Pre-concentration

Gel permeation chromatography Liquid-liquid adsorption chromatography (adsorption column) 

Gomez-Ariza, E. Morales, I. Giraldez, D. Sanchez-Rodas and A. J. Velasco,/. Chromatogr. A 938,211 (2001). 

AlbertiandG. Raxaet,Mikrochim.Acta 109,39(1992). 

Freitag andO. iohm. Die Angew. Makromol. Chem. 175, 181 (1990). 

Lopez-Avila, R. Young and W. Beckert, Anal. Chem. 66, 1097 (1994). 

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Stripping voltammetry involves the pre-concentration of the analyte species at the electrode surface prior to the voltannnetric scan. The pre-concentration step is carried out under fixed potential control for a predetennined time, where the species of interest is accumulated at the surface of the working electrode at a rate dependent on the applied potential. The detemiination step leads to a current peak, the height and area of which is proportional to the concentration of the accumulated species and hence to the concentration in the bulk solution. The stripping step can involve a variety of potential wavefomis, from linear-potential scan to differential pulse or square-wave scan. Different types of stripping voltaimnetries exist, all of which coimnonly use mercury electrodes (dropping mercury electrodes (DMEs) or mercury film electrodes) [7, 17]. 

Anodic-stripping voltaimnetry (ASV) is used for the analysis of cations in solution, particularly to detemiine trace heavy metals. It involves pre-concentrating the metals at the electrode surface by reducmg the dissolved metal species in the sample to the zero oxidation state, where they tend to fomi amalgams with Hg. Subsequently, the potential is swept anodically resulting in the dissolution of tire metal species back into solution at their respective fomial potential values. The detemiination step often utilizes a square-wave scan (SWASV), since it increases the rapidity of tlie analysis, avoiding interference from oxygen in solution, and improves the sensitivity. This teclmique has been shown to enable the simultaneous detemiination of four to six trace metals at concentrations down to fractional parts per billion and has found widespread use in seawater analysis. 

Adsorptive stripping analysis involves pre-concentration of the analyte, or a derivative of it, by adsorption onto the working electrode, followed by voltanmietric iiieasurement of the surface species. Many species with surface-active properties are measurable at Hg electrodes down to nanoniolar levels and below, with detection limits comparable to those for trace metal detemiination with ASV. 

Improved sensitivities can be attained by the use of longer collection times, more efficient mass transport or pulsed wavefomis to eliminate charging currents from the small faradic currents. Major problems with these methods are the toxicity of mercury, which makes the analysis less attractive from an eiivironmental point of view, and surface fouling, which coimnonly occurs during the analysis of a complex solution matrix. Several methods have been reported for the improvement of the pre-concentration step [17,18]. The latter is, in fact. 

All main aspects of analytical and bioanalytical sciences is covered by the conference program. AC CA-05 consists of 12 invited lectures and seven symposia General Aspects of Analytical Chemistry, Analytical Methods, Objects of the Analysis,. Sensors and Tests, Separation and Pre-concentration, Pharmaceutical and Biomedical Analysis, History and Methodology of Analytical Chemistry. Conference program includes two special symposia Memorial one, dedicated to Anatoly Babko and Analytical Russian-Germany-Ukrainian symposium (ARGUS-9). 

ICP-SFMS (Thermo Finnigan, Flement) with cold vapour generation was developed with a guard electrode and a gold amalgamation device using an Au-sorbent for sample pre-concentration to improve the sensitivity. Instrumental parameters of ICP-SFMS such as take-up time, heating temperature of Au-sorbent, additional gas flow, and sample gas flow were optimized. Detection limit calculated as 3 times the standard deviation of 10 blanks was 0,05 ng/1, RSD = 7-9 %. 

As atomic fluorescence spectrometer a mercury analyzer Mercur , (Analytik-Jena, Germany) was used. In the amalgamation mode an increase of sensitivity by a factor of approximately 7-8 is obtained compared with direct introduction, resulting in a detection limit of 0,09 ng/1. This detection limit has been improved further by pre-concentration of larger volumes of samples and optimization of instrumental parameters. Detection limit 0,02 ng/1 was achieved, RSD = 1-6 %. 

In this work, atmospheric particles (PM 10 and PM 2.5) were collected by a dichotomos air sampler. Several leaching procedures were investigated for decomposition of heavy metals. The digests were pre-concentrated with sodium diethyldithiocarbamate. The determinations were canted out on a Vartan Model AA-220 atomic absorption spectrometer. The instrarment was equipped with a GTA-110 graphite furnace system. Table 1 shows the concentrations of heavy metals associated with PM 10 and PM 2.5 particles. Table 1. Concentrations of heavy metals in PM 10 and PM 2.5 atmospheric particles (ng/m )... 

Application of rotating coiled columns has become attractive for preparative-scale separations of various substances from different samples (natural products, food and environmental samples) due to advantages over traditional liquid-liquid extraction methods and other chromatographic techniques. The studies mainly made during the last fifteen years have shown that using rotating coiled columns is also promising for analytical chemistry, particularly for the extraction, separation and pre-concentration of substances to be determined (analytes) before their on-line or off-line analysis by different determination techniques. 

