Formation and control of disinfection by-products during the trichloroisocyanuric acid disinfection in swimming pool water.

The increasing demand for trichloroisocyanuric acid (TCCA) in swimming pool disinfection highlights the need to evaluate its applicability in terms of disinfection by-product (DBP) formation. Nevertheless, there is limited understanding of DBP formation and control during TCCA disinfection, particularly concerning the effects of various management parameters. This study aimed to fill this knowledge gap by comprehensively investigating DBP formation during TCCA chlorination, with a particular focus on assessing the contribution and interaction of influencing factors using Box-Behnken Design and response surface methodology. Results indicated that the concentrations of trichloroacetaldehyde, chloroform, dichloroacetic acid, trichloroacetic acid, and dichloroacetonitrile produced by TCCA disinfectant were 42.5%, 74.0%, 48.1%, 94.7% and 42.6% of those by the conventional sodium hypochlorite disinfectant, respectively. Temperature exhibited the most significant impact on chloroform formation (49%), while pH played a major role in trichloroacetaldehyde formation (44%). pH2 emerged as the primary contributor to dichloroacetic acid (90%) and trichloroacetic acid (93%) formation. The optimum water quality conditions were determined based on the minimum total DBPs (pH = 7.32, Temperature = 23.7 °C, [Cl-] = 437 mg/L). Chlorine dosage and contact time exhibited greater influence than precursor concentration on chloroform, dichloroacetonitrile, trichloroacetaldehyde, trichloroacetic acid, and total DBPs. Although the interaction between water quality parameters was weak, the interaction between disinfection operating parameters demonstrated substantial effects on DBP formation (8.56-19.06%). Furthermore, the DBP predictive models during TCCA disinfection were provided for the first time, which provides valuable insights for DBP control and early warning programs.

Visual signal sensor coupling to nitrification for sustainable monitoring of trichloroacetaldehyde and the response mechanisms.

In this work, a toxicity monitoring microbial system (TMMS) with a nitrifying biofilm as a sensing element and cathode oxygen reduction as an electrical signal was successfully constructed for trichloroacetaldehyde (TCAL) detection. The current and nitrification rate showed a linear relationship with TCAL concentration from 0 to 100 µg/L (R2current = 0.9892, R2nitrification = 0.9858), indicating that the target substrate concentration can be directly obtained from an electrical signal without further sample concentration. High-throughput sequencing revealed that the TMMS was composed of autotrophic/heterotrophic nitrifying and denitrifying microorganisms. Further analysis via a symbiotic relationship network demonstrated that unclassified_Comamonadaceae and unclassified_Xanthobacteraceae were the core nodes for maintaining the interaction between autotropic and heterotrophic nitrifying bacteria. Kyoto Encyclopedia of Genes and Genomes analysis showed that the electron transfer process primarily relied on ferredoxin and cytochromes under TCAL stress, and the abundance of functional enzymes involved in the process of nitrification was decreased, resulting in changes in electrical signal output. This work explored a visual signal sensor combined with electrochemistry and autotrophic/heterotrophic nitrification, which provided new insights into recognition and response mechanisms for microbial monitoring of toxic substances.

Iron foam coupled hydrolysis acidification for trichloroacetaldehyde treatment: Strengthening characteristics and mechanism.

This research studied transformative characteristics and enhanced mechanism of trichloroacetaldehyde (TCAL), one of chlorinated acetaldehydes (CAAs), by coupled-type iron foam enhanced hydrolysis acidification (HA) reactor. Main results were given that better dechlorination and aldehyde removal were achieved at this process than coupled-type iron foam enhanced HA, alone iron foam and HA reactor. The reasons were due to better strengthening effects of iron foam and HA, iron foam reduced TCAL toxicity to microbes caused an improvement of microbial activity, therefore, volatile fatty acids (VFAs) content and acetate acid (Ac) ratio were increased compared with HA. Moreover, it promoted the enrichment of Actinobacteriota and Firmicutes, and more extracellular polymeric substance (EPS) and enzymes enhanced dechlorination and aldehyde removal. Certainly, microbes reduced iron foam passivation and facilitated its oxidation further improved the strengthening effect.

Occurrence and fate of ozonation disinfection by-products in two Canadian drinking water systems.

