• Journal of Korean Society of Water and Wastewater
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• v.18 no.5
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• pp.628-637
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• 2004

In many drinking water treatment plants, chlorination process is one of the main techniques used for the disinfection of water. This disinfecting treatment leads to the formation of disinfection by-products (DBPs) such as haloacetonitriles (HANs), trihalomethanes (THMs), haloacetic acids (HAAs). In this study, headspace-solid phase microextraction (HS- SPME) technique was applied for the analysis of HANs in drinking water. The effects of experimental parameters such as selection of SPME fiber, the addition of salts, magnetic stirring, extraction temperature, extraction time and desorption time on the analysis were investigated. Analytical parameters such as linearity, repeatability and detection limits were also evaluated. The $50/30{\mu}m$-divinylbenzene/carboxen/polydimethylsiloxane fiber, extraction time of 30 minutes, extraction temperature of $20^{\circ}C$ and desorption time of 1 minute at $260^{\circ}C$ were the optimal experimental conditions for the analysis of HANs. The correlation coefficients ($r^2$) for HANs was 0.9979~0.9991, respectively. The relative standard deviations (%RSD) for HANs was 2.3~7.6%, respectively. Detection limits (LDs) for HANs was $0.01{\sim}0.5{\mu}g/L$, respectively.

• Journal of Environmental Science International
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• v.21 no.9
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• pp.1031-1041
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• 2012

This study was carried out to investigate the characteristics of disinfection by-products (DBPs-trihalomethanes (THMs), haloacetic acids (HAAs) and haloacetonitriles (HANs) formation in chlorination of principal raw waters used for drinking water on Jeju Island, Korea. The domestic water supply of other area and humic acid solution (HA) were used as a reference point. The effects of chlorine contact time, solution temperature and pH on DBPs formation potential (DBPFP) were investigated for raw waters. In addition, the effect of $Br^-$ was studied for HA. The DBPFP (THMFP, HAAFP and HANFP) were increased with increasing chlorine contact time. Comparing the individual DBPFPs for raw waters, they decreased in the order of HAAFP > THMFP ${\geq}$ HANFP. As the solution temperature was increased, the THMFP, HAAFP and HANFP increased. With increasing the solution pH, the THMFP was increased, but HAAFP and HANFP were decreased. With the addition of 0.3 mg/L $Br^-$ for HA, the DBPFP was increased and the major chemical species changed: from trichloromethane to dibromochloromethane and tribromomethane for THMs; from dichloroacetic acid and trichloroacetic acid to tribromoacetic acid for HAAs; and from dichloroacetonitrile to dibromoacetonitrile for HANs.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1783-1790
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• 2013

A simultaneous analytical method has been developed for the fluorimetric determination of haloacetonitriles (HANs) [dichloroacetonitrile (DCAN), trichloroacetonitrile (TCAN), dibromoacetonitrile (DBAN), haloacetamides [dichloroacetamide (DCAD), and trichloroacetamde (TCAD)] in drinking water by using the combined on-line perconcentration/reversed phase liquid chromatography (RPLC)-postcolumn detection system. This on-line perconcentration system was achieved by employing a precolumn packed with a commercial solid phase extraction (SPE) sorbent for the enrichment and purification of the target analytes. The haloacetonitriles and haloacetamides were separated on CN analytical column in a 7.5% methanol-0.02 M phosphate buffered mobile phase at pH 3. The column effluents were reacted with postcolumn reagents of ophthaldialdehyde (OPA) and sulfite ion at pH 11.5, to produce a highly fluorescent isoindole fluorophore, which were measured with a fluorescence detector. Under the optimized conditions for RPLC and the postcolumn derivatization system all of the coefficient of determination of the standard calibration curves for the target analytes were over 0.99 and had a linear range from 5 to 100 ${\mu}g/L$. The detection limits showed 1.6 ${\mu}g/L$ for DCAD, 0.1 ${\mu}g/L$ for TCAD, 0.6 ${\mu}g/L$ for DCAN, 1.6 ${\mu}g/L$ for TCAN and 1 ${\mu}g/L$ for DBAN, and the recoveries were ranged from 64 to 99% except for DCAD with precisions less than 4.9% in distilled water, and from 72(${\pm}4%$) to 116%(${\pm}2%$) in tap water.