There ai e noted the most convenient, simple and chip methods, which ensure the high quality of specimens and can be easily combined with different techniques for analytical pre-concentration of impurities. In particulaidy, it is proposed to make specimens in the form of gel, film or glass in the case of XRF analysis of concentrates obtained by low-temperature crystallization of aqueous solutions. One can prepai e film or organogel specimens from organic concentrates obtained by means of extraction of impurities by organic solvent. Techniques for XRF analysis of drinking, natural and wastewater using considered specimens ai e adduced. 

ANALYTICAL APPLICATION OF SILICAS WITH COVALENT AND ION-EXCHANGE BONDING OF IMMOBILIZED ORGANIC COMPOUNDS FOR SELECTIVE PRE-CONCENTRATION AND DETERMINATION OF PHENOLIC POLLUTANTS... 

Eor the selective pre-concentration of deactivated phenols a new silica-based material with the grafted 2,3,5-triphenyltetrazole was proposed. This method is based on the formation of molecular chai ge-transfer comlexes of 2,3,5-triphenyltetrazole (7t-acceptor) with picric acid (7t-donor) in the phase of the sorbent. Proposed SPE is suitable for HPEC analysis of nitrophenols after their desorption by acetonitrile. Test-system for visual monitoring of polynitrophenols under their maximum concentration limits was developed using the proposed adsorbent. 

Sample pre-treatment. Novel procedures of electrochemical sample treatment have been proposed to decrease the signal interference with native cholinesterase inhibitors present in fruits and vegetables. Polyphenolic compounds were removed by electrolysis with soluble A1 anode followed by the oxidation of thionic pesticides with electrogenerated chlorine. The procedure proposed makes it possible to decrease the background current and the matrix effect by 80-90%. Thus, the detection limits of about 5 ppb of Pai athion-Methyl and Chloropyrifos-Methyl were obtained in spiked grape juice without any additional sepai ation or pre-concentration stages. 

Spectrophotometry-Colorimetry One of most useful and versatile methods but can be time consuming 10- to 10- M (10- with pre-concentration)... 

The system can be made more sophisticated through the addition of fused silica restrictors acting as bleeds, thus preventing back diffusion of analytes towards the solenoid valves. Additional pre-concentration stages can also be provided between the primary and secondary columns to reduce the peak widths introduced to the secondary column. 

The direct mode is used when the concentration of the SEE extract is enough for direct analysis in the CE instrument without the need for a pre-concentration step. In this case, the sample concentrator is by-passed and the SEE extract goes directly to the CE instrument. The extract is collected in a CE vial containing an appropriate solvent and is thus ready for the CE analysis (Eigure 6.12). 

J. T. B. Strode and L. T. Taylor, Supercritical fluid exti action employing a vai iable restrictor coupled to gas chi omatography via a sample pre-concentration cap , ]. High Resolut. Chromatogr. 19 651-654 (1996). 

J. H. Beattie, R. Self and M. P. Richards, The use of solid phase concenti ators for online pre-concentration of metallothionein prior to isofom separation by capillary zone electrophoresis , Electrophoresis 16 322-328 (1995). 

Completion of the analysis. The technique of solvent extraction permits the separation and often the pre-concentration of a particular element or substance (or of a group of elements or substances). Following this separation procedure, the final step of the analysis involves the quantitative determination of the species of interest by an appropriate technique. 

Many polarographic analysers are available commercially which can be used for the pre-concentration electrolysis step, and will then apply the requisite stripping procedure and produce a recorder chart of the result. In many modem instruments, microprocessor control is incorporated so that the requisite series of operations take place automatically. 

Marvin, C. H., Brindle, I. D., Singh, R. P., Hall, C. D., and Chiba, M., Simultaneous determination of trace concentrations of benomyl, carbendazim (MBC) and nine other pesticides in water using an automated on-line pre-concentration high-performance liquid chromatographic method, /. Chromatogr., 518, 242, 1990. 

The sample volume initially introduced onto the sorbent, the choice of sorbent and solvent system and careful control of the amount of solvent used are of paramount importance for effective pre-concentration and/or clean-up of the analyte in the sample. The number of theoretical plates in an SPE column is low (/V = 10-25). SPE is a multistage separation method and as such requires only a reasonable difference in extractability to separate two solutes. In SPE concentration factors of 1000 or more are possible, as compared to up to 100 for LLE with vortex mixing. 

The great attraction of SV lies in the effect of pre-concentration of the analyte at the electrode with, as a consequence for the stripping current, a very high ratio of faraday current to charging and impurity currents it is this high ratio which has made SV the most sensitive voltammetric analysis method to date. 

Interferences in SV. As a consequence of the pre-concentration, the influence of charging and impurity currents will be slight. Moreover, as the surface area of stationary electrodes is constant, their capacity C can only... 

In these flow systems a certain kind of separation, be it pre-concentration or a more sophisticated separation such as chromatography, of individual analyte components preceeds the detection in treating the subject we shall distinguish between the techniques for gaseous samples and those for liquid samples, while concentrating on electrochemical detection. 

Stripping analysis with inherent pre-concentration seems attractive to CFA, but until recently such a procedure appeared rather exceptional. It has been used in the automatic determination of heavy metals in water by anodic stripping voltammetry (ASV12S) in a continuous flow cell with a mercury-covered graphite electrode, having the advantage that one can distinguish... 

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