Spectrotitration of ethane-1-hydroxy-1,1-diphosphonic acid (EHDP(tm)) with thorium diaminocyclohexanetetra-acetate.
An automatic spectrotitration procedure for EHDP has been developed. It is applicable to samples containing 50mug or more of EHDP, with a relative standard deviation of 3% if no interfering materials are present. The sensitivity can be extended down to about 5mug, but titration blanks become significant and the standard deviation increases markedly. Thorium diaminocyclohexanetetra-acetate (Th-DCTA) is used as the titrant, to give a ternary species (Th-DCTA)(2)-EHDP. The end-point in the spectrotitration is due to deprotonation of Xylenol Orange indicator when it is incorporated into a weaker ternary species after all the EHDP has reacted. Salts such as NaCl, NaClO(4), Na(2)SO(4) and NaNO(3) interfere if present at concentrations of 0.1-0.5M. The method is much more sensitive to orthophosphate, but this interference can be averted by isolating the EHDP before titration by selectively adsorbing the phosphonate on calcium hydroxyapatite.
Trace-level determination of phosphonates in liquid and solid phase of wastewater and environmental samples by IC-ESI-MS/MS
Phosphonates are increasingly used as water-softening agents in detergents, care products, and industrial processes. Despite poor biodegradability, high removal rates during wastewater treatment (WWT) have been observed, owing to strong adsorption affinity to activated sludge and mineral surfaces. Due to phosphonates representing challenging analytes, no method for the compound-specific quantification of phosphonates from solid samples has hitherto been published. In order to improve the data foundation on the environmental fate of phosphonates, an analytical method based on anion exchange chromatography and detection by electrospray ionization coupled to tandem mass spectrometry (IC-ESI-MS/MS) was developed, allowing the trace quantification of phosphonates from surface water (LOQs between 0.04 and 0.16 μg/L), wastewater (LOQs between 0.6 and 2.3 μg/L), sediment and suspended matter of rivers (LOQ < 0.1 mg/kg), and suspended matter of wastewater (LOQ < 1 mg/kg). Specificity and selectivity were enhanced by the implementation of isotope-labeled internal phosphonate standards derived through synthesis. This study describes the development of a comprehensive tool set for the determination of aminotris(methylenephosphonic acid) (ATMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMP), ethylenediaminetetra(methylenephosphonic acid) (EDTMP), 1-hydroxyethanediphosphonic acid (HEDP), and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) during WWT and in the aqueous environment. In the investigated matrices, HEDP and PBTC were generally present in highest and EDTMP in lowest abundance. The phosphonate contents detected in river water were in the sub to low μg/L range, depending on the wastewater burden, whereas contents in the low to medium μg/L range were found in untreated wastewater. The loads of the solid phases exceeded the contents of the corresponding liquid phases by roughly three orders of magnitude. Current data imply that phosphonates undergo significant partitioning to the solid phase during WWT and in natural water bodies. Graphical abstract
CONTRIBUTIONS TO THE BASIC PROBLEMS OF COMPLEXOMETRY. XII. SUCCESSIVE DETERMINATION OF THORIUM, RARE EARTHS AND SOME OTHER ELEMENTS
Abstract The successive determination of thorium and rare earths with diethylenetriaminepenta-acetic acid (DTPA) and triethylenetri-aminehexa-acetic acid (TTHA) is described. Such a determination cannot be carried out with the commonly used EDTA or diamino-cyclohexanetetraacetic acid (DCTA). By combined titrations with DTPA and TTHA it is possible to determine successively not only thorium and rare earths, but also some bivalent elements which might be present in the material to be analysed.