Journal of Korean Society of Environmental Engineers (대한환경공학회지)

Korean Society of Environmental Engineers (대한환경공학회)
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HPLC-MS/MS Detection and Sonodegradation of Bisphenol A in Water

HPLC-MS/MS를 이용한 Bisphenol A 분석 및 초음파에 의한 분해 특성 조사

  • Park, Jong-Sung (Department of Chemistry and Environmental Sciences, Korea Army Academy) ;
  • Yoon, Yeo-Min (Department of Civil and Environmental Engineering, University of South Carolina) ;
  • Her, Nam-Guk (Department of Chemistry and Environmental Sciences, Korea Army Academy)
  • 박종성 (육군3사관학교 화학환경과학과) ;
  • 윤여민 (미국사우스캐롤라이나대학교 토목환경공학과) ;
  • 허남국 (육군3사관학교 화학환경과학과)
  • Received : 2010.05.04
  • Accepted : 2010.06.29
  • Published : 2010.06.30
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Abstract

The optimal conditions for the analysis of BPA by HPLC-MS/MS was investigated and the ultrasound degradation capacity of the BPA, with the goal to establish the proper directions for analyzing infinitesimal quantities of BPA by HPLC-MS/MS was examined. The MDL and LOQ of BPA analyzed by HPLC-MS/MS were measured 0.13 nM and 1.3 nM respectively, its sensitivity about 620 and 32 times greater than HPLC-UV (MDL: 81.1 nM, LOQ: 811 nM) and FLD (MDL: 4.6 nM, LOQ: 46 nM). In other words, the new method enables the analysis of BPA with the accuracy up to one 1,180th of the amount specified in U.S. EPA guideline for drinking water. Degradation rate of BPA by ultrasound measured over 95% under 580 kHz and 1000 kHz frequency within 30 minutes of treatment, whereas the rate showed some decrease at 28 kHz frequency. At 580 kHz of ultrasound has proven to be the most effective among others at degradation rate and $k_1$ value, so we concluded that this frequency of ultrasound creates hospitable condition for the combined process of degradation by pyrolysis and oxidization. With the addition of 0.01 mM of $CCl_4$, BPA with the initial concentration of 1 ${\mu}M$ was degraded by more than 98% within 30 minutes, the $k_1$ value measured 5 minutes and 30 minutes into the experiment both showed increases by 1.4 and 1.1 times, respectively, compared with BPA without $CCl_4$. It is also found that the main degradation mechanism of BPA by ultrasound is oxidization process by OH radical, based on the fact that the addition of 10 mM of t-BuOH decreased the rate of BPA degradation by around 60%. However, 33% of BPA degradation rate obtained with the addition of t-BuOH implies further degradation done by pyrolysis or other sorts of radical beside OH radical.

본 연구는 극미량의 BPA 분석법을 정립하기 위하여 HPLC-MS/MS를 이용한 BPA 분석 조건을 개발하였고, 초음파를 이용한 BPA의 분해 특성을 조사하였다. HPLC-MS/MS에 의한 BPA의 MDL과 LOQ는 각각 0.13 nM과 1.3 nM로 조사되었는데, 이는 기존의 HPLC-UV (MDL: 81.1 nM, LOQ: 811 nM) 및 FLD (MDL: 4.6 nM, LOQ: 46 nM) 보다 약 620배 및 35배 우수하였으며, U.S. EPA의 음용수 권고기준(1.53 ${\mu}M$ 혹은 350 ${\mu}g/{\ell}$)의 약 1,180배 이하까지 정량분석이 가능하였다. 초음파 조사에 따른 BPA의 분해효율은 저주파(28 kHz)를 제외한 중?고주파 조건(580 and 1000 kHz)에서 반응 30분 이내에 95%이상 제거되었다. 특히 BPA의 분해효율 및 k1의 결과는 580 kHz에서 가장 우수하였는데, 이는 580 kHz 근처의 주파수 영역에서 최적의 초음파 공동현상 및 열분해/산화분해가 일어남을 알 수 있었다. 0.01 mM의 $CCl_4$를 첨가하여 분해효율을 측정한 결과 30분 이내에 BPA 초기농도(1 ${\mu}M$)의 98% 이상까지 제거되었으며, 반응 초기(5분)와 후기(30분)의 $k_1$값은 무첨가 반응에 비해 각각 1.4배 및 1.1배씩 증가하였다. 10 mM의 t-BuOH이 첨가된 결과 무첨가 반응에 비해 약 60% 이상 BPA 분해효율이 감소한 것을 감안할 때 BPA의 주된 초음파 기전은 OH 라디칼에 의한 산화분해임을 알 수 있었다. 그러나 t-BuOH이 첨가된 반응시간 동안(30분) 약 33%의 BPA가 분해가 일어난 것은 OH 라디칼 뿐 아니라 열분해 및 기타 라디칼 등에 의한 분해가 진행되었을 것으로 판단된다.

Keywords

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