The occurrence and the fate of 18 ozonation by-products (OBPs) (17 different aldehydes and bromate) were studied over one year in two Canadian drinking water systems. This is the first and only study reporting the occurrence of all these non-halogenated aldehydes (NON-HALs) and haloacetaldehydes (HALs) simultaneously, based on the multi-point monitoring of water in full-scale conditions from source to distribution network. In general, the application of both post-ozonation and liquid chlorine contributed to the formation of OBPs (aldehydes and bromate). NON-HALs were present in higher concentrations than HALs. Formaldehyde, acetaldehyde, glyoxal and methylglyoxal were the most common forms of NON-HALs in the two water systems that were studied. Chloral hydrate (CH), the hydrated form of trichloroacetaldehyde, was the most dominant HAL observed. The nature of the organic matter and the water temperature proved to be important parameters for explaining the variability of aldehydes. Summer and autumn (warm seasons) were more favorable for the formation of chloral hydrate and bromate. The highest concentrations of NON-HALs were observed in spring.

Inhibition and removal of trichloroacetaldehyde by biological acidification with glucose co-metabolism.

Biological acidification plays a crucial role in biological removal of organic compounds during petrochemical wastewater treatment. Trichloroacetaldehyde is a typical organic pollutant in petrochemical wastewater, however, no studies have been conducted on its effect on biological acidification. In this study, batch bioassays of volatile fatty acids were conducted to explore the inhibitory effect of trichloroacetaldehyde on biological acidification, the variations of key enzymes and extracellular polymeric substances under trichloroacetaldehyde shock, and the mechanism of trichloroacetaldehyde removal. The results of these bioassays indicated that trichloroacetaldehyde inhibited the acid yield at higher concentrations (EC50 112.20 mg/L), and butyric fermentation was predominant. Moreover, the contents of extracellular polymeric substances and several key acidifying enzymes greatly decreased when the trichloroacetaldehyde concentration exceeded 100 mg/L, which was due to the toxicity that trichloroacetaldehyde poses to the microbes involved in biological acidification. The trichloroacetaldehyde mechanism was as follows: first, trichloroacetaldehyde was adsorbed by extracellular polymeric substances and anaerobic granular sludge, and then transformed into trichloroethanol, trichloroethane, dichloroacetaldehyde, and dichloroethanol under the combined action of the aldehyde reductase and reductive dehalogenases secreted from the microbial consortium. The ability of biological acidification to remove trichloroacetaldehyde was limited; therefore, trichloroacetaldehyde should be pretreated before it enters biological treatment systems.

500 days of swimmers: the chemical water quality of swimming pool waters from the beginning.

Many studies of disinfection by-products (DBPs) in pools have focused on haloacetic acids, trihalomethanes, and chloramines, with less studies investigating the occurrence of other DBPs, such as haloketones, haloacetaldehydes, haloacetonitriles, halonitromethanes, and haloacetamides. Furthermore, while many studies have achieved a broadscreen analysis across several pools, fewer studies have followed the water quality of pools over time, with information regarding the production and fate of DBPs in pools over extended periods (e.g. > 1 year) being limited. This study reports the occurrence of 39 DBPs and several general water quality parameters in two newly built and filled swimming pools over 15 months, where investigations began prior to opening. DBP concentrations measured in this study were generally similar to or higher than those previously reported in chlorinated pools, with concentrations of chloroacetic acid, dichloroacetic acid, trichloroacetic acid, and chloral hydrate (trichloroacetaldehyde) in some samples being higher than previously reported maximum concentrations. Considering both pools, lower concentrations of DBPs were measured in the pool where a steady state non-purgeable organic carbon concentration was achieved, highlighting the importance of the establishment of a steady state balance of mineralisation versus addition of organic carbon to reduce precursors for DBP formation in pools. Pools were found to exhibit significantly higher estimated cytotoxicity than their filling water, which reflects the significantly higher concentrations of DBPs measured in the pools in comparison to the filling water. Chloral hydrate accounted for up to 99% the total estimated cytotoxicity and was found to be correlated to the number of pool entries, suggesting that swimmers may be a potential source of chloral hydrate precursors in pools. The presence and subsequent peak of non-purgeable organic carbon and DBPs prior to, and soon after, opening suggest that the building process and/or new pool infrastructure may have had a significant impact on the chemical water quality, particularly on DBP formation. This study includes the first quantification of bromochloroacetaldehyde, bromodichloroacetaldehyde, bromochloronitromethane, and dichloronitromethane in chlorinated swimming pools, and provides important new knowledge on the long-term trends of DBPs in pools.

