Generation efficiency of four mercury species, namely elemental mercury and hydrides of methyl-, ethyl- and phenylmercury from liquid samples was quantified. The species chemically generated were quantitatively trapped on a gold-coated amalgamator to be subsequently determined by AMA-254 technique. Three types of construction of volatile species generators were compared. Generation effciciency among the species was comparable, fluctuating around 60% in the conventional flow injection generator equipped with a gas liquid separator with forced outlet. Better results were reached for elemental mercury and methylmercury hydride in an automated batch generator system. Generation efficiency was higher than 90% for these two species and between 60 to 80% for ethyl- and phenylmercury hydrides, respectively. Speciation analysis of elemental mercury and sublimate in gaseous samples was optimized. These two species dominate in flue gases produced during coal combustion or waste incineration. Combination of two sorbent tubes packed with alumina and gold-coated alumina enables selective and quantitative retention of both species. Sublimate is trapped on a column packed with alumina while elemental mercury is retained on gold-coated alumina. The capacity of both sorbents was investigated as well as the effect of...

Atomization of arsine in a novel hydride atomizer for atomic absorption spectrometry (HG-AAS) was thoroughly optimized. This plasma atomizer is based on a dielectric barrier discharge (DBD). Sensitivity and detection limit reached 0.48 s ng-1 As and 0.16 ng ml-1 As, respectively, under optimum atomization conditions (Ar discharge using a flow rate of 60 ml min-1 Ar, DBD power 17 W). Analytical figures of merit reached in DBD are comparable to those found in an externally heated quartz tube multiatomizer (MMQTA) that was chosen as a model of conventional approach to hydride atomization in HG-AAS. An extent of interferences (Se, Sb, Bi) during As determination was investigated comparing both MMQTA and DBD atomizers. The later one was found to be more resistant towards interferences. A simple preconcentration of As in a DBD atomizer was reached after oxygen introduction into the Ar plasma in the DBD resulting in analyte retention in the atomizer followed by its volatilization once the oxygen flow is switched off. Preconcentration efficiency of 100 % was reached and detection limit improvement by a factor of ten was achieved (0.01 ng ml-1 As, preconcentration period 300 s).

The determination of inorganic speciations of arsenic, antimony, selenium and tellurium in natural waters demands often separation and preconcentration. Solid phase extraction is a very effective method for these purposes. In this paper the separation and preconcentration of these microelements is realised on the basis of modified silica Separon SGX C18, SGX C8, SGX CN, SGX NH2, SGX Phenyl and strongly basic anion Exchanger SGX AX. The sorption was provided in the presence of cationic surfactants such as benzyldimethyl dodecylammonium bromide (Ajatin), benzyldimethyltetradecylammonium chloride (Zephyramine), 1-ethoxycarbonylpentadecyltrimetrhylammonium bromide (Septonex) and selected complexing agents 4-(2-pyridylazo)resorcinol (PAR), 8-hydroxyquinoline-5-sulphonic acide (8-HQS), 1,2-dihydroxybenzene (PYR), amonium 1-pyrrolidinecarbodithioate (APDC), sodium diethyldithiocarbamate (DTC) or thiourea(Thur). The interactions of the formed ion associate with the sorbent shows a complicated character which has not been cleared as yet. The previous conditioning of the sorbent plays an outstanding role. Thus, the sorption efficiency was studied in the presence and absence of surfactant and of selected organic complexing agents. Moreover, the influence of pH of the sorbed solution as well as the speed and the volume of the solution running through the sorbent and the type and volume of the eluent on the resulting sorption efficiency was evaluated. The sorption was successfully carried out from 50-1000 ml of solution which allows the 100 fold increase of the preconcentration factor and the determination of the microelements in g.l-1 instead of mg.l-1 by using the common ICP-AES. The influence of macroelements occurring in waters as well as B, Be, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sr, Ti, V and Zn in comparable concentrations involve less than 5% error. After the quantitative elution of microelements, the organic solvents were evaporated under IR lamps prior to the determination by ICP-AES and |ICP-MS. The conditions for the direct determination of arsenic, antimony, selenium and tellurium in g.l-1 with ICP-MS were also described in detail in the absence and presence of internal standards Ge and Bi. However, even in this case the preconcentration on silica in the presence of surfactant and selected organic complexants was also tested. When the sorption was followed from 500 ml a 50 fold enrichment factor is reached and the sensitivity for the microelements is improved. The direct determination and the sorption of microelements were applied on synthetic and real waters (dirinking, surface, mineral and sea waters). Instrumental and practical detection limits for various water samples were evaluated according to IUPAC. The results from 1000 ml solution of real waters after sorption on modified silica and the final determination of microelements with ICP-AES were compared with those from ICP-MS without sorption using the method of standards addition in the presence of suitable internal standards. By comparison of results for synthetic and real water samples the error of the determination of microelements was evaluated.

In this master thesis, during 2009, 2010 and 2011, has been done measurement of total content of mercury in ambient air and soil air in urban and rural locations agglomeration of České Budějovice. The goal was to develop suitable method in order to provide sampling of air to evaluate rate of contamination from chosen locations. The aquaristic compressor was used for admission of air, thus collected air could pass through external amalgamator, which secured pre-concentration of mercury from air. Consecutively, captured mercury has been determined in laboratory by atomic absorption spectrometer AMA-254. In urban background locations has been found total average concentration of mercury in rate 4,01 +/- 3,5 ng.m-3 and urban locations influenced by traffic in rate 29,5 +/- 50,07 ng.m-3. The concentration of mercury in soil air taken from filter bed of constructed wetland (CW) was 16 +/- 9,44 ng.m-3 with average mercury flux 14,5 +/- 8,3 ng.m-2.h-1. In rural compared location has been concentration of mercury in rate 15,4 +/- 7,83 ng.m-3 and mercury flux in soil air was 16 +/- 9,3 ng.m-2.h-1 at this location. Significant differences in contamination of mercury among partial locations have not been ascertained to the exception. The statutory limit for amount of mercury in atmosphere is 50 ng.m-3, whose value has not been mostly reached in any of measured locations. Thus, it has been proved that air contamination is low at selected locations.

The aim of this thesis was to optimize atomization conditions for selenium hydride in a novel plasma atomizer based on dielectric barrier discharge (DBD) using atomic absorption spectrometry as a detector. Analytical characteristics have been subsequently determined and compared to those reached in a conventional externally heated quartz tube atomizer which was replaced by a sofisticated design of a multiatomizer (MMQTA) in this work. The limit of detection reached in DBD (0,24 ng ml−1 Se) is slightly worse to that observed in MMQTA (0,15 ng ml−1 Se). On the contrary, slightly better resistance towards interferences of Sb, Bi and As was observed in DBD atomizer in comparison with MMQTA. Possibility of selenium preconcentration in a DBD atomizer was studied reaching an overall preconcentration efficiency of 75 ± 5%. The detection limit in a preconcentration mode employing preconcentration period of 300 s has reached 0,012 ng ml−1 Se. Key words: hydride generation atomic absorption spectrometry, dielectric barrier discharge, hydride atomization, hydride trapping, selenium