• Analytical Science and Technology
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• v.16 no.3
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• pp.249-260
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• 2003

The disinfection of drinking water to control microbial contaminants results in the formation of secondary chemical contaminants, DBPs (disinfection by-products). It was studied the formation pattern of DBPs in drinking raw water after hypochlorite, chlorine disinfectant, was added in this study. It was determined TOC (total organic carbon), residual chlorine, turbidity and DBPs in raw water from Han-river during 1~14 days. Total DBPs was $101.3ng/m{\ell}$ (789.6 nM) after 7days and THMs (trihalomethanes) are the dominant portion of 69%. HAAs (haloacetic acids) and chloral hydrate were determined 19% and 10% respectively, and HANs (haloacetonitriles), HKs (haloketones) and chloropicrin were analyzed in trace level. Chloroform occupied about 89% in total THMs in concentration of $61.5ng/m{\ell}$, 95% of HANs was DCAN (dichloroacetonitrile) in $0.72ng/m{\ell}$, 50% of HAAs was TCAA (trichloroacetic acid). On the study of relationship in formation among the DBPs, HANs forms with THMs competitively to the point of the concentration of $40ng/m{\ell}$ of THMs. For HAAs, it did not show the prominent tendency. But it was observed that the compounds of large oxidation state are formed at first, and becomes to the compounds of low oxidation states.

• Journal of Environmental Science International
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• v.21 no.8
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• pp.1015-1021
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• 2012

Formation of disinfection by-products (DBPs) including trihalomethans (THMs), haloacetic acid (HAAs), haloacetonitriles (HANs) and others from chlorination of algogenic organic matter (AOM) of Microcystis sp., a blue-green algae. AOM of Microcystis sp. exhibited a high potential for DBPs formation. HAAs formation potential was higher than THMs and HANs formation potential. The percentages of dichloroacetic acid (DCAA) and trichloroacetic acid (TCAA) formation potential were 43.4% and 51.4% in the total HAAs formation potential. In the case of HANs formation potential, percentage of dichloroacetonitrile (DCAN) formation potential was 97.7%. Other DBPs were aldehydes and nitriles such as acetaldehyde, methylene chloride, isobutyronitrile, cyclobutanecarbonitrile, pentanenitrile, benzaldehyde, propanal, 2-methyl, benzyl chloride, (2-chloroethyl)-benzene, benzyl nitrile, 2-probenenitrile and hexanal.

• Analytical Science and Technology
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• v.17 no.1
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• pp.69-81
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• 2004

The formation pattern of DBPs (disinfection by-products) in raw water treated with hypochlorite, chlorine disinfectant was studied. TOC (total organic carbon), residual chlorine, turbidity and 14 DBPs in raw water from Han-river and Nakdong river during 1 ~ 14 days were determined. Total DBPs in Han river was 101.3 ng/mL (789.6 nM) after 7days and THMs (trihalomethanes) are the dominant portion of 68%. HAAs (haloacetic acids) and chloral hydrate were determined 19% and 10% respectively. In Nakdong river total DBPs was 98.4 ng/mL (678.6 nM) and dominant class was HAAs. (55.8 ng/mL, 57%) THMs(34%) and N-compounds like HANs (haloacetonitriles, 5%) and chloropicrin were increased. It may be explained that high concentration of NH4-N in Nakdong river react with chlorine produced chloramine and this formed different pattern of DBPs. As a result, total DBPs formation pattern depends on raw water and disinfectant and in generally the initial concentration of acidic HAAs was high and THMs was increased gradually.

• Environmental Engineering Research
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• v.20 no.4
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• pp.342-346
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• 2015

Haloacetonitriles (HANs) are nitrogenous disinfection by-products (DBPs) that have been reported to have a higher toxicity than the other groups of DBPs. The adsorption process is mostly used to remove HANs in aqueous solutions. Functionalized composite materials tend to be effective adsorbents due to their hydrophobicity and specific adsorptive mechanism. In this study, the removal of dichloroacetonitrile (DCAN) from tap water by adsorption on thiol-functionalized mesoporous composites made from natural rubber (NR) and hexagonal mesoporous silica (HMS-SH) was investigated. Fourier-transform infrared spectroscopy (FTIR) results revealed that the thiol group of NR/HMS was covered with NR molecules. X-ray diffraction (XRD) analysis indicated an expansion of the hexagonal unit cell. Adsorption kinetic and isotherm models were used to determine the adsorption mechanisms and the experiments revealed that NR/HMS-SH had a higher DCAN adsorption capacity than powered activated carbon (PAC). NR/HMS-SH adsorption reached equilibrium after 12 hours and its adsorption kinetics fit well with a pseudo-second-order model. A linear model was found to fit well with the DCAN adsorption isotherm at a low concentration level.