Effect of trichloroacetaldehyde on the activation of CD4+T cells in occupational medicamentosa-like dermatitis: An in vivo and in vitro study.

Occupational medicamentosa-like dermatitis induced by trichloroethylene (OMLDT) is a hypersensitivity disease with autoimmune liver injury, which has increasingly become a serious occupational health problem in China. However, the pathogenesis of OMLDT remained undefined. In this study, 30 TCE-induced OMLDT patients, 58 exposure controls, and 40 non-exposure controls were recruited. We showed that the ratio of activated CD4+ T cells (downregulation of CD62 L) was dramatically increased in OMLDT patients compared to exposure and non-exposure control, suggesting that CD4+ T cells activation was a key cellular event in the development of OMLDT. In parallel, the expression of cytokine including IL-2, IFN-γ, TNF-α and IL-17A were increased obviously and IL-4 decreased in CD4+ T cells from OMLDT patients. in vitro assay, we found that trichloroethylene metabolites trichloroacetaldehyde (TCAH), not trichloroacetic acid (TCA) or Trichloroethanol (TCOH) could activate the naïve CD4+ T cells characterized by a rise in intracellular calcium, down-regulated CD62 L and subsequently trigger the secretion of IL-2, IFN-γ and TNF-α. Notably, the phosphorylation status of NF-κB and p38MAPK were elevated in OMLDT patients. Moreover, TCAH also could activate the p38MAPK and NF-κB, suggesting the role of p38MAPK and NF-κB pathways in the activation of CD4+ T cells. In addition, we found that the inhibition of Schiff base formation decreased the ability of TCAH to induce the activation of naïve CD4+ T cells and p38MAPK and NF-κB pathway. In conclusion, we revealed that the CD4+ T activation and increased the cytokines including IL-2, IFN-γ and TNF-α but decreased IL-4 in CD4+ T cells were associated with OMLDT. TCAH could activate naïve CD4+ T cells through NF-κB and p38MAPK activation induced by Schiff base formation, which might contribute to the development of OMLDT. These findings provide a new insight into the pathogenesis of OMLDT.

Yield of trihalomethane, haloacetic acid and chloral upon chlorinating algae after coagulation-filtration: Is pre-oxidation necessarily negative for disinfection by-product control?

Effect of pre-chlorination and pre-ozonation on Microcystis aeruginosa (MA) and Coccomyxa subellipsoidea (CS) as disinfection by-products (DBPs) precursors was investigated after coagulation-filtration. Pre-chlorination considerably decreased the autofluorescence of algae cells but barely influenced cell granularity. In comparison, after pre-ozonation more algae cells were associated with decreased cell size; yet less reduction in the autofluorescence was observed. In MA case, pre-chlorination increased the residual algae density after coagulation-filtration by 132%-146% while pre-ozonation enhanced the algae removal by 26%-28%. In CS case, algae removal was improved by pre-chlorination (32%-45%) and pre-ozonation (7%-45%). Pre-chlorination enhanced the removal of algogenic organic matters (AOM) by coagulation-filtration, especially for tryptophan-like and soluble microbial products. Effect of pre-ozonation on the fluorescence intensity of AOM after coauglation-filtration depended on AOM species and the ratio of [ozone dose]:[algae density]. In both MA and CS cases, chlorine increased the yields of trihalomethane (THM, 25%-78% and 51%-103%), haloacetic acid (HAA, 140%-360% and 167%-233%) and chloral (50%-161% and 68%-108%), respectively. Pre-ozonation decreased the total DBPs yields. For MA-added suspensions, ozone decreased the production of THM, HAA and chloral by 15%-37%, 28%-39% and 60%, respectively. In CS case, chloral yield was decreased by 12%-31% while THM formation was largely unchanged. HAA production varied by ± 1.5 µg/L.

