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Determination of tungsten species in natural waters by HPLC-ICP-MS


Tungsten metal is used in many industrial, military, and consumer applications, and interest in its biogeochemistry is increasing partially due to its potential mobility and biological effects. Various tungsten species exist in solution depending on the concentration, pH, redox conditions and aging time. In neutral and alkaline natural water, tungsten generally exists in the form of tungstate (i.e., WO42-). In weakly acidic tungsten-rich water, it undergoes several polycondensation reactions to form polyoxotungstates, which have been proven to be more toxic and migratory than tungstate. Similar to other trace elements, such as arsenic, antimony, and molybdenum, thiolation (substitution of sulfhydryl for oxhydryl) of tungstate, namely thiotungstate (WOnS4-n2-, n = 0-4), has been observed in sulfide-rich water. The variable speciation observed directly affects biogeochemical processes, such as solubility, sorption, mobility, and toxicity. In order to understand the environmental implications and health effects the distribution of tungsten species and its concentrations is a mandatory information. In order to differentiate the different species in real environmental water samples, the method for speciation analysis should be both highly sensitive and selective. Spectroscopic methods such as NMR, Raman, FTIR and UV-VIS cannot provide either the sensitivity or selectivity required for complex samples.

The new study:

A group of researchers from China now optimized reversed-phase ion-pair chromatography (RP-IPC) coupled with ICP-MS for the sensitive detection of tungstates, thiotungstates and polytungstates in a single run. A Dionex IonPac NS1 RP column was used for the separation of species with tetrabutylammonium/sodium carbonate as mobile phase under gradient elution conditions with 12-48% ethanol within the mobile phase.

ICP-MS was used for the detection of tungsten in the eluent, calling for a PFA nebulizer for reducing interactions of tungsten with the sample introduction system. Oxygen was added to the injected gas flow in order to avoid carbon formation from the ethanol. Oxygen was also added to the collision cell of the ICP-MS in order to mass shift the analyte to 184W16O+. Using this method, six aqueous species of tungsten, including tungstate, monothiotungstate, dithiotungstate, trithiotungstate, tetrathiotungstate and polytungstates were efficiently separated within 35 min.

Figure 1: W species distribution for a geothermal sample collected at Banglazhang hydrothermal area

The detection limit of the late eluting polytungstates was 1.5 μg/L. Quantification of species was performed by using compound independent external calibration and peak area evaluation. The results of a typical geothermal water collected at Banglazhang hydrothermal area are shown in table 1. The accuracy of the method was shown by comparing the result of the sum of all species with the determined total tungsten concentration of the same sample.

Table 1: Result of tungsten species in a representative geothermal water sample
W species
Concentration (µg/L) 
RSD, n=3
 WO42- 64.3 4.5 %
 WO3S2- 21.4 3.7 %
 WO2S22- 33.9 4.0 %
 WOS32- 173.9 2.2 %
 WS42- 1.9 3.9 %
 polytungstates 4.9 4.9 %
 sum of W species
 total W

The authors further concluded, that acidification of samples was not suitable for tungsten speciation analysis, as the reduced pH would lead to the formation of polytungstates.

The original study

Qian Zhao and Qinghai Guo, Simultaneous Determination of Tungstates, Thiotungstates, and Polytungstates in NaturalWaters by Reverse Phase Ion Pair Chromatography Coupled with ICP-MS, At. Spectrosc., 43/3 (2022) 230-235. DOI: 10.46770/AS.2022.032

Instrumentation used:

Thermo Scientific - iCAP-RQ ICP-MS System
Dionex - ICS-6000 Ion Chromatography System

Related studies (newest first)

Q.H. Guo, B. Planer-Friedrich, K.T. Yan, Tungstate thiolation promoting the formation of high-tungsten geothermal waters and its environmental implications, J. Hydrol., 603 (2021) 127016. DOI: 10.1016/j.jhydrol.2021.127016

B. Planer-Friedrich, J. Forberg, R. Lohmayer, C.F. Kerl, F. Boeing, H. Kaasalainen, A. Stefansson, Relative Abundance of Thiolated Species of As, Mo, W, and Sb in Hot Springs of Yellowstone National Park and Iceland, Environ. Sci. Technol., 54/7 (2020) 4295–4304. DOI: 10.1021/acs.est.0c00668

