• 상하수도학회지
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• 제18권5호
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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.

• 한국환경과학회지
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• 제21권9호
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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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• 제34권6호
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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.

• 분석과학
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• 제16권3호
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• pp.249-260
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• 2003

한강에서 채취한 원수에 염소소독제인 hypochlorite를 $10{\mu}g/m{\ell}$의 농도로 투여한 후 1시간~14일까지 TOC (total organic carbon), 잔류염소량 및 탁도 등을 측정하고 THMs (trihalomethanes), HANs (haloacetonitriles), HKs (haloketones), chloral hydrate 및 HAAs (haloacetic acids) 등의 염소소독 부산물의 생성율을 조사하였다. 그 결과 잔류염소량은 투여후 1시간 경과 시 $6{\mu}g/m{\ell}$ 이상에서 14일째에 $1.23{\mu}g/m{\ell}$으로 감소하였으며 TOC 및 탁도는 큰 차이가 없었다. 7일 후 발생한 총 소독부산 물의 농도는 $101.3ng/m{\ell}$ (789.6 nM)이며 이 중 THMs이 69%로 가장 큰 비중을 차지하였다. 그 외에 HAAs가 19%, chloral hydrate가 10% 정도 검출되었으며, HANs와 HKs 및 chloropicrin 등은 미량 검출되었다. THMs 중에서는 chloroform이 $61.5ng/m{\ell}$로 총 THMs 중 약 89% 정도를 차지하였으며 HANs 중에서는 DCAN이 95%인 $0.72ng/m{\ell}$, HAAs 중에서는 TCAA가 50% 등으로 가장 높은 비율로 검출되었다. 각 부산물의 발생량의 상관관계를 조사한 결과 THMs과 HANs의 경우 THMs의 농도가 $40ng/m{\ell}$인 지점을 경계로 HANs과 경쟁적 발생관계가 있음이 나타났다. HAAs의 경우는 특별한 경향성을 나타내지 않았으나 전체적으로 초기에 산화상태가 큰 화합물에서 산화상태가 작은 화합물로 점차 변화하는 것으로 관찰되었다.

• 한국환경과학회지
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• 제21권8호
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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.

• 분석과학
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• 제17권1호
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• pp.69-81
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• 2004

한강과 낙동강에서 채취한 원수에 염소소독제인 hypochlorite를 $10{\mu}g/mL$의 농도로 투여한 후 1시간 ~ 14일까지 TOC (total organic carbon), 잔류염소량 및 14종의 염소소독부산물 생성율을 조사하였다. 그 결과 TOC 및 탁도는 큰 차이가 없었으며 잔류염소량은 한강에서 투여 후 1시간 경과 시 $6{\mu}g/mL$ 이상에서 14일째에 $1.23{\mu}g/mL$으로 감소한 반면 낙동강의 경우 3일 이후 거의 존재하지 않았다. 7일 후 발생한 총 소독부산물의 농도는 한강의 경우 101.3 ng/mL (789.6 nM)이며 이 중 THMs (trihalomethanes)가 68%로 가장 큰 비중을 차지하였다. 그 외에 HAAs (haloacetic acids, 19%), chloral hydrate(10%)가 검출되었으며, 낙동강의 경우 총 소독부산물의 농도가 98.4 ng/mL (678.6 nM)이며 이 중 HAAs가 57%로 가장 큰 비중을 차지하였다. 그 외에 THMs (34%), HANs (haloacetonitriles, 5%) 및 chloropicrin등 질소화합물의 농도가 증가하였다. 이는 낙동강의 경우 한강에 비해 상대적으로 많이 포함된 암모니아성 질소가 소독제인 염소와 반응하여 클로라민을 생성함으로써 염소에 의한 소독효과와 클로라민에 의한 소독효과를 함께 나타내기 때문인 것으로 사료되며 전체적인 소독부산물들의 생성비율 경향을 살펴보면 소독제의 종류에 따라 소독부산물의 생성패턴에 차이가 있으나 산성도가 큰 HAAs의 초기 생성농도가 높고 점차 THMs의 생성속도가 증가하였다.

• Environmental Engineering Research
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• 제20권4호
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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.

• 한국환경과학회지
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• 제13권1호
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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.

• 분석과학
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• 제22권3호
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• pp.272-276
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• 2009

하수처리장 방류수의 염소 소독효율과 소독부산물 발생 특성에 대해 고찰하였다. 총대장균군의 소독효율을 조사한 결과 99% 이상의 소독 효율을 얻기 위해서는 0.5 mg/L에서는 30분, 1.0 mg/L에서는 20분, 1.5 mg/L이상의 농도에서는 10분의 접촉시간이 필요한 것으로 나타났다. 염소주입농도 0.5 mg/L에서 10분간 접촉시킬 때 THMs의 최대 농도는 $32.2{\mu}g/L$이었으며, 이중 chloroform은 최대 $28.4{\mu}g/L$가 생성되어 THMs의 88.1%를 차지하였다. HANs의 최대 농도는 $2.97{\mu}g/L$이었으며, HAAs의 최대 농도는 $16.29{\mu}g/L$로 상당히 낮게 나타났다. 연구대상 하수처리장 최종 방류수의 연평균 잔류염소 농도는 0.4 mg/L이었으며, 염소소독부산물 실험 결과 THMs은 최대 $9.21{\mu}g/L$, 평균 $2.79{\mu}g/L$로 나타났으며 HANs과 HAAs는 검출한계 이하로 나타났다.

• Environmental Analysis Health and Toxicology
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• 제12권3_4호
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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.