Oxidative Stress Challenge Uncovers Trichloroacetaldehyde Hydrate-Induced Mitoplasticity in Autistic and Control Lymphoblastoid Cell Lines.

Mitoplasticity occurs when mitochondria adapt to tolerate stressors. Previously we hypothesized that a subset of lymphoblastoid cell lines (LCLs) from children with autistic disorder (AD) show mitoplasticity (AD-A), presumably due to previous environmental exposures; another subset of AD LCLs demonstrated normal mitochondrial activity (AD-N). To better understand mitoplasticity in the AD-A LCLs we examined changes in mitochondrial function using the Seahorse XF96 analyzer in AD and Control LCLs after exposure to trichloroacetaldehyde hydrate (TCAH), an in vivo metabolite of the environmental toxicant and common environmental pollutant trichloroethylene. To better understand the role of reactive oxygen species (ROS) in mitoplasticity, TCAH exposure was followed by acute exposure to 2,3-dimethoxy-1,4-napthoquinone (DMNQ), an agent that increases ROS. TCAH exposure by itself resulted in a decline in mitochondrial respiration in all LCL groups. This effect was mitigated when TCAH was followed by acute DMNQ exposure but this varied across LCL groups. DMNQ did not affect AD-N LCLs, while it neutralized the detrimental effect of TCAH in Control LCLs and resulted in a increase in mitochondrial respiration in AD-A LCLs. These data suggest that acute increases in ROS can activate mitochondrial protective pathways and that AD-A LCLs are better able to activate these protective pathways.

Formation Pathways and Trade-Offs between Haloacetamides and Haloacetaldehydes during Combined Chlorination and Chloramination of Lignin Phenols and Natural Waters.

In vitro bioassays have indicated that haloacetamides and haloacetaldehydes exhibit the highest cytotoxicity among DBP classes. Previous research has focused on their potential formation from the chlorination or chloramination of aliphatic compounds, particularly nonaromatic amino acids, and acetaldehyde. The present work found that acetaldehyde served as a relatively poor precursor for trichloroacetaldehyde and dichloroacetamide, generally the most prevalent of the haloacetaldehydes and haloacetamides, during chlorination or chlorination/chloramination. Using phenolic model compounds, particularly 4-hydroxybenzoic acid, as models for structures in humic substances, we found significantly higher formation of trichloroacetaldehyde and dichloroacetamide from prechlorination followed by chloramination. Evaluation of the stoichiometry of chlorine reactions with 4-hydroxybenzoic acid and several intermediates indicated that seven successive Cl[+1] transfers, faster with chlorination than chloramination, can form 2,3,5,5,6-pentachloro-6-hydroxy-cyclohexa-2-ene-1,4-dione via chlorophenol and chlorobenzoquinone intermediates. Formation of 2,3,5,5,6-pentachloro-6-hydroxy-cyclohexa-2-ene-1,4-dione may serve as a key branching point, with chloramines promoting the formation of dichloroacetamide and chlorination promoting the formation of trichloroacetaldehyde. The behavior of 4-hydroxybenzoic acid with respect to yields of dichloroacetamide and trichloroacetaldehyde during chlorination followed by chloramination was similar to the behavior observed for model humic acids and several surface waters, suggesting that phenolic structures in natural waters may serve as the predominant, and common pool of precursors for haloacetamides and haloacetaldehydes. Experiments with natural waters indicated that the branching point is reached over prechlorine exposures (100-500 mg-min/L) relevant to drinking water utilities using chlorine as a primary disinfectant and chloramines for maintenance of a distribution system residual.

Synthesis, characterization and non-isothermal decomposition kinetic of a new galactochloralose based polymer.

