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Preservation of arsenic speciation in natural water samples for up to three months


The influencing factors
Arsenic is well-known to exist in two oxidation states (arsenite and arsenate) in water samples which can easily change. With regard to preservation of the species in their original state when sampling takes place, the influencing factors of the two arsenic species on the redox-reaction have to be discussed. The following points have to be considered:
  1. redox potential,
  2. redox couples,
  3. precipitation/sorption,
  4. microbial activity,
  5. light, and
  6. temperature.

While theoretically, the redox potential together with the pH value determines the ratio between the two arsenic species, in reality arsenic species are often not in equilibrium due to kinetic effects.

Preservation Strategies
Another strategy for preservation consists of the removal or complexation of potential redox counterparts without influencing the equilibrium between the different arsenic species. Since oxygen alone, originating from air, is not able to oxidize arsenite, an additional redox counterpart, such as  dissolved or colloidal iron or manganese compounds seems to be necessary to mediate the reactions. Consequently, the exclusion of these counterparts from the reaction could be a possible method for successful preservation by means of complexation. However, due to the possibility of co-porecipitation, a prevention of all precipitation processes is imperative for species preservation.

Light and temperature are additional factors, which have to be considered. The influence of light on the oxidation of arsenite is important and therefore keeping the water samples in the dark is advisable. Temperature has influence on microbial activity as well as on chemical reactions (endothermic/exothermic) and therefore cooling the water samples is also advisable.

The analytical research group at the UFZ headed by Reiner Wennrich found that the pH should be 2 or less in order to avoid precipitation with respect to iron phosphates. Using 10 mM H3PO4 for preservation water samples were stable with respect to arsenic speciation for 28 days in the presence of high concentrations of both iron and manganese (up to 100 mg L-1). The concentration of arsenic species in all samples was higher than 90% of the initial value after 3 months, with the tendency towards a slight diminution of arsenite.

The UFZ study

 Birgit Daus, H. Weiss, Jürgen Mattusch, Rainer Wennrich, Preservation of arsenic species in water samples using phosphoric acid - Limitations and long-term stability, Talanta, 69/2 (2006) 430-434. doi:10.1016/j.talanta.2005.10.012

Related Studies

Venghuot Cheam, Haig Agemian, Preservation of Inorganic Arsenic Species at Microgram Levels in Water Samples,  Analyst (London), 105 (1980) 737-743. doi: 10.1039/AN9800500737

John Aggett, Michelle R. Kriegman, Preservation of Arsenic(III) and Arsenic(V) in Samples of Sediment Interstitial Water with a Graphite Furnace Technique, Analyst (London), 112 (1987) 153-157. DOI: 10.1039/AN9871200153

John Aggett, Michelle R. Kriegman, The extent of formation of arsenic III in sediment interstitial waters and its release to hypolimnetic waters in Lake Ohakuri, Water Research, 22/4 (1988) 407-411. DOI:10.1016/0043-1354(88)90034-6

J.T. van Elteren, J. Hoegee, E.E. van der Hoek, H.A. Das, C.L. de Ligny, J. Agterdenbos, Preservation of As(III) and As(V) in some water samples, J. Radioanal. Nucl. Chem., 154/5 (1991) 343-355. DOI: 10.1007/BF02165490

G.E.M. Hall, G. Gauthier, J.C. Pelchat, Preservation of arsenic species in natural waters, in: R.B. Wanty, S.P. Marsh, L.P. Gough (eds.), Proc. 4th Int. Symp. Environ. Geochem., USGS Open-File Report 97-0496, 1997, pp. 33

P. Volke, B. Merkel, Anwendung eines neuen Feldanalysenverfahrens zur Untersuchung der Stabilität von Arsen und seinen anorganischen Spezies in aquatischen Systemen, Acta Hydrochim. Hydrobiol., 27/4 (1999) 230-238.
DOI: 10.1002/(SICI)1521-401X(199907)27:4<230::AID-AHEH230>3.0.CO;2-E

Torsten Lindemann, Andreas Prange, Walter Dannecker, Bernd Neidhart, Stability studies of arsenic, selenium, antimony and tellurium species in water, urine, fish and soil extracts using HPLC/ICP-MS, Fresenius J. Anal. Chem., 368/2-3 (2000) 214-220. doi: 10.1007/s002160051368

Patricia A. Gallagher, Carol A. Schwegel, Xinyi Wei, John T. Creed, Speciation and preservation of inorganic arsenic in drinking water sources using EDTA with IC separation and ICP-MS detection, J. Environ. Monit., 3/4 (2001) 371-376. DOI: 10.1039/b101658j

A. J. Bednar, J. R. Garbarino, J. F. Ranville, T. R. Wildeman, Preserving the Distribution of Inorganic Arsenic Species in Groundwater and Acid Mine Drainage Samples, Environ. Sci. Technol., 36/11 (2002) 2213-2218. DOI: 10.1021/es0157651

Birgit Daus, Jürgen Mattusch, Rainer Wennrich, H. Weiss, Investigation on stability and preservation of arsenic species in iron rich water samples, Talanta, 58/1 (2002) 57-65. doi:10.1016/S0039-9140(02)00256-4

Patricia A. Gallagher, Carol A. Schwegel, Amy Parks, Bryan M. Gamble, Lar Wymer, John T. Creed, Preservation of As(III) and As(V) in Drinking Water Supply Samples from Across the United States Using EDTA and Acetic Acid as a Means of Minimizing Iron-Arsenic Coprecipitation, Environ. Sci. Technol.,  38/10 (2004) 2919-2927. DOI: 10.1021/es035071n

Andrew G. Gault, Joydeb Jana, Sudipto Chakraborty, Partha Mukherjee, Mitali Sarkar, Bibash Nath, David A. Polya, Debashis Chatterjee, Preservation strategies for inorganic arsenic species in high iron, low- Eh groundwater from West Bengal, India, Anal. Bioanal. Chem., 381/2 (2005) 347-353. DOI: 10.1007/s00216-004-2861-1

V. Oliveira, A.M. Sarmiento, J.L. Gómez-Ariza, J.M. Nieto, D. Sánchez-Rodas, New preservation method for inorganic arsenic speciation in acid mine drainage samples, Talanta, 69/5 (2006) 1182-1189. DOI:10.1016/j.talanta.2005.12.034

G.J. Liu, X.R. Zhang, J. Jain, J.W. Talley, C.R. Neal, Stability of inorganic arsenic species in simulated raw waters with the presence of NOM, Water Sci. Technol., 6/6 (2006) 175-182. doi:10.2166/ws.2006.954

last time updated: November 25, 2008

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