Solvent PAHs using

Alternatively, LC is used for the separation and quantification of PAHs using both UV and fluorescence detection. The analytes are identified based on their relative retention times and UV and/or fluorescence emission spectra. For UV detection an efficient cleanup is a prerequisite since this detection method is not very selective (almost universal for PAHs), and hence it also responds to many coeluting compounds. Due to the high specificity of fluorescence detection for most PAHs, this LC detection method is less susceptible to potential interferences. As in the case of GC the apphcation of internal standard(s) is mandatory since solvents have to be evaporated during the cleanup, which may result in partial losses of some of the more volatile analytes. 

The first use of supercritical fluid extraction (SFE) as an extraction technique was reported by Zosel [379]. Since then there have been many reports on the use of SFE to extract PCBs, phenols, PAHs, and other organic compounds from particulate matter, soils and sediments [362, 363, 380-389]. The attraction of SFE as an extraction technique is directly related to the unique properties of the supercritical fluid [390]. Supercritical fluids, which have been used, have low viscosities, high diffusion coefficients, and low flammabilities, which are all clearly superior to the organic solvents normally used. Carbon dioxide (C02, [362,363]) is the most common supercritical fluid used for SFE, since it is inexpensive and has a low critical temperature (31.3 °C) and pressure (72.2 bar). Other less commonly used fluids include nitrous oxide (N20), ammonia, fluoro-form, methane, pentane, methanol, ethanol, sulfur hexafluoride (SF6), and dichlorofluoromethane [362, 363, 391]. Most of these fluids are clearly less attractive as solvents in terms of toxicity or as environmentally benign chemicals. Commercial SFE systems are available, but some workers have also made inexpensive modular systems [390]. 

Quality Assurance/Quality Control. QA/QC measures included field blanks, solvent blanks, method blanks, matrix spikes, and surrogates. Percent recovery was determined using three surrogate compounds (nitrobenzene-d5, 2-fluorobiphenyl, d-terphenyl-diQ and matrix spikes (naphthalene, pyrene, benzo[ghi]perylene) the recoveries ranged from 80 to 102%. Separate calibration models were built for each of the 16 PAHs using internal standards (naphthalene-dg, phenanthrene-dio, perylene-di2). Validation was performed using a contaminated river sediment (SRM 1944) obtained from NIST (Gaithersburg, MD) accuracy was <20% for each of the 16 analytes. 

Total petroleum hydrocarbons (TPHs). A method for the determination of TPHs could be GC-FID. As before, the optional benefits of MSD (see PAHs) may be advantageous. However, as information is only required on total petroleum hydrocarbons, an alternative analytical technique is possible, i.e. FTIR spectroscopy. In this situation, C-H bands are observed in the region 2800-3000 cm-1. Care, however, must be taken in the choice of the solvent used for the preparation of standards and samples. The solvent must not contain carbon and hydrogen. A typical solvent to use, therefore, would be tetrachloroethylene. 

Phytoremediation has been used to treat sites contaminated with a variety of contaminants including heavy metals, solvents, PAHs, PCBs, hydrocarbons, radionuclides, explosives, and pesticides.20,21,24 The approaches are probably... 

The analytical procedure for extraction and class separation was adapted from Venkatesan et al. (1987) and consisted of repeated ultrasonic solvent extractions using hexane/acetone followed by saponification of the free fatty acids in KOH/methanol. The organic extract was then divided into three fractions containing aliphatics (w-alkanes), PAH and n-alcohols, and sterols using open column chromatography on 10% water-deactivated silica. Free fatty acids and n-alcohols were derivatized by BSTFA prior to analysis on GC-MS. All determinations were performed using a Hewlett Packard 5890 series 11 gas chromatograph equipped with a split/splitless injector and an electronic pressure control. The column was a 30 m X 0.25 mm ID coated with a 0.25 /rm, 5% phenyl-methylsilicone phase (J W DB-5MS) at a head pressure... 

In situ generated micelles have been applied to the inspection of aniline pesticidic metabolites in lake water. The separation of 16 PAH in SUA oligomer electrolytes was reported. Creosote-contaminated soil samples were extracted by accelerated solvent extraction using methylene chloride-acetone mixtures. The extracts were further fractioned by gel permeation chromatography before analysis. The EKC chromatogram of a creosote-contaminated soil fraction shows the resolution of at least 50 peaks. The separation of the 11 priority phenols in river and sea water was demonstrated in MEKC with DBTD surfactants, whereas examples of the use of liposomes as carriers include the separation of benzene derivatives and phenols." ... 

Polycyclic aromatic hydrocarbons (PAHs) are nonpolar analytes regulated by the EPA. One standard method, US EPA SW-846 Method 8310, dictates that an acetonitrile/water gradient on a Cig column be used. However, PAH solubility decreases rapidly as the ring number increases fiom naphthalene (two fused rings) to benzo[g,/i,/]perylene (six fused rings). Such solubility limitations are not a problem when alkane solvents are used. 

The aqueous micellai solutions of some surfactants exhibit the cloud point, or turbidity, phenomenon when the solution is heated or cooled above or below a certain temperature. Then the phase sepai ation into two isotropic liquid phases occurs a concentrated phase containing most of the surfactant and an aqueous phase containing a surfactant concentration close to the critical micellar concentration. The anionic surfactant solutions show this phenomenon in acid media without any temperature modifications. The aim of the present work is to explore the analytical possibilities of acid-induced cloud point extraction in the extraction and preconcentration of polycyclic ai omatic hydrocai bons (PAHs) from water solutions. The combination of extraction, preconcentration and luminescence detection of PAHs in one step under their trace determination in objects mentioned allows to exclude the use of lai ge volumes of expensive, high-purity and toxic organic solvents and replace the known time and solvent consuming procedures by more simple and convenient methods. 

Some groups of pollutants also have specific problems. For instance, PAHs tend to adsorb on the walls of the system with which they come into contact and so an organic solvent or surfactant must be added to the sample. Several solvents have been tested (66, 67) isopropanol or acetonitrile are the most often used solvents, while Brij is the most recommended surfactant (66). A very critical parameter in these cases is their concentration. 

Standardization. Standardization in analytical chemistry, in which standards are used to relate the instrument signal to compound concentration, is the critical function for determining the relative concentrations of species In a wide variety of matrices. Environmental Standard Reference Materials (SRM s) have been developed for various polynuclear aromatic hydrocarbons (PAH s). Information on SRM s can be obtained from the Office of Standard Reference Materials, National Bureau of Standards, Gaithersburg, MