Analytical separation, aqueous environmental samples

Most of the articles in the scientific literature dealing with analytical methods using HPLC technology for the analysis of aqueous environmental samples employ the reversed-phase mode. This finding is not surprising, as the data in Table V attest to. The flexibility of the reversed-phase mode suits environmental analyses. Many metabolites of environmentally important organic compounds are ionic or ionizable and ideally suited to separation by ion-pair techniques. A variety of... 

In the past 5 years the frequency of reports on the use of HPLC technology for the determination of trace organic compounds in aqueous environmental samples has been steadily increasing. Many innovative approaches to sample cleanup and analyte isolation have been reported. Reversed-phase separation, with its many mobile-phase adaptations, has been and continues to be the most popular HPLC separation mode. The development of fast columns and microbore columns should provide optimal configurations for particular applications. The operating characteristics of microbore columns also make... 

Modern analytical techniques usually have sufficient sensitivity to determine the concentration of uranium in aqueous environmental samples and in most cases mass spectrometric techniques can also provide isotopic composition data. However, in some samples, especially where the precise content of minor uranium isotopes is required then preconcentration, separation, and purification can improve the accuracy of the measurement. Several methods have been developed for this purpose based on solid phase extraction (SPE), electro-analytical selective absorption techniques, liquid-extraction, ion-exchange and chromatographic columns, co-precipitation, and selective sorption. Other methods, like single-drop microextraction, are being developed and may serve for microanalysis (Jain and Verma 2011). Some of these techniques are discussed in the context of the specific sample preparation procedures throughout the book, so in this section only a few select methods will be discussed. 

Various liquid chromatographic techniques have been frequently employed for the purification of commercial dyes for theoretical studies or for the exact determination of their toxicity and environmental pollution capacity. Thus, several sulphonated azo dyes were purified by using reversed-phase preparative HPLC. The chemical strctures, colour index names and numbers, and molecular masses of the sulphonated azo dyes included in the experiments are listed in Fig. 3.114. In order to determine the non-sulphonated azo dyes impurities, commercial dye samples were extracted with hexane, chloroform and ethyl acetate. Colourization of the organic phase indicated impurities. TLC carried out on silica and ODS stationary phases was also applied to control impurities. Mobile phases were composed of methanol, chloroform, acetone, ACN, 2-propanol, water and 0.1 M sodium sulphate depending on the type of stationary phase. Two ODS columns were employed for the analytical separation of dyes. The parameters of the columns were 150 X 3.9 mm i.d. particle size 4 /jm and 250 X 4.6 mm i.d. particle size 5 //m. Mobile phases consisted of methanol and 0.05 M aqueous ammonium acetate in various volume ratios. The flow rate was 0.9 ml/min and dyes were detected at 254 nm. Preparative separations were carried out in an ODS column (250 X 21.2 mm i.d.) using a flow rate of 13.5 ml/min. The composition of the mobile phases employed for the analytical and preparative separation of dyes is compiled in Table 3.33. 

Despite the remarkable sensitivity of modern instrumental detection techniques, analysis of environmental water samples nearly always requires enrichment of the analytes. This, together with separation from the matrix, are the two main functions of sample preparation appropriate sample preparation techniques address both issues at the same time, while striving to impose as few restrictions as possible on the subsequent instrumental determination (separation and detection). Sample preparation is strongly dependent on the nature of the analyte and the matrix, particularly with regard to its volatility and polarity. Figure 13.8 gives a general overview of common sample preparation (enrichment) techniques for aqueous and other matrices. 

Much smaller amounts of Hquid organic solvents are used. The large quantities of organic solvents used in analytical separations have become an environmental concern. Aqueous samples become contaminated with organic solvents and evaporative concentration of the extracts pollutes the air with organic vapors. 

The separation and characterization of environmental pollutants in aqueous samples is a demanding task. The concentration of contaminants is usually very low (typical < 10 xg/L) and the matrices may be complex. GC is necessary for analyte separation while, in most cases, IR is very suitable for this purpose because of its unique molecular fingerprinting properties. Applications of GC/ FTIR are found in a wide variety of analytical fields. Most applications have been reported on the analysis of environmental samples. A representative example of what can be achieved nowadays is the identification of pesticides in water samples at the European alert and alarm levels of 0.1-1 ng/ml, as described by Hankemeier et al., ... 

Two examples from the analysis of water samples illustrate how a separation and preconcentration can be accomplished simultaneously. In the gas chromatographic analysis for organophosphorous pesticides in environmental waters, the analytes in a 1000-mL sample may be separated from their aqueous matrix by a solid-phase extraction using 15 mb of ethyl acetate. After the extraction, the analytes are present in the ethyl acetate at a concentration that is 67 times greater than that in... 

The possibility of making such MIP membrane disks has been well demonstrated yet we do not know of real-life analytical applications. This may be related to the low selective capacity of the MIPs, the slow adsorption kinetics, and the known bleeding of MIPs which may be disturbing in environmental ultratrace analysis. A further problem is that the matrix of the large sample volume (typically aqueous) may not be compatible with the MIP separation. 

A similar concept was used for other environmental applications, for example, phenoxy acids, sulfonureas, phenolic compounds, and other environmentally important persistent pollutants [68, 76, 141, 143, 155-166]. Also, in the same manner, several drugs were enriched and determined in body fluids such as urine [144-146, 167-172] or blood [147, 156, 157, 173, 174]. A very advanced apphcation of SLM for analytical purposes, where transport process was based on simple diffusion with pH adjustment of aqueous phase, is the extraction of the basic drug, bambuterol, for pretreatment of plasma samples before analysis with capfflary zone electrophoresis (CZE) [147]. Bambuterol was used as a model substance in a separation system, where either 6-undecanone or a mixture of di- -hexyl ether (DHE) and tri- -octylphosphine oxide (TOPO) was used as membrane phase. It was possible not only to achieve a very low hmit of detection ( 50 nmol/1) but also to ensure the removal of salts from the sample. It helped to obtain the low ionic strength of the blood plasma samples and permitted subsequent sample stacking in the caphlary electrophoresis step. 

As in other areas of analysis, HPLC is a useful complementary technique to GLC in analyzing pollutants in the environment. An advantage of HPLC in environmental analysis is that molecules of varying polarity (e.g. pesticide + metabolite mixtures) can be analyzed in one chromatographic run. Since aqueous mobile phases can be used in reversed-phase HPLC (including ion-pair partition modes) sample preparation is often less extensive than in GLC. The number of clean-up steps can also be reduced by the use of a precolumn to protect the analytical column or by a preliminary size separation of a crude extract on an exclusion column. 

Highlights Various procedures have been deployed to selectively preconcentrate uranyl ions from aqueous media. These processes also separate the uranium from potential interferences and alleviate matrix effects. The selection of an exphcit technique depends on the required hmits of detection and the analytical device used for measurement of uranium. The use of DGT probes scans to be gaining popularity, especially for sampling sahne media. These methods may be helpful in environmental analysis despite the fact the limit of detection of modem analytical techniques is well below the uranium level found in almost aU reahstic samples. 

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