Development of Analytical Methods for Micro Levels of Naphthalene and TNT in Groundwater by HPLC-FLD and MSD

HPLC-FLD와 MSD를 이용한 지하수 중 나프탈렌 및 TNT의 미량 분석법 개발

  • Park, Jong-Sung (Department of Chemistry and Environmental Sciences, Korea Army Academy at Young-Cheon) ;
  • Oh, Je-Ill (Department of Civil and Environmental Engineering, Chung-Ang University) ;
  • Jeong, Sang-Jo (Department of Civil Engineering and Environmental Sciences, Korea Military Academy) ;
  • Choi, Yoon-Dae (Department of Chemistry and Environmental Sciences, Korea Army Academy at Young-Cheon) ;
  • Her, Nam-Guk (Department of Chemistry and Environmental Sciences, Korea Army Academy at Young-Cheon)
  • 박종성 (육군3사관학교 화학환경과학과) ;
  • 오재일 (중앙대학교 건설환경공학과) ;
  • 정상조 (육군사관학교 토목환경학과) ;
  • 최윤대 (육군3사관학교 화학환경과학과) ;
  • 허남국 (육군3사관학교 화학환경과학과)
  • Received : 2009.08.19
  • Accepted : 2009.10.05
  • Published : 2009.12.31

Abstract

Naphthalene and TNT (2,4,6-trinitrotoluene) are defined by U.S. EPA as possible carcinogenic compounds known to have detrimental effects on the aquatic ecosystem and human body. There are, however, few researches on methods of analyzing micro-levels of naphthalene and TNT dissolved in groundwater. This study introduces and evaluates the newly developed analytical methods of measuring naphthalene and TNT in groundwater by using HPLC-FLD (Fluorescence detector) and MSD (Mass detector). The MDL, LOQ and salt effect of these methods, respectively, are compared with those of conventional methods which use HPLC-UV. For the analysis of naphthalene, HPLC-FLD was set in the maxima wavelength (Ex: 270 nM, Em: 330 nM) obtained from 3D-Fluorescence to be compared with HPLC-UV in 266 nM wavelength. The MDL ($0.3\;{\mu}g/L$) and LOQ ($2.0\;{\mu}g/L$) of naphthalene by using HPLC-FLD were approximately 80 times lower than those analyzed by HPLC-UV (MDL: $23.3\;{\mu}g/L$, LOQ: $163.1\;{\mu}g/L$). HPLC-MSD were used in comparison with HPLC-UV in 230 and 254 nM wavelength for the analysis of TNT. The MDL ($0.13\;{\mu}g/L$) and LOQ ($0.88\;{\mu}g/L$) of TNT analyzed by using HPLC-MSD were approximately 130 times lower than those obtained by using HPLC-UV in 230 nM (MDL: $16.8\;{\mu}g/L$, LOQ: $117.5\;{\mu}g/L$). The chromatogram of TNT analyzed by using HPLC-UV in 230 nM displayed elevated baseline as the concentration of ${NO_3}^-$ increases beyond 21 mg/L, while the analysis using HPLC-MSD did not demonstrate any change in baseline in presence of ${NO_3}^-$ of 63.7 mg/L which is 3.5 times higher than average concentration in groundwater. In conclusion, HPLC-FLD and HPLC-MSD may be used as suitable methods for the analysis of naphthalene and TNT in groundwater and drinking water. These methods can be applied to the monitoring of naphthalene and TNT concentration in groundwater or drinking water.

나프탈렌과 TNT는 미국 환경청(U.S. EPA)에서 규정한 발암가능성 물질로(Group C), 환경으로 방출될 경우 수생태계와 인체에 심각한 영향을 주는 것으로 알려져 있다. 그러나 지하수 내 두 물질의 미량 분석법에 대한 기존연구는 매우 미비한 실정이다. 이에 본 연구에서는 HPLC-FLD(Fluorescence etector)와 MSD(Mass detector)를 이용한 지하수 내 나프탈렌 및 TNT의 미량분석법을 개발하여, MDL과 LOQ 및 이온영향을 조사하고, 현재 사용되고 있는 HPLC-UV 분석법과 비교 평가하였다. 나프탈렌의 경우, 3D-Fluorescence를 통하여 확인된 최고의 파장(Ex: 270 nM, Em: 330 nM)이 HPLC-FLD에 적용되었고, $0.3\;{\mu}g/L$의 MDL과 $2.0\;{\mu}g/L$의 LOQ가 획득되었다. 이는 현재 방법(HPLC-UV; MDL: $23.3\;{\mu}g/L$, LOQ: $163.1\;{\mu}g/L$)보다 약 80배 우수한 결과이며, U.S. EPA의 음용수 권고기준($700\;{\mu}g/L$)의 약 350배 이하까지 정량분석이 가능한 수치이다. TNT의 경우, 새롭게 제시된 HPLC-MSD로 측정한 방법(MDL: $0.13\;{\mu}g/L$, LOQ: $0.88\;{\mu}g/L$)이 HPLC-UV(MDL: $16.8\;{\mu}g/L$, LOQ: $117.5\;{\mu}g/L$ at 230 nM)보다 약 130 배 우수한 것으로 조사되었고, U.S. EPA의 음용수 권고기준($20\;{\mu}g/L$)보다 약 23배 낮은 농도까지 정량분석이 가능한 것을 확인하였다. 또한 HPLC-UV(230 nM)의 분석법은 ${NO_3}^-$ 농도가 증가할수록(특히 21 mg/L 이상) 크로마토그램의 기준선이 증가하여 정량에 방해를 주었으나, HPLC-MSD 분석법은 국내 지하수 평균 농도보다 약 3.5배인 63.7 mg/L에서도 분석의 영향 없이 안정한 크로마토그램을 보여주었다. 따라서 새롭게 제시된 HPLC-FLD와 MSD에의한 나프탈렌과 TNT 분석법은 지하수 및 음용수 미량분석에 적합하며, 관련분야 연구에 크게 도움이 될 것이다.

Keywords

Acknowledgement

Supported by : 환경부

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