A glycopolymer, poly(3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose) (PMIPTEG) was synthesized from the sugar-carrying methacrylate monomer, 3-O-methacroyl-5,6-O-isopropylidene-1,2-O-(S)-trichloroethylidene-α-d-galactofuranose (MIPTEG) via conventional free radical polymerization with AIBN in 1,4-dioxane. The structures of glycomonomer and their polymers were confirmed by UV-vis, FT-IR, (1)H NMR, (13)C NMR, GPC, TG/DTG-DTA, DSC, and SEM techniques. SEM images showed that PMIPTEG had a straight-chain length structure. On the other hand, the thermal decomposition kinetics of polymer were investigated by means of thermogravimetric analysis in dynamic nitrogen atmosphere at different heating rates. The apparent activation energies for thermal decomposition of the PMIPTEG were calculated using the Kissinger, Kim-Park, Tang, Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS) and Friedman methods and were found to be 100.15, 104.40, 102.0, 102.2, 103.2 and 99.6 kJ/mol, respectively. The most likely process mechanism related to the thermal decomposition stage of PMIPTEG was determined to be a Dn deceleration type in terms of master plots results.

Adsorption and hydrolysis of alcohols and carbonyls on ice at temperatures of the upper troposphere.

The uptake of gaseous ethanol, 1,1,1-trifluoroethanol, acetone, chloral (CCl(3)CHO), and fluoral (CF(3)CHO) on ice films has been investigated using a coated-wall flow tube at temperatures 208-228 K corresponding to the upper troposphere (UT), with a mass spectrometric measurement of gas concentration. The uptake was largely reversible and followed Langmuir-type kinetic behavior, i.e., surface coverage increased with the trace gas concentration approaching a maximum surface coverage at a gas phase concentration of N(max) ∼ (2-4) × 10(14) molecules cm(-3), corresponding to a surface coverage of ∼30% of a monolayer (ML). The equilibrium partition coefficients, K(LinC), were obtained from the experimental data by analysis using the simple Langmuir model for specific conditions of temperature and concentration. The analysis showed that the K(LinC) depend only weakly on surface coverages. The following expressions described the temperature dependence of the partition coefficients (K(LinC)) in centimeters, at low coverage for ethanol, trifluoroethanol, acetone, chloral, and fluoral: K(LinC) = 1.36 × 10(-11) exp(5573.5/T), K(LinC) = 3.74 × 10(-12) exp(6427/T), K(LinC) = 3.04 × 10(-9) exp(4625/T), K(LinC) = 7.52 × 10(-4) exp(2069/T), and K(LinC) = 1.06 × 10(-2) exp(904/T). For acetone and ethanol the enthalpies and entropies of adsorption derived from all available data showed systematic temperature dependence, which is attributed to temperature dependent surface modifications, e.g., QLL formation. For chloral and fluoral, there was an irreversible component of uptake, which was attributed to hydrate formation on the surface. Rate constants for these surface reactions derived using a Langmuir-Hinshelwood mechanism are reported.

Micro liquid-liquid extraction combined with large-volume injection gas chromatography-mass spectrometry for the determination of haloacetaldehydes in treated water.

Haloacetaldehydes (HAs) are becoming the most widespread disinfection by-products (DBPs) found in drinking water, besides trihalomethanes and haloacetic acids, generated by the interaction of chemical disinfectants with organic matter naturally present in water. Because of their high potential toxicity, HAs have currently received a singular attention, especially trichloroacetaldehyde (chloral hydrate, CH), the most common and abundant compound found in treated water. The aims of this study are focused on the miniaturisation of EPA Method 551.1, including some innovations such as the use of ethyl acetate as the extracting solvent, the enhancement of HAs stability in aqueous solutions by adjusting the pH ~3.2 and the use of a large-volume sample injection (30 µL) coupled to programmed temperature vaporizer-gas chromatography-mass spectrometry to improve both sensitivity and selectivity. In optimised experimental conditions, the limits of detection for the 7 HAs studied ranged from 6 to 20 ng/L. Swimming pools have recently been recognized as an important source of exposure to DBPs and as a result, in this research for the first time, HAs have been determined in this type of water. Two HAs have been found in the analysed water: CH at concentrations between 1.2-38 and 53-340 µg/L and dichloroacetaldehyde between 0.07-4.0 and 1.8-23 µg/L in tap and swimming pool waters, respectively.

Disinfection byproduct formation and fractionation behavior of natural organic matter surrogates.

