BDE-209) were applied, and their toxic effects on the swimming behavior,population growth and reproduction of Brachionus plicatilis were investigated. The results showed that:(1) The actual concentrations of BDE-47 and-209 in the seawater phase measured by GC–MS(Gas Chromatography-Mass Spectrometer) were much lower than their nominal concentrations.(2) In accordance with the 24-hr acute tests, BDE-209 did not show any obvious swimming inhibition to rotifers, but a good correlation did exist between the swimming inhibition rate and BDE-47 concentration suggesting that BDE-47 is more toxic than BDE-209.(3) Both BDE-47 and-209 had a significant influence on the population growth and reproduction parameters of B. plicatilis including the population growth rate, the ratio of ovigerous females/non-ovigerous females(OF/NOF), the ratio of mictic females/amictic females(MF/AF), resting egg production and the mictic rate, which indicate that these parameters in B. plicatilis population were suitable for monitoring and assessing PBDEs. Our results suggest that BDE-47 and-209 are not acute lethal toxicants and may pose a low risk to marine rotifers at environmental concentrations for short-term exposure. They also accumulate differently into rotifers. Further research data are needed to understand the mechanisms responsible for the effects caused by PBDEs and to assess their risks accurately.     

Effects of two polybrominated diphenyl ethers (BDE-47, BDE-209) on the swimming behavior, population growth and reproduction of the rotifer Brachionus plicatilis

Polybrominated diphenyl ethers (PBDEs) are new kinds of persistent organic pollutants (POPs) and their potential threats to the equilibrium and sustainability of marine ecosystems have raised worldwide concerns. Here, two kinds of PBDEs, tetra-BDE (BDE-47) and deca-BDE (BDE-209) were applied, and their toxic effects on the swimming behavior, population growth and reproduction of Brachionus plicatilis were investigated. The results showed that: (1) The actual concentrations of BDE-47 and -209 in the seawater phase measured by GC-MS (Gas Chromatography-Mass Spectrometer) were much lower than their nominal concentrations. (2) In accordance with the 24-hr acute tests, BDE-209 did not show any obvious swimming inhibition to rotifers, but a good correlation did exist between the swimming inhibition rate and BDE-47 concentration suggesting that BDE-47 ismore toxic than BDE-209. (3) Both BDE-47 and -209 had a significant influence on the population growth and reproduction parameters of B. plicatilis including the population growth rate, the ratio of ovigerous females/non-ovigerous females (OF/NOF), the ratio of mictic females/amictic females (MF/AF), resting egg production and the mictic rate, which indicate that these parameters in B. plicatilis population were suitable for monitoring and assessing PBDEs. Our results suggest that BDE-47 and -209 are not acute lethal toxicants and may pose a low risk to marine rotifers at environmental concentrations for short-term exposure. They also accumulate differently into rotifers. Further research data are needed to understand the mechanisms responsible for the effects caused by PBDEs and to assess their risks accurately.     

Disinfection byproducts in chlorinated or brominated swimming pools and spas: Role of brominated DBPs and association with mutagenicity

Although the health benefits of swimming are well-documented, health effects such as asthma and bladder cancer are linked to disinfection by-products (DBPs) in pool water. DBPs are formed from the reaction of disinfectants such as chlorine (Cl) or bromine (Br) with organics in the water. Our previous study (Daiber et al., Environ. Sci. Technol. 50, 6652; 2016) found correlations between the concentrations of classes of DBPs and the mutagenic potencies of waters from chlorinated or brominated swimming pools and spas. We extended this study by identifying significantly different concentrations of 21 individual DBPs in brominated or chlorinated pool and spa waters as well as identifying which DBPs and additional DBP classes were most associated with the mutagenicity of these waters. Using data from our previous study, we found that among 21 DBPs analyzed in 21 pool and spa waters, the concentration of bromoacetic acid was significantly higher in Br-waters versus Cl-waters, whereas the concentration of trichloroacetic acid was significantly higher in Cl-waters. Five Br-DBPs (tribromomethane, dibromochloroacetic acid, dibromoacetonitrile, bromoacetic acid, and tribromoacetic acid) had significantly higher concentrations in Br-spa versus Cl-spa waters. Cl-pools had significantly higher concentrations of Cl-DBPs (trichloroacetaldehyde, trichloromethane, dichloroacetic acid, and chloroacetic acid), whereas Br-pools had significantly higher concentrations of Br-DBPs (tribromomethane, dibromoacetic acid, dibromoacetonitrile, and tribromoacetic acid). The concentrations of the sum of all 4 trihalomethanes, all 11 Br-DBPs, and all 5 nitrogen-containing DBPs were each significantly higher in brominated than in chlorinated pools and spas. The 8 Br-DBPs were the only DBPs whose individual concentrations were significantly correlated with the mutagenic potencies of the pool and spa waters. These results, along with those from our earlier study, highlight the importance of Br-DBPs in the mutagenicity of these recreational waters.