0478439 - ÚIACH 2018 CZ eng D - Thesis
Marschner, Karel
Vývoj instrumentace a metodologie pro prvkovou a speciační analýzu arsenu založenou na generování hydridů a na detekci atomovou fluorescenční spektrometrií.
[Development of Instrumentation and Methodology for Elemental and Speciation Analysis of Arsenic Based on Hydride Generation and on Atomic Fluorescence Spectrometric Detection.]
Ústav analytické chemie AV ČR, v. v. i. Defended: Praha. 22.09.2017. - Praha: Univerzita Karlova v Praze, 2017. 109 s.
R&D Projects: GA ČR(CZ) GA17-04329S; GA ČR GA14-23532S; GA MŠMT LH12040; GA MŠMT(CZ) LH15174
Institutional support: RVO:68081715
Keywords : arsenic * arsenic species * atomic fluorescence spectrometry * hydride generation
Subject RIV: CB - Analytical Chemistry, Separation

The presented dissertation is devoted to hydride generation from arsenic species and
its application for speciation analysis based on atomic fluorescence detection.
Hydride generation from toxicologically relevant arsenic species was optimized in
order to achieve a 100% efficiency. The resulted experimental setup was subsequently used
for speciation analysis of arsenic in human urine by high performance liquid
chromatography with detection by atomic fluorescence spectrometry. The accuracy of the
developed method was verified by comparative analyses of human urine samples collected
from five individuals with an independent reference method.
The cleavage of As–C bond during the reaction of methylated arsenic species with
tetrahydridoborate(1–) (THB) in acidic media was studied in detail. Pronounced
demethylation of methylated arsenic species was found during the reaction of THB with
HCl, H2SO4, and HClO4 while hydride generation from CH3COOH or TRIS buffer after
prereduction with L-cysteine resulted in the exclusive formation of the corresponding
hydrides. Firstly, this phenomenon can endanger the accuracy of arsenic speciation which is
based on hydride generation of substituted arsanes. Secondly, the more complex arsenic
species can be converted to the hydride. That was demonstrated on hydride generation of
arsenosugars.
Permanent Link: http://hdl.handle.net/11104/0274559