Journal of Korean Society of Environmental Engineers (대한환경공학회지)

Korean Society of Environmental Engineers (대한환경공학회)
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Speciation Analysis of Arsenic Species in Surface Water

수중의 비소 종 분리 분석

  • Jeong, Gwan-Jo (Department of Chemical Engineering, University of Seoul) ;
  • Kim, Dok-Chan (Department of Chemical Engineering, University of Seoul)
  • 정관조 (서울시립대학교 화학공학과) ;
  • 김덕찬 (서울시립대학교 화학공학과)
  • Published : 2008.06.30
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Abstract

In this study, a technique of speciation and determination of the trace inorganic arsenic(As(III) and As(V)) in water sample using HPLC-DRC-ICP-MS has been developed. Isocratic mobile phase of 10 mM ammonium nitrate and 10 mM ammonium phosphate monobasic was used and methanol(5 v/v%) was used as flushing solvent. Selection of the best flow rate of reaction gas, O$_2$, and optimization of the parameters such as pH and flow rate of mobile phase, and injection volume of sample for the separation and detection of arsenic species were carried out. The oxygen flow rate of 0.5 mL/min, pH of 9.4 and flow rate of 1.5 mL/min of mobile phase, and injection volume of sample of 100 $\mu$L were found to be the best parameters for the speciation and determination of arsenic species. The analytical features of the method were detection limit 0.10 and 0.08 $\mu$g/L, precision(RSD) 4.3% and 3.6%, and recovery 95.2% and 96.4% for As(III) and As(V), respectively. Analysis time was 4 minutes per sample. Linear calibration graphs with r$^2$ = 0.998 were obtained for both As(III) and As(V). Speciation analysis of arsenic species in the raw water samples collected from the tributary streams to Han River and main stream of Paldnag were performed by the proposed method. The concentrations of As(III) ranged from 0.10 to 0.22 $\mu$g/L and As(V) concentrations ranged from 0.44 to 1.19 $\mu$g/L, and 93.5% of total arsenic was found to be As(V).

본 연구에서는 물속 As(III)와 As(V)의 종 규명분석에 필요한 HPLC와 DRC-ICP-MS의 최적조건을 설정하고, 이를 이용하여 한강 팔당수계 10개 지류 천으로부터 채취한 시료중의 As(III)와 As(V)를 분석 검토하였다. 종 분리를 위한 HPLC의 이동상으로는 10 mM ammonium nitrate와 10 mM ammonium phosphate monobasic을 사용하였으며, flushing solvent로는 5% v/v 메탄올을 사용하였다. 검출기는 DRC-ICP-MS를, 반응기체는 산소를 사용하였다. 최적 분석조건을 설정하기 위하여 이동상의 pH, 유량 및 시료 주입량과 DRC의 산소 유량을 달리하여 검토한 결과, 이동상의 pH는 9.4, 유량은 1.5 mL/min, 시료 주입량은 100 $\mu$L, 산소의 유량은 0.5 mL/min이었을 때 가장 좋은 분석조건으로 나타났다. 검정곡선은 As(III)와 As(V)에 대해 모두 r$^2$ = 0.998 이상의 선형성을 나타냈으며, As(III)의 검출한계는 0.10 $\mu$g/L, 정확도(RSD)는 4.3%, 회수율은 95.2%, As(V)의 검출한계는 0.08 $\mu$g/L, 정확도(RSD)는 3.6%, 회수율은 96.4%로 나타났다. 분석시간은 4분이었다. 설정된 파라미터를 적용하여 한강 팔당수계 유입 10개 지류 천에서 채수한 시료를 분석한 결과, As(III)는 0.10$\sim$0.22 $\mu$g/L, As(V)는 0.44$\sim$1.19 $\mu$g/L의 범위로 나타났으며, 총 비소의 93.5%가 As(V)의 형태인 것을 확인할 수 있었다.

