Influence of chlorination pH and chlorine dose on the formation of mutagenic activity and the strong bacterial mutagen 3-chloro-4-(dichloromethyl)-5-hydroxy-5(2H)-furanone (MX) in water

Samples from two Dutch raw water sources were chlorinated in the laboratory at different pH:s and chlorine doses, and were analysed for mutagenic activity and the mutagenic compound 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX). Chlorination produced mutagenic activity as well as MX in both waters. The formation of MX was favoured by acidic reaction conditions and high chlorine doses, but in waters treated with excess chlorine at pH 9, no MX was detected. The mutagenicity was approximately on the same level after chlorination of both water types but the MX concentration was significantly higher in the water containing mainly humic material.

MX was found to be quantitatively extracted from acidified waters by the XAD resin adsorption technique.     

南方某市饮用水源三氯乙醛生成特性

以我国南方某市饮用水源为研究对象,分析了不同反应条件下的三氯乙醛 (CH) 生成情况、CH与常规消毒副产物 (DBPs) 的相关关系及水质指标与CH生成势(CHFP)的相关关系.结果表明,5~35℃温度范围内,CH生成量随着温度的升高而逐渐升高,45℃时,反应约30 h后CH降解速率大于生成速率,生成量逐渐减少;CH生成量随着pH的升高而逐渐降低,当pH = 11时,CH已经完全降解;Cl2:TOC=1:1~4:1(质量比)时,CH的生成量随着加氯量的增加而增加,但是当Cl2:TOC>4:1时,CH的生成量基本保持不变.CH与两类常规DBPs(三卤甲烷 (THMs) 和卤乙酸 (HAAs))之间均为正相关关系,且CH与卤乙酸(HAAs)的相关关系更为显著.与UV254和SUVA254相比,CHFP与TOC线性关系更为显著,可以根据原水的TOC来简单预测水体中的CHFP.     

Modeling the formation of chlorination by-products in river waters with different quality

Water chlorination results in formation of a variety of organic compounds, known as chlorination by-products (CBPs), mainly trihalomethanes (THMs) and haloacetic acids (HAAs). Factors affecting their concentrations have been found to be organic matter content of water, pH, temperature, chlorine dose, contact time and bromide concentration, but the mechanisms of their formation are still under investigation. Within this scope, chlorination experiments have been conducted with river waters from Lesvos island, Greece, with different water quality regarding bromide concentration and organic matter content. The factors studied were pH, time and chlorine dose. The determination of CBPs was carried out by gas chromatography techniques. Statistical analysis of the results was focused on the development of multiple regression models for predicting the concentrations of total trihalomethanes and total HAAs based on the use of pH, reaction time and chlorine dose. The developed models, although providing satisfactory estimations of the concentrations of the CBPs, showed lower correlation coefficients than the multiple regression models developed for THMs only during previous study. It seems that the different water quality characteristics of the two river waters in the present study is responsible for this phenomenon. The results indicate that under these conditions the formation of THMs and HAAs in water has a more stochastic character, which is difficult to be described by the conventional regression techniques.     

Trichloroacetic acid in Norway spruce/soil-system. I. Biodegradation in soil

Trichloroacetic acid (TCA) as a phytotoxic substance affects health status of coniferous trees. It is known as a secondary air pollutant (formed by photooxidation of tetrachloroethene and 1,1,1-trichloroethane) and as a product of chlorination of humic substances in soil. Its break-down in soil, however, influences considerably the TCA level, i.e. the extent of TCA uptake by spruce roots. In connection with our investigations of TCA effects on Norway spruce, microbial processes in soil were studied using 14C-labeling. It was shown that TCA degradation in soil is a fast process depending on TCA concentration, soil properties, humidity and temperature. As a result, the TCA level in soil is determined by a steady state between uptake from the atmosphere, formation in soil, leaching and degradation. The process of TCA degradation in soil thus participates significantly in the chlorine cycle in forest ecosystems.     

Modeling and optimization of trihalomethanes formation potential of surface water (a drinking water source) using Box–Behnken design

Purpose  

The present research aims to investigate the individual and interactive effects of chlorine dose/dissolved organic carbon ratio, pH, temperature, bromide concentration, and reaction time on trihalomethanes (THMs) formation in surface water (a drinking water source) during disinfection by chlorination in a prototype laboratory-scale simulation and to develop a model for the prediction and optimization of THMs levels in chlorinated water for their effective control.     

Wastewater reuse: modeling chloroform formation

The chloroform is a substance that presents a significant risk to or via the aquatic environment. Thus, the emissions, discharges and losses of this substance need to be controlled during wastewater disinfection for reclamation and reuse purposes. Due to its carcinogenetic potential, multiple studies have been carried out on drinking and surface/natural waters but less consideration has been directed to the wastewater disinfection. The focus of this work studied the formation of chloroform during chlorination in prepared waters or artificial matrices that intended to simulate wastewaters stored in landscape ponds for green areas irrigation. The relation between reaction time, chlorine dose, and chloroform formation and the variation of the dissolved organic carbon (DOC) content during the reaction was assessed. A two-variant model was proposed to simulate breakpoint chlorination practices (when chlorine dose is equal or lower than chlorine demand) and super chlorination techniques (when chlorine dose tends to surpass chlorine demand). The model was validated by the application of actual data from working conditions of six wastewater treatment plants located in Algarve, Portugal, including other data obtained in previous research studies that were not used in the model development, and by comparing the predicted values with real measured ones.     

Relationship between chlorine consumption and chlorination by-products formation for model compounds

The objective of this research is to investigate the relationship between chlorine decay and the formations of disinfection by-products (DBP), including trichloromethane (TCM) and chloroacetic acid (CAA) in the presence of four model compounds, i.e., resorcinol, phloroglucinol, p-hydroxybenzoic acid, and m-hydroxybenzoic acid. The chlorine degradation in model compounds with OH and/or COOH functional groups were rapid after chlorination. The TCM yields of carboxylic group substituted compounds (3-hydroxybenzoic acid [3-HBA], 4-hydroxybenzoic acid [4-HBA]) were found to be lower than that of the m-dihydroxy substituted compounds. Phloroglucinol, with one more OH substitution group than resorcinol, tends to form significant amounts of CAA after chlorination. However, it was observed that with the COOH substitution of 3-HBA and 4-HBA tend to exhibit more CAA formation potential than resorcinol. The developed parallel second and first-order reaction model for chlorine demand has been successfully utilized for TCM, CAA and DBP formation modeling. A high correlation between CAA and TCM was observed for the model compounds.     

Chloroperoxidase-mediated chlorination of aromatic groups in fulvic acid

The aim of the present study is to investigate whether exo-enzymatically mediated chlorination of fulvic acid (FA) results in the formation of chlorinated groups within the macromolecules which correspond to those which were previously detected in soil and surface water samples. The chlorination was carried out by exposing FA to a commercial chloroperoxidase (CPO) in the presence of chloride and hydrogen peroxide. The exposed FA was then chemically degraded using an oxidative technique and finally analysed for four different aromatic groups and their chlorinated analogues. The particular aromatic groups included were the methyl esters of 4-ethoxybenzoic acid, 3-methoxy-4-ethoxybenzoic acid, 3,4-diethoxybenzoic acid, and 3,5-dimethoxy-4-ethoxybenzoic acid, along with their mono- and dichlorinated analogues. Prior to the chemical degradation procedure, the FA was analysed for AOX (adsorbable organic halogens) and chlorinated acetic acids. The original FA contained 1.4 mg Cl(org) g(-1) and detectable amounts of two chlorinated aromatic groups. After exposure to the enzyme, the concentration of AOX increased to 44.3 mg Cl(org) g(-1) and detectable amounts of four chlorinated aromatic groups as well as di- and trichloroacetic acid were found.     

Rate of abiotic formation of 1,1-dichloroethylene from 1,1,1-trichloroethane in groundwater

The abiotic transformation of the halogenated aliphatic compound, 1,1,1-trichloroethane (TCA), to 1,1-dichloroethylene (1,1-DCE) in groundwater was measured in the laboratory at 20°C and neutral pH. The measured pseudo first-order disappearance rate constant for TCA was 0.11 ± 0.16yr⁻¹ (95% confidence interval). The formation rate constant for 1,1-DCE could be determined with greater precision, and was found to be 0.040 ± 0.003 yr^-1. These results indicate the 95% confidence interval for TCA half-life at 20°C and pH 7 in homogeneous solution is 2.8 to 19 yrs. While these results confirm that 1,1-DCE is a product from the abiotic transformation of TCA, other products such as acetic acid are also possible, although they were not measured.     

Photodecomposition of humic acid and natural organic matter in swamp water using a TiO2-coated ceramic foam filter: Potential for the formation of disinfection byproducts

This paper reports on the photodecomposition of aqueous humic acid (HA) by a TiO₂-coated ceramic foam filter (TCF) reactor and on the potential for the formation of disinfection byproducts (DBPs) upon chlorination of the photocatalytically treated solutions. This photocatalytic reactor can also be applied to the removal of natural organic matter (NOM) in swamp waters. The proposed photocatalytic reaction system was operated as per standardized methodologies. First, the ability of the TCF to decompose HA (a representative compound of NOM) was evaluated from the changes in the total organic carbon (TOC) and UV₂₅₄ with the reaction time. Remarkably, TOC removal and UV₂₅₄ values ranging from 44% to 61% and from 60% to 83%, respectively, were achieved. The potential for the formation of DBPs (total trihalomethane and total haloacetic acid) by chlorination of the phototreated solution was strongly dependent on the TOC removal and UV₂₅₄ values in the solution. The degree of photodecomposition of NOMs in the swamp water samples and the DBP formation potential showed similar trends as in the case of the standard solutions containing HA. The method used in this study could be effectively used to evaluate the efficiency of TCF for reducing HA and NOM, while suppressing the formation of DBP products.     

Bromide affecting drinking water mutagenicity

The effect of bromide on the mutagenicity of artificially recharged groundwater and purified artificially recharged groundwater after chlorine, ozone, hydrogen peroxide, permanganate, and UV treatments alone and in various combinations was studied. The highest mutagenicity was observed after chlorination, while hydrogen peroxide-ozone-chlorine treatment produced the lowest value for both waters. Chlorinated waters, which were spiked with bromide, had up to 3.7 times more mutagenic activity than waters without bromide after every preoxidation method. 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) was found to correspond as much as 76% of the overall mutagenicity in the waters not spiked with bromide. MX formation was found to be lower when the treated water contained bromide, implicating the formation of brominated MX analogues. Trihalomethane formation increased when the treated water contained bromide.     

Formation of chloroacetic acids from soil,humic acid and phenolic moieties

The mechanism of formation of chloroacetates, which are important toxic environmental substances, has been controversial. Whereas the anthropogenic production has been well established, a natural formation has also been suggested. In this study the natural formation of chloroacetic acids from soil, as well as from humic material which is present in soil and from phenolic model substances has been investigated. It is shown that chloroacetates are formed from humic material with a linear relationship between the amount of humic acid used and chloroacetates found. More dichloroacetate (DCA) than trichloroacetate (TCA) is produced. The addition of Fe(2+), Fe(3+) and H(2)O(2) leads to an increased yield. NaCl was added as a source of chloride. We further examined the relationship between the structure and reactivity of phenolic substances, which can be considered as monomeric units of humic acids. Ethoxyphenol with built-in ethyl groups forms large amounts of DCA and TCA. The experiments with phenoxyacetic acid yielded large amounts of monochloroacetate (MCA). With other phenolic substances a ring cleavage was observed. Our investigations indicate that chloroacetates are formed abiotically from humic material and soils in addition to their known biotic mode of formation.     

Effects of thiocyanate on the formation of free cyanide during chlorination and ultraviolet disinfection of publicly owned treatment works secondary effluent.

Cyanide has been detected in effluent of some publicly owned treatment works (POTWs) at levels exceeding influent concentration. Thiocyanate (SCN-) is a cyanide-related compound encountered in most POTW influents and may be decomposed to free cyanide (CN-) under some circumstances. Effects of SCN- on the formation of cyanide during chlorination and UV disinfection were studied through a laboratory study with synthetic solutions and POTW secondary effluent. Results indicated that CN- was detected in SCN- solutions after chlorination in which the chlorine dose or reaction time was not sufficient to destroy SCN-completely, thus ensuring no residual chlorine to destroy any CN-produced. It was also found that SCN can be broken down to yield cyanide by UV irradiation. In addition, SCN- was observed to cause significant positive error in the conventional total cyanide analysis technique involving acidic distillation and colorimetric measurement when nitrate was present in the sample.     

Breakpoint chlorination curves of greywater.

A study on chlorination of raw greywater with hypochlorite is reported in this paper. Samples were chlorinated in a variety of conditions, and residual chlorine (Cl2) was measured spectrophotometrically. For each sample, the chlorination curve (chlorine residuals versus chlorine dose) was obtained. Curves showed the typical hump-and-dip profile attributable to the formation and destruction of chloramines. It was observed that, after reactions with strong reductants and chloramines-forming compounds, the remaining organic matter exerted a certain demand of chlorine. The evolution of chlorination curves with addition of ammonia and dodecylbencene sulfonate sodium salt and with dilution of the greywater sample were studied. In addition, chlorination curves at several contact times have been obtained, resulting in slower chlorine decay in the hump zone than in the dip zone. In addition, the decay of coliforms in chlorinated samples was also investigated. It was found that, for a chlorination dosage corresponding to the maximum of the hump zone (average 8.9 mg Cl2/ L), samples were negative in coliforms after 10 to 30 minutes of contact time. After-growth was not observed within 3 days after chlorination. Implications in chlorination treatments of raw greywater can be derived from these results.     

Formation of disinfection by-products in chlorinated swimming pool water.

The formation of five volatile disinfection by-products (DBPs: chloroform, bromodichloromethane, chloral hydrate, dichloroacetonitrile, and 1,1,1-trichloropropanone) by the chlorination of the materials of human origin (MHOs: hair, lotion, saliva, skin, and urine) in a swimming pool model system was examined. Chlorination reactions took place with a sufficient supply of chlorine residuals (0.84 mg Cl2/l < total chlorine < 6.0 mg Cl2/l) in 300 ml glass bottles containing either ground water or surface water as a reaction medium at 30 degrees C and pH 7.0, for either 24 or 72 h. A longer reaction period of 72 h or a higher content of organic materials led to the increased formation of DBPs. Of the DBPs formed by the reaction, chloroform was a major compound found in both ground and surface waters. The formation of chloroform and bromodichloromethane per unit total organic carbon (TOC) concentration was suppressed when all types of MHOs were added to the surface water that already contained DBP precursors such as humic substances. However, the formation of dichloroacetonitrile was promoted, probably due to the increased degradation reactions of nitrogen-containing compounds such as urea and proteins of human origin. In conclusion, the materials of swimmers' origin including hair, lotion, saliva, skin, and urine add to the levels of DBPs in swimming pool water, and any mitigation measures such as periodic change of water are needed to protect swimmers from elevated exposures to these compounds.     

MBR出水氯、紫外、臭氧单独与组合消毒

采用氯、紫外和臭氧单独与2种组合工艺对MBR工艺中试出水进行了消毒实验,研究了不同消毒方式对指示性微生物的去除效果以及消毒副产物三卤甲烷(THMs)生成量随有效氯投加量的变化.结果表明,组合工艺消毒效果明显优于单独消毒效果,紫外剂量为25 mJ/cm2与有效氯投加量为3 mg/L的紫外与氯组合、臭氧投加量为6 mg/L与有效氯投加量为4 mg/L的臭氧与氯组合2种工艺消毒后出水中的总大肠菌群指标均满足《污水再生利用城市杂用水水质》(GB/T 18920-2002)的要求.THMs生成量随着有效氯投加量的增加而增加.相对紫外与氯组合消毒,臭氧与氯组合消毒可以大幅度降低THMs生成量,有效氯投加量为4 mg/L时,THMs生成浓度为14.11 μg/L,比氯单独消毒过程降低了37.19%.     

松花江饮用水氯消毒中氯仿形成的优化控制

通过对松花江水进行大量实验 ,找出TOC的含量、投氯量、温度和 pH值等对氯仿形成的定量关系 ,确定了饮用水氯化的优化条件 ,使饮用水氯化过程中形成的氯仿含量不超过国家饮用水的标准     

微纳米气泡/UV/K2S2O8协同处理模拟垃圾渗沥液

以垃圾渗沥液中的主要污染物冰乙酸、正丁酸、正己酸和氨组成的混合物为处理对象,采用微纳米气泡联合紫外灯活化过硫酸盐法处理模拟垃圾渗沥液,考察了反应时间、过硫酸钾投加量、pH、紫外灯功率、微纳米气泡进气量对污染物去除效果的影响。结果表明：微纳米气泡对紫外灯活化过硫酸盐法有显著的协同作用。当反应时间为180 min、过硫酸钾投加量为4 g·L⁻¹、pH=6、紫外灯功率为10 W、微纳米气泡进气量为30 mL·min⁻¹时,污染物的去除效果最佳,COD去除率为60.68%,TOC去除率为48.05%,氨氮去除率为42.1%。自由基淬灭实验结合EPR表征结果表明,羟基自由基和硫酸根自由基为降解过程中主要的活性物质。溶液中无机碳含量增加,说明废水中有机物分解为二氧化碳和水。     

Precursors and nitrogen origins of trichloronitromethane and dichloroacetonitrile during chlorination/chloramination

The formation of trichloronitromethane (TCNM) and dichloroacetonitrile (DCAN) was investigated during chlorination and chloramination of 31 organic nitrogen (org-N) compounds, including amino acids, amines, dipeptides, purines, pyrimidones and pyrroles. Tryptophan and alanine generated the greatest amount of TCNM during chlorination process and asparagine and tyrosine yielded the highest amount of TCNM during chloramination process. Tryptophan, tyrosine, asparagine, and alanine produced more DCAN than other org-N compounds regardless of chlorination or chloramination. TCNM and DCAN formation was higher by chlorination than by chloramination. NH₂Cl:org-N molar ratios, reaction time, and pH affected N-DBPs formation in varying degrees. TCNM and DCAN yields were usually high during chloramination of tyrosine, asparagine, and methylpyrrole under the following reaction conditions: NH₂Cl:org-N molar ratios greater than 10, reaction time for 1 d, and at pH 7.2. NH₂Cl as a major nitrogen origin in TCNM and DCAN was confirmed via labeled ¹⁵N-monochloramine during chloramination of tyrosine, asparagine and methylpyrrole. In contrast, the majority of nitrogen in TCNM originated from glycine, and that in DCAN originated from pyrrole. Based on the intermediates identified by gas chromatography/mass spectrometry (GC/MS), a pathway scheme was proposed for TCNM and DCAN formation.     

水源地生态工程对消毒副产物生成的影响

水源地生态工程可改善饮用水水源水质,但其中的水生生物代谢物可能是消毒副产物(DBPs)前体物的来源。本文构建现场实验装置探究了水源地生态工程对原水水质的影响及原水中主要消毒副产物前体物的来源,考察了氯投量、温度以及pH对香蒲根分泌物、菰根分泌物和鲢鱼排泄物氯化后消毒副产物生成的影响。结果表明,实验装置对NH₄⁺-N、TN和TP的平均总去除率分别为74.93%、53.98%和73.02%,总DOC沿程增加。溶解性有机物(DOM)中分子质量分布在<500 Da的DOC含量总体上呈沿程减少的趋势,>3 000 Da的DOC沿程有所增加。总三卤甲烷生成势(TTHMFP)和总卤乙酸生成势(THAAFP)沿程呈现增加的趋势,分子质量<3 000 Da的有机物中TTHMFP和THAAFP沿程有所下降,分子质量>3 000 Da的TTHMFP和THAAFP呈沿程增加的趋势。考察了装置中3种水生生物代谢物经氯化后得到的二氯乙酸(DCAA)、三氯乙酸(TCAA)、三氯甲烷(TCM)和二氯乙腈(DCAN)4种消毒副产物生成势,均随着氯投量和温度的增加而升高,主要消毒副产物为TCAA。酸性条件有利于抑制DCAA和TCM的生成,碱性条件有利于抑制TCAA的生成,DCAN的生成量总体上随着pH的升高呈现先上升后下降的趋势。