While natural organic matter (NOM) surrogates are established in disinfection byproduct (DBP) research, their use in fractionation studies is rare. To understand how surrogates relate to drinking waters, a range of NOM surrogates were fractionated with XAD resins. Their trihalomethane (THM), haloacetic acid (HAA), haloacetaldehyde, haloacetonitrile, and haloketone formations after chlorination were recorded. While compounds with higher log K(ow) values behaved as hydrophobic acids, fractionation of the more hydrophilic compounds did not clearly correlate to the log K(ow). High HAA formation from ferulic and aspartic acids and 1,1,1-trichloropropanone (1,1,1-TCP) formation from 3-oxopropanoic acid were notable. Three amino acids, asparagine, aspartic acid, and tryptophan, formed significant levels of dichloroacetonitrile (DCAN) and trichloroacetaldehyde (TCA). Formation of DBPs did not correlate to any compound physical property; however, there were several correlations between DBP groups. The most significant were between dichloroacetic acid (DCAA) and dichloroacetonitrile (DCAN), DCAN and TCA, and dichloroacetaldehyde (DCA) and trichloroacetaldehyde, indicating the possibility of similar relationships in natural waters.

Life threatening intracerebral hemorrhage with isometheptene mucate, dichlorophenazine and acetaminophen combination therapy.

A 45 year old female with no stroke risk factors suffered a massive intracerebral hemorrhage (ICH) after ingesting Midrin--a combination of isometheptene mucate, dichlorophenazine and acetaminophen. Neuroimaging revealed no evidence of structural disease or underlying vasculopathy. This is the first reported case of isometheptene induced ICH in the absence of underlying cerebrovascular disease. Physicians must be aware of the potential for this complication, and inquire about the use of isometheptene in unexplained cerebral hemorrhages. Neurological communities in countries with nonprescription isometheptene should discourage unsupervised or excessive use of the drug.

Chronic exposure to a trichloroethylene metabolite in autoimmune-prone MRL+/+ mice promotes immune modulation and alopecia.

The industrial solvent trichloroethylene (TCE) is a widespread environmental contaminant known to impact the immune system. In the present study, female MRL+/+ mice were treated for 40 weeks with trichloroacetaldehyde hydrate (TCAH), a metabolite of TCE, in the drinking water. The results were compared with the data from an earlier study in which MRL+/+ mice were exposed to TCAH for 4 weeks. Following a 40-week exposure, the mice developed skin inflammation and dose-dependent alopecia. In addition, TCAH appeared to modulate the CD4(+) T-cell subset by promoting the expression of an activated/effector (i.e., CD62L(lo)) phenotype with an increased capacity to secrete the proinflammatory cytokine interferon-gamma. However, unlike what was observed after only 4 weeks of exposure, TCAH did not significantly attenuate activation-induced cell death (AICD) or the expression of the death receptor FasL in CD4(+) T cells. Some metalloproteinases (MMPs) are thought to play a role in susceptibility to AICD by inducing FasL shedding. Thus, both the 4- and 40-week sera were tested for MMP-7 levels in an attempt to explain the disparate results of TCAH on AICD and FasL expression. Serum MMP-7 levels were significantly higher in mice exposed to TCAH for 4 weeks. In contrast, the serum MMP-7 levels were increased in all the mice by 40 weeks when compared with a nonautoimmune strain. Taken together, a chronic exposure to TCAH promotes alopecia and skin inflammation. The early effects of TCAH on MMP-7 levels may provide a mechanism by which TCAH promotes skin pathology.

[Study on decomposed products of trichlorfon in process of gas chromatographic analysis by mass spectrometry].

The decomposed products of trichlorfon in gas chromatographic analysis were identified by mass spectrometry (MS). After MS interpretation, three decomposed products, trichloroacetaldehyde, dimethyl phosphite and dichlorvos were identified. The effects of gas chromatographic conditions on decomposed products of trichlorfon, e. g. injection temperature, injection mode and oven ramp, were studied. The experiments showed that all of the factors have effects on decomposed products of trichlorfon, however, the injection temperature is the key factor to cause trichlorfon being decomposed. The higher the injection temperature is, the bigger the amount of trichlorfon being decomposed. When the injection temperature was raised from 150 degrees C to 250 degrees C, the remaining trichlorfon fell from 86% to 20%. Therefore, on-cold column injection mode gas chromatography or high performance liquid chromatography was recommended for exact quantification of trace trichlorfon.