Keywords

References

  1. Mandal, B. K. and Suzuki, K. T., "Arsenic round the world : a review," Talanta, 58, 201-235(2002). https://doi.org/10.1016/S0039-9140(02)00268-0
  2. IARC, "IARC monographs on the evaluation of carcinogenic risk to human: overall evaluations of carcinogenicity: an updating of IARC monographs, International Agency for Research on Cancer," pp. 100-206(1987).
  3. U.S Environmental Protection Agency, "Arsenic in drinking water," http://www.epa.gov/safewater/arsenic/, September (2006).
  4. APHA, AWWA, and WEF, Standard Methods for the Examination of Water and Wastewater, 19th ed., American Public Health Association, Washington D.C.(1995).
  5. WHO, Guidelines for drinking-water quality, Volume 1- Recommendation, 3rd ed., Geneva(2004).
  6. Terlecka, E., "Arsenic speciation analysis in water samples: A review of the hyphenated techniques," Environmental Monitoring and Assesment, 107, 259-284(2005). https://doi.org/10.1007/s10661-005-3109-z
  7. Featherstone, A. M., Butler, E. C. V., O'Grady, B. V., and Michel, P., "Determination of arsenic species in seawater by hydride generation atomic fluorescence spectroscopy," J. Anal. At. Spectrom., 19, 1355-1360(1998).
  8. Nakazato, T., Taniguchi, T., Tao, H., Tominaga, M., and Miyazaki, A., "Ion-exclusion chromatography combined with ICP-MS and hydride generation-ICP-MS for the determination of arsenic species in biological matrices," J. Anal. At. Spectrom., 15, 1546-1552(2000). https://doi.org/10.1039/b005981l
  9. B'Hymer, C., and Caruso, J. A., "Arsenic and its speciation analysis using high performance liquid chromatography and inductively coupled plasma mass spectrometry," J. Chromatogr. A., 1045, 1-13(2004). https://doi.org/10.1016/j.chroma.2004.06.016
  10. Tanner, S. and Baranov, V., "Theory, design, and operation of a dynamic reaction cell for ICP-MS," Atomic Spectroscopy, 20, 45-52(1999).
  11. 정관조, 김덕찬, 박현, "ICP-DRC/MS를 이용한 수중의 비소 측정," 대한환경공학회지, 28(8), 620-625(2006).
  12. Ronkart, S. N., Laurent, V., Carbonnelle, P., Mabon, N., Copin, A., and Barthelemy, J., "Speciation of five arsenic species(arsenite, arsenate, MMAAV, DMAAV and AsBet) in different kind of water by HPLC-ICP-MS," Chemosphere, 66, 738-745(2007). https://doi.org/10.1016/j.chemosphere.2006.07.056
  13. D'Ilio, S., Violante, N., Di Gregorio, M., Senofonte, O., and Petrucci, F., "Simultaneous quantification of 17 trace elements in blood by dynamic reaction cell inductively coupled plasma mass spectrometry(DRC-ICP-MS) equipped with a high-efficiency sample introduction system," Anal. Chim. Acta, 579, 202-208(2006). https://doi.org/10.1016/j.aca.2006.07.027
  14. Olesik, J. W. and Jones, D. R., "Strategies to develop methods using ion-molecule reactions in a quadrupole reaction cell to overcome spectral overlaps in inductively coupled plasma mass spectrometry," J. Anal. At. Spectrom., 21, 141-159(2006). https://doi.org/10.1039/b511464k
  15. Reuter, W. M., Davidowski, L., and Neubauer, K., "Speciation of five arsenic compounds in urine by HPLC/ ICP-MS," PerkinElmer-SCIEX, application note(2003).
  16. Neubauer, K. R., Reuter, W. M., Perrone, P. A., and Grosser Z. A., "Simultaneous arsenic and chromium speciation by HPLC/ICP-MS in environmental waters," Perkin- Elmer-SCIEX, application note(2004).