title: Evaluation of electrospray ionisation mass spectrometry as a technique for the investigation of competitive interactions: a case study of the ternary Th-Mn-EDTA system.
abstract: BACKGROUND
  Electrospray ionisation mass spectrometry (ESI-MS) is a useful tool for exploring the speciation of solution-phase metal complexes; however, the quantification of ternary systems is challenging due to the differences in the electrospray response of different species. Here, the Th-Mn-EDTA system was investigated to evaluate the capability of ESI-MS for quantifying the species present.
  
  
  METHODS
  Increasingly complex mixtures of Th(IV), Mn(II) and EDTA were analysed using manual flow injection of samples into an HPLC grade water mobile phase delivered to an ion trap mass spectrometer fitted with an ESI interface (ThermoQuest Finnigan Mat LCQ). Mass spectra were obtained in the positive and negative ion modes over a mass-to-charge (m/z) range from 50-2000.
  
  
  RESULTS
  The instrumental response to EDTA was affected by the addition of Th(NO(3))(4) but not MnCl(2), while the response to both Th-EDTA and Mn-EDTA species was affected by addition of the other metal salt. Internal standards were also found to suppress signals to different extents. Therefore, each signal suppression was carefully quantified as the solution became more complex, and signal correction factors were used in conjunction with regular external calibration. Mixed metal signals were quantified adequately.
  
  
  CONCLUSIONS
  This study showed the complexity of quantifying a ternary system involving different co-existing species. Nonetheless, the step-wise protocol developed provided quantitative data on the displacement of Mn from its EDTA complex by Th.
authors.affiliation: Biogeochemistry and Environmental Analytical Chemistry Group, Biogeochemistry Research Centre, University of Plymouth, Plymouth, PL4 8AA, UK. estela.reinoso-maset@cea.fr
authors.forename: Estela
authors.initials: E
authors.lastname: Reinoso-Maset
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Worsfold
authors.forename: Miranda J
authors.initials: MJ
authors.lastname: Keith-Roach
mesh_terms: D002851:Chromatography, High Pressure Liquid; D056831:Coordination Complexes / Q000737:chemistry; D004492:Edetic Acid / Q000737:chemistry*; D015636:Magnesium Chloride / Q000737:chemistry; D008345:Manganese / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013910:Thorium / Q000737:chemistry*; D017970:Thorium Compounds / Q000737:chemistry
chemical_list: D056831:Coordination Complexes; D017970:Thorium Compounds; D015636:Magnesium Chloride; D008345:Manganese; D013910:Thorium; D004492:Edetic Acid; C036680:thorium nitrate