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Determination of Thallium Speciation in Water Samples by HPLC-ICP-MS


Thallium (Tl) is used in various industrial applications such as semiconductors, pharmaceutical products, catalysts, glass production, pigments, thereby increasing the risk of occupational poisoning and environmental pollution. It is also a byproduct of heavy-metal sulfide ore mining, and is present in flue dust from coal fired power plants and cement kilns and thus is being distributed in the environment as anthropogenic pollution. Soluble Tl salts are toxic, and they were historically used as rat poisons and insecticides, but later banned because of their nonselective toxicity and their popularity as a murder weapon. Thallium is one of the 13 priority metal pollutants listed by the US EPA and for mammals is known to be more toxic than Hg(II), Pb(II) or Cd(II).  

In the aquatic environment, Tl may be present in two oxidation states, Tl(I) and Tl(III), with Tl(I) being the more stable species and therefore often the dominating species. Tl(III), the more reactive species is also the much more toxic species. For a meaningful risk assessment and understanding of the environmental behavior, speciation analysis differentiating the two species is mandatory.

The new study: 
The group of researchers from China focused their study on the optimization of the chromatographic separation of the two thallium species by using ion exchange methodology under isocratic conditions. The key mechanism used for separation is complex formation of Tl(III) with DTPA whereby the charge of the Tl-DTPA complex depends on pH. While at pH<2, the complex is protonated and therefore positively charged, at pH>6 the complex is negatively charged. Anyhow, in  principle, Tl(I) and Tl(III)-DTPA can be separated using IEC.

The authors compared anion and cation exchange chromatography and optimized pH, mobile phase (DTPA and ammonium acetate concentration) injection volume and flow rate. Best detection power was obtained by AEC. Optimum values for the mobile phase used for anion exchange column were pH=4.2, 3 mmol/L DTPA and 200 mmol/L ammonium acetate. In order to obtain high detection power, the injection volume was maximized to 100 µL and the flow was set to 1 mL/min because of pressure limitations. Under these conditions LODs of 3 and 6 ng/L were obtained for Tl(1) and Tl(III) within a chromatographic run of 10 min.

When a cation-exchange column was used, the LODs were a factor of 2-3 worse, however separation was achieved within less than 6 min. The mobile phase for cation exchange chromatography was 15 mmol/L HNO3 and 3 mmol/L DTPA.

The authors mentioned that real natural water samplers could contain redox active species such as iron leading to the oxidation of Tl. For such reason, samples should be analysed as soon  as possible.

The original study:

Yuexin Zhao, Fang Cheng, Bin Men, Yi He, Hui Xu, Xiaofang Yang, Dongsheng Wang, Simultaneous separation and determination of thallium in water samples by high-performance liquid chromatography with inductively coupled plasma mass spectrometry, J. Sep. Sci., 42/21 (2019) 3311-3318. DOI: 10.1002/jssc.201900593

Used techniques and instrumentation:

Thermo Scientific: ICAP Q - ICP-MS

Related studies

Beatrice Campanella, Corinne Casiot, Massimo Onor, Martina Perotti, Riccardo Petrini, Emilia Bramanti, Thallium release from acid mine drainages: Speciation in river and tap water from Valdicastello mining district (northwest Tuscany). Talanta, 171 (2017) 255–261. DOI: 10.1016/j.talanta.2017.05.009

Nelson Belzile, Yu-Wei Chen, Thallium in the environment: A critical review focused on natural waters, soils, sediments and airborne particles, Appl. Geochem., 84 (2017) 218-243. DOI: 10.1016/j.apgeochem.2017.06.013

Bozena Karbowska, Presence of thallium in the environment: sources of contaminations, distribution and monitoring methods, Environ Monit Assess, 188 (2016) 640. DOI 10.1007/s10661-016-5647-y

Sven Sindern, Jan Schwarzbauer, Lars Gronen, Alexander Görtz, Stefan Heister, Manuela Bruchmann, Tl-speciation of aqueous samples – a review of methods and application of IC-ICP-MS/LC-MS procedures for the detection of (CH3)2Tl+ and Tl+ in river water, Int. J.  Environ. Anal. Chem., 95/9 (2015) 790-807. DOI: 10.1080/03067319.2015.1058932

Y.-L. Chu, R.-Y. Wang, S.-J. Jiang, Speciation analysis of thallium by reversed-phase liquid chromatography - inductively coupled plasma mass spectrometry, J. Chin. Chem Soc-Taip. 59 (2012) 219–225. DOI: 10.1002/jccs.201100389.

Corinne Casiot, Marion Egal, Odile Bruneel, Neelam Verma, Marc Parmentier,  Francoise Elbaz-Poulichet, Predominance of Aqueous Tl(I) Species in the River SystemDownstream from the Abandoned Carnoules Mine (Southern France), Environ. Sci. Technol., 45 (2011) 2056–2064. DOI: 10.1021/es102064r

A.K. Das, M. Dutta, M.L. Cervera, M. de la Guardia, Determination of thallium in water samples, Microchem. J., 86/1 (2007) 2–8. DOI: 10.1016/j.microc.2006.07.003 

Ulrika Karlsson, Anders Düker, Stefan Karlsson, Separation and Quantificationof Tl(I) and Tl(III) in Fresh Water Samples, J. Environ. Sci. Health Part A, 41 (2006) 1157–1169. DOI: 10.1080/10934520600655747

U. Karlsson, S. Karlsson, A. Düker, The effect of light and iron(II)/iron(III) on the distribution of Tl(I)/Tl(III) in fresh water systems, J. Environ. Monitor., 8 (2006) 634–640. DOI: 10.1039/b516445a

P.P. Coetzee, J.L. Fischer, M. Hu, Simultaneous separation and determination of Tl(I) and Tl(III) by IC-ICP-OES and IC-ICP-MS. Water. SA., 29/1 (2003)  17–22. DOI: 10.4314/wsa.v29i1.4940

last time modified: November 17, 2019

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