title: Direct Determination of Trace Antimony in Natural Waters by Photochemical Vapor Generation ICPMS: Method Optimization and Comparison of Quantitation Strategies.
abstract: A novel and sensitive approach for the accurate determination of antimony (Sb) in natural waters is described using photochemical vapor generation (PVG) coupled with inductively coupled plasma mass spectrometry (ICPMS) for detection. Utilizing a unique flow-through photochemical reactor capable of subjecting the samples to deep-UV (185 nm) radiation, generation efficiency was found to be independent of whether Sb(III), Sb(V), or organometallic species [trimethyltantimony(V)dibromine, TMSb(V)] were present, eliminating the shortcoming of Sb species depended sensitivity encountered during direct solution nebulization by ICPMS. Furthermore, the potentially severe matrix effect from seawater was efficiently eliminated by using a mixture of 5% (v/v) formic and 15% acetic acids (v/v) as the photochemical reductant, making direct determination of Sb in seawater feasible. The proposed method provides a 15-fold improvement in sensitivity over direct solution nebulization. A method detection limit of 0.0006 ng g(-1) based on external calibration was obtained (0.0002 ng g(-1) for isotope dilution), yielding a 15-fold improvement over that for direct solution nebulization. Accuracy is demonstrated by analysis of two water certified reference materials (CRMs, e.g., SLRS-6 and NIST 1640a) with satisfying results. In addition, spike recoveries of 100.6 ± 5.5% and 100.8 ± 3.8% (standard deviation, n = 3) were obtained for NASS-6 and CASS-5 seawater CRMs, respectively, since no certified values for Sb has been established for these materials. The performance of several calibration strategies, including double isotope dilution (ID), multiple and single-point gravimetric standard additions with internal standardization, as well as multiple and single-point gravimetric standard additions alone was examined. High precision of determination of Sb in four natural water samples (0.51-1.4%) was realized based on ID calibration, whereas one-point gravimetric standard addition calibration with internal standardization provided precisions of 1.6% and 3.3% at 0.22 and 0.44 ng g(-1) levels, respectively, in seawater.
authors.affiliation: †National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada.|‡College of Geosciences, Chengdu University of Technology, Chengdu 610059, China.
authors.forename: Ying
authors.initials: Y
authors.lastname: Gao
authors.affiliation: †National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada.
authors.forename: Ralph E
authors.initials: RE
authors.lastname: Sturgeon
authors.affiliation: †National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada.
authors.forename: Zoltán
authors.initials: Z
authors.lastname: Mester
authors.affiliation: §Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China.
authors.forename: Xiandeng
authors.initials: X
authors.lastname: Hou
authors.affiliation: §Key Laboratory of Green Chemistry and Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, Sichuan 610064, China.
authors.forename: Chengbin
authors.initials: C
authors.lastname: Zheng
authors.affiliation: †National Research Council Canada, Ottawa, Ontario K1A 0R6, Canada.
authors.forename: Lu
authors.initials: L
authors.lastname: Yang