Abstract
A fully automated online ultraviolet (UV) digestion method for subsequent mercury (Hg) quantification in humic matter containing river waters is reported. The new developed flow injection analysis system (FIAS) consists basically of a UV lamp, a meander-form quartz glass reaction tube for online irradiation of the sample, and a nano-gold collector for preconcentration of dissolved mercury species. The FIAS is coupled to an atomic fluorescence spectrometer (AFS) for Hg detection. The optimized procedure allows accurate mercury quantification in water samples with up to 15 mg C L−1 as dissolved organic carbon by addition of only 1% (v/v) of hydrogen peroxide solution and online UV irradiation for 6 min. Addition of strong oxidants and any other reagents is avoided due to the use of the catalytic active nano-gold collector. Here, preconcentration of Hg species, release of mercury as Hg0, and AFS measurement are performed without addition of any reagents. Hence, the proposed approach offers significant advantages over existing methods. Analytical figures of merit showed the good performance of the developed method: The limit of quantification was found to be as low as 0.14 ng Hg L−1. The linear working range is from 0.1 to 200 ng Hg L−1 and relative standard deviation is <6.0% (n = 9). The system was successfully validated by comparison of the mercury concentrations found in model and real water samples obtained by the reference method EPA 1631 and the proposed method. Furthermore, application to six real river waters confirmed the feasibility of the proposed approach.
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Abbreviations
- AFS:
-
Atomic fluorescence spectrometry
- C:
-
Carrier
- CV:
-
Cold vapor
- DOC:
-
Dissolved organic carbon
- EPA:
-
Environmental protection agency
- FIAS:
-
Flow injection analysis system
- GLS:
-
Gas–liquid separator
- ID:
-
Inner diameter
- NPOC:
-
Non-particular organic carbon
- OD:
-
Outer diameter
- P:
-
Peristaltic pump
- PET:
-
Polyethylene terephthalate
- S:
-
Sample
- SL:
-
Sample loop
- UPW:
-
Ultra-pure water
- UV:
-
Ultraviolet
References
EU Directive 2001/22/EG
Mason RP, Reinfelder JR, Morel FMM (1995) Water Air Soil Pollut 80:915–921
Mason RP, Fitzgerald WF, Morel FMM (1994) Geochim Cosmochim Acta 58:3191–3198
Pacyna EG, Pacyna JM, Steenhuisen F, Wilson S (2006) Atmos Environ 40:4048–4063
Selin NE (2009) Annu Rev Environ Resource 34:43–63
Cossa D, Martin J-M, Takayanagi K, Sanjuan J (1997) Deep-Sea Res Part II 44:721–740
Mason RP, Rolfhus KR, Fitzgerald WF (1998) Mar Chem 61:37–53
Bloom N (1989) Can J Fish Aquat Sci 46:1131–1140
Meili M (1997) Metal ions in biological systems. In: Sigel A, Sigel H (eds) Mercury and its effect on environment and biology, vol 34. Marcel Dekker, New York, pp 21–51
Leopold K, Foulkes M, Worsfold P (2010) Anal Chim Acta 663:127–138
Leopold K, Foulkes M, Worsfold P (2009) Trends Anal Chem 28(4):426–435
Ullrich SM, Tanton TW, Abdrashitova SA (2001) Crit Rev Env Sci Technol 31:241–293
Lockwood RA, Chen KY (1973) Environ Sci Technol 7:1028–1034
Leopold K, Harwardt L, Schuster M, Schlemmer G (2008) Talanta 76:382–388
European Standard EN 13506, 2001 (RefNrEN 13506:2001)
Telliard WA, United States Environmental Protection Agency, Federal Register, vol. 67, no. 209 EPA-821-R-01-033 Method 1631 Revision C, 2001
Zierhut A, Leopold K, Harwardt L, Schuster M (2010) Talanta 81:1529–1535
Zierhut A, Leopold K, Harwardt L, Worsfold PJ, Schuster M (2009) J Anal At Spectrom 24:767–774
DIN (1997) Deutsches Institut für Normung e.V., DIN EN 1484, Anleitung zur Bestimmung des gesamten organischen Kohlenstoffs (TOC) und des gelösten organischen Kohlenstoffs (DOC). Beuth Verlag, Berlin
Leopold K, Foulkes M, Worsfold PJ (2009) Anal Chem 81:3421–3428
Amyot M, Mierle G, Lena D, McQueen DJ (1997) Geochim Cosmochim Acta 61(5):975–987
Gómez-Ariza JL, Lorenzo F, Garcia-Barrera T (2004) J Chromatograph A 1056:139–144
Tsalev DL, Sperling M, Welz B (2000) Spectrochim Acta B 55:339–353
Achterberg EP, Van den Berg CMG (1994) Anal Chim Acta 291:213–232
Batley GE, Florence TM (1976) Mar Chem 4:347–363
Hubaux A, Vos G (1970) Anal Chem 42:849–855
Linsinger TPJ (2005) Comparison of measurement result with the certified value, application Note 1 EC-JRC, IRMM
Acknowledgments
The presented work was funded by the German Federal ministry for Economy and Technology (BMWi) in a ZIM project. We would like to express our gratitude to our co-operation partners from Analytik Jena AG in this project for provision of instrumentation. Special thanks are given to T. Labatzke (Analytik Jena AG, Germany) for checking UV-lamps for compatibility with the automated FIA system. Furthermore, we would like to thank S. West (Technische Universität München, Germany) for TOC and DOC analysis. We are also thankful to R. Schindl, N. Feichtmeier (University of Ulm, Germany), and H. Sievers (Technische Universität München, Germany) for helping with river water sampling. Furthermore, we are gratefully indebted to Prof. Dr. M. Schuster (Technische Universität München, Germany) to make the clean room facility available.
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Published in the special issue Young Investigators in Analytical and Bioanalytical Science with guest editors S. Daunert J. Bettmer, T. Hasegawa, Q. Wang, and Y. Wei.
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Leopold, K., Zierhut, A. & Huber, J. Ultra-trace determination of mercury in river waters after online UV digestion of humic matter. Anal Bioanal Chem 403, 2419–2428 (2012). https://doi.org/10.1007/s00216-012-5851-8
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DOI: https://doi.org/10.1007/s00216-012-5851-8