• Journal of Environmental Science International
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• v.13 no.1
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• pp.55-59
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• 2004

The effect of ozone on the formation and the removal of disinfection byproducts(DBPs) of chlorination process was studied to elucidate the performance of water treatment process. The samples of raw water, prechlorination process, and preozonation process were analyzed quantitatively according to the Standard Methods for the Examination of drinking water. As a result, most of total trihalomethanes(THMs) which were formed in prechlorine treatment process was not removed in the preozonation process. Most of haloacetic acids(HAAs), haloacetonitriles(HANs), and chloral hydrate(CH) was removed in sedimentation and biological activated carbon(BAC) filtration processes. However, DBPs were increased more or less by postchlorine step. In particular, the formation of THMs and HAAs depends on ozone more than chlorine, but, the formation of HANs and CH depends on chlorine more than ozone. The seasonal variation of DBPs concentration for the year needs to be investigated to study the temperature effect because DBPs strongly depend on temperature among various efficient factors.

• Analytical Science and Technology
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• v.22 no.3
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• pp.272-276
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• 2009

This study was performed to investigate the disinfection efficiency and the generation characteristics of disinfection by-products (DBPs) in the sewage effluent. In the case of total coliforms, disinfection efficiency higher than 99%, the required contact time was 30 min at chlorine dose of 0.5 mg/L, 20 min at 1.0 mg/L, and 10 min at 1.5 mg/L, respectively. When the sewage effluent was disinfected with chlorine dose of 0.5 mg/L for 10 min, the maximum generation concentration of trihalomethanes (THMs), haloacetonitriles (HANs) and haloacetic acid (HAAs) were $32.2{\mu}g/L$, $2.97{\mu}g/L$, and $16.29{\mu}g/L$, respectively. The concentration of chloroform was $28.4{\mu}g/L$ corresponding to 88.1% of the THMs. The concentration of HANs and HAAs were found to be inconsiderable. The average residual chlorine concentration of sewage effluent was 0.4 mg/L, the generation concentration of THMs was maximum $1.72{\mu}g/L$ and average $2.79{\mu}g/L$. HANs and HAAs were under the detection limit by GC/MSD.

• Environmental Analysis Health and Toxicology
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• v.12 no.3_4
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• pp.23-29
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• 1997

The main reason of applying chlorination is to sterilize microbes existing in the drinking water treatment. But chlorination could lead to the formation of disinfection by-products (DBPs) by the reaction of free chlorine with humic substance in the water. Especially the DBPs including trihalomethanes (THMs), haloacetic acids (HAAs), haloacetonitriles (HANs), and haloketones (HKs) exist in the tap water. The US environmental protection agency (US EPA) defines that trihalomethanes, dichloroacetic acid, trichloroacetic acid, and dichloroacetonitrile among DBPs are probable/possible human carcinogens. US EPA suggests maximum contaminant levels (MCLs) for THMs (80$\mu$g/L) and HAAs (60$\mu$g/L) in drinking water. In Korea, THMs in drinking water has been surveyed but DBPs in general has not been studied in drinking water practically. Therefore only THMs have been regulating as criteria compounds since 1990 but neither HAAs nor HANs. Researches on HAAs are yet to be found. HAA formation potentials(HAAFPs) have not been practiced. HAAs depends on the characteristics of water sources by chlorination. In this study, HAAFPs from three distinct sources were investigated by laboratory chlorination experiments. This study was performed to measure the level of HAAs in drinking water in Seoul area. At April 1996, after collecting the raw waters from the three sites with the different properties, the water samples were chlorinated at various conditions(pH 5.5, pH 7.0 and without pH adjustment) in the state of raw water to have 0. 5mg/L of residual chlorine concentration. And the raw water, treated water, and tap water of water treatment were collected to measure the HAAs concentration. The quantitative analysis of HAAs was conducted by US EPA methods.