Q.H. Guo, Y.M. Li, L. Luo, Tungsten from typical magmatic hydrothermal systems in China and its environmental transport, Sci. Total Environ., 657 (2019) 1523–1534. DOI: 10.1016/j.scitotenv.2018.12.146

R. Lohmayer, G.M.S. Reithmaier, E. Bura-Nakic, B. Planer-Friedrich, Ion-Pair Chromatography Coupled to Inductively Coupled Plasma−Mass Spectrometry (IPC-ICP-MS) as a Method for Thiomolybdate Speciation in Natural Waters, Anal. Chem., 87/6 (2015) 3388–3395. DOI: 10.1021/ac5046406

T.J. Mohajerin, G.R. Helz, C. White, K.H. Johannesson, Tungsten speciation in sulfidic waters: Determination of thiotungstate formation constants and modeling their distribution in natural waters, Geochim. Cosmochim. Ac., 144 (2014) 157–172. DOI: 10.1016/j.gca.2014.08.037

K.H. Johannesson, H.B. Dave, T.J. Mohajerin, S. Datta, Controls on tungsten concentrations in groundwater flow systems: The role of adsorption, aquifer sediment Fe(III) oxide/oxyhydroxide content, and thiotungstate formation, Chem. Geol., 351 (2013) 76–94. DOI: 10.1016/j.chemgeo.2013.05.002

N. Strigul, Does speciation matter for tungsten ecotoxicology?, Ecotox. Environ. Safe., 73 (2010) 1099–1113. DOI: 10.1016/j.ecoenv.2010.05.005

N. Strigul, C. Galdun, L. Vaccari, T. Ryan, W. Braida, C. Christodoulatos, Influence of speciation on tungsten toxicity, Desalination, 248/1-3 (2009) 869-879. DOI: 10.1016/j.desal.2009.01.016

A.J. Bednar, R.A. Kirgan, D.R. Johnson, A.L. Russell, C.A. Hayes, C.J. McGrath, Polytungstate analysis by SEC-ICP-MS and direct-infusion ESI-MS, Land Contamination & Reclamation, 17/1 (2009) 129–137. DOI: 10.2462/09670513.929

A.J. Bednar, R.E. Boyd, W.T. Jones, C.J. McGrath, D.R. Johnson, M.A. Chappell, D.B. Ringelberg, Investigations of tungsten mobility in soil using column tests, Chemosphere, 75/8 (2009) 1049–1056. DOI: 10.1016/j.chemosphere.2009.01.039

A.J. Bednar, W.T. Jones, R.E. Boyd, D.B. Ringelberg, S.L. Larson, Geochemical Parameters Infl uencing Tungsten Mobility in Soils, J. Environ. Qual., 37/1 (2008) 229–233. DOI: 10.2134/jeq2007.0305

D.L. Long, C. Streb, Y.F. Song, S. Mitchell, L. Cronin, Unravelling the Complexities of Polyoxometalates in Solution Using Mass Spectrometry: Protonation versus Heteroatom Inclusion, J. Am. Chem. Soc., 130/6 (2008) 1830–1832. DOI: 10.1021/ja075940z

A.J. Bednar, J.E. Mirecki, L.S. Inouye, L.E. Winfield, S.L. Larson, D.B. Ringelberg, The determination of tungsten, molybdenum, and phosphorus oxyanions by high performance liquid chromatography inductively coupled plasma mass spectrometery, Talanta, 72 (2007) 1828–1832. DOI: 10.1016/j.talanta.2007.02.016

K. Kishida, Y. Sohrin, K. Okamura, J.I. Ishibashi, Tungsten enriched in submarine hydrothermal fluids, Earth Planet. Sci. Lett., 222/3-4 (2004) 819–827. DOI: 10.1016/j.epsl.2004.03.034

C.S. Truebenbach, M. Houalla, D.M. Hercules, Characterization of isopoly metal oxyanions using electrospray time-of-flight mass spectrometry, J. Mass Spectrom., 35/9 (2000) 1121–1127. DOI: 10.1002/1096-9888(200009)35:9<1121::AID-JMS40>3.0.CO;2-7

G.E.M. Hall, C.W. Jefferson, F.A. Michel, Determination of W and Mo in natural spring waters by ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometry) and ICP-MS (Inductively Coupled Plasma Mass Spectrometry): Application to South Nahanni river area, N.W.T., Canada, J. Geochem. Explor., 30 (1988) 63–84. DOI: 10.1016/0375-6742(88)90050-7


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