Retention of thio- and selenometalates in mobile-phase ion chromatography

Weiß, J.; Möckel, H. J.; Müller, Achim; Diemann, E.; Walberg, Heinz‐Jürgen

doi:10.1016/s0021-9673(01)81678-2

Cited by 19 publications

(23 citation statements)

References 17 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Consistent with expectations(Weiss et al, 1988;Bidlingmeyer et al, 1979), retention of the thiomolybdates increases parabolically as the number of sulfide ligands increases. Elution times for each species were 6.10.…”

supporting

confidence: 83%

“…Unfortunately, some thiometalates can experience extreme retention on AEC columns. For example, excessive retention of thiomolybdates on AEC columns has been noted (Weiss et al, 1988). To test whether the thioperrhenates also exhibit extreme retention, we attempted to separate the thioperrhenates by AEC using the same column (Dionex IonPac AS-16/AG-16) and similar eluent conditions (100 mM KOH; isocratic at 1.2 mL/min; conductivity detection) as those used for the successful AEC isolation of thioarsenates (Planer-Friedrich et al, 2007).…”

Section: Accepted Manuscriptmentioning

confidence: 99%

See 1 more Smart Citation

A new analytical approach to determining Mo and Re speciation in sulfidic waters

et al. 2015

View full text Add to dashboard Cite

supporting

confidence: 83%

Section: Accepted Manuscriptmentioning

confidence: 99%

A new analytical approach to determining Mo and Re speciation in sulfidic waters

et al. 2015

View full text Add to dashboard Cite

“…18 Thiomolybdate polymers (such as [Mo 2 O 2 S 2 (S 2 ) 2 ] 2− ) cannot be detected with this IPC−ICP− MS method. 18 A stronger eluent would be required, such as acetonitrile, 27 which is, however, not compatible with ICP− MS. The same method was used to determine W species concentrations including tungstate and mono-, di-, tri-, and tetrathiotungstate (Figure S2).…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

Relative Abundance of Thiolated Species of As, Mo, W, and Sb in Hot Springs of Yellowstone National Park and Iceland

Planer-Friedrich

Forberg

Lohmayer

et al. 2020

Environ. Sci. Technol.

View full text Add to dashboard Cite

Geothermal waters often are enriched in trace metal(loid)s, such as arsenic, antimony, molybdenum, and tungsten. The presence of sulfide can lead to the formation of thiolated anions; however, their contributions to total element concentrations typically remain unknown because nonsuitable sample stabilization and chromatographic separation methods convert them to oxyanions. Here, the concurrent widespread occurrence of thioarsenates, thiomolybdates, thiotungstates, and thioantimonates, in sulfide-rich hot springs from Yellowstone National Park and Iceland is shown. More thiolation was generally observed at higher molar sulfide to metal(loid) excess (Iceland > Yellowstone). Thioarsenates were the most prominent and ubiquitous thiolated species, with trithioarsenate typically dominating arsenic speciation. In some Icelandic hot springs, arsenic was nearly quantitatively thiolated. Also, for molybdenum, thioanions dominated over oxyanions in many Icelandic hot springs. For tungsten and antimony, oxyanions typically dominated and thioanions were observed less frequently, but still contributed up to a few tens of percent in some springs. This order of relative abundance (thioarsenates > thiomolybdates > thiotungstates ≈ thioantimonates) was also observed when looking at processes triggering transformation of thioanions such as mixing with non-geothermal waters or H2S degassing and oxidation with increasing distance from a discharge. Even though to different extents, thiolation contributed substantially to speciation of all four elements studied, indicating that their analysis is required when studying geothermal systems.

show abstract

“…from MoS2O2 2as suggested previously. 39 Figure 2C,D shows the δ 98 Mo values for the individual thiomolybdate species from the above described experiments. As expected, in both experiments, MoO4 2-+MoO3S 2became enriched in heavier isotopes with the reaction proceeding until day 7 (δ 98 Mo=+3.67 in the 1:20 and +2.76‰ in the 1:50 experiment, Tab.…”

Section: Isotope Fractionation During Formation Of Thiomolybdatesmentioning

confidence: 99%

Experimental Confirmation of Isotope Fractionation in Thiomolybdates Using Ion Chromatographic Separation and Detection by Multicollector ICPMS

et al. 2017

View full text Add to dashboard Cite

Molybdenum Mo/Mo isotope ratios are a sediment paleo proxy for the redox state of the ancient ocean. Under sulfidic conditions, no fractionation between seawater and sediment should be observed if molybdate (MoO) is quantitatively transformed to tetrathiomolybdate (MoS) and precipitated. However, quantum mechanical calculations previously suggested that incomplete sulfidation could be associated with substantial fractionation. To experimentally confirm isotope fractionation in thiomolybdates, a new approach for determination of isotope ratios of individual thiomolybdate species was developed that uses chromatography (HPLC-UV) to separate individual thiomolybdates, collecting each peak and analyzing isotope ratios with multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). Using commercially available MoO and MoS standards, the method was evaluated and excellent reproducibility and accuracy were obtained. For species with longer retention times, complete chromatographic peaks had to be collected to avoid isotope fractionation within peaks. Isotope fractionation during formation of thiomolybdates could be experimentally proven for the first time in the reaction of MoO with 20-fold or 50-fold excess of sulfide. The previously calculated isotope fractionation for MoS was confirmed, and the result for MoOS was in the predicted range. Isotopic fractionation during MoS transformation with pressurized air was dominated by kinetic fractionation. Further optimization and online-coupling of the HPLC-MC-ICPMS approach for determination of low concentrations in natural samples will greatly help to obtain more accurate species-selective isotope information.

show abstract

Retention of thio- and selenometalates in mobile-phase ion chromatography

Cited by 19 publications

References 17 publications

A new analytical approach to determining Mo and Re speciation in sulfidic waters

A new analytical approach to determining Mo and Re speciation in sulfidic waters

Relative Abundance of Thiolated Species of As, Mo, W, and Sb in Hot Springs of Yellowstone National Park and Iceland

Experimental Confirmation of Isotope Fractionation in Thiomolybdates Using Ion Chromatographic Separation and Detection by Multicollector ICPMS

Contact Info

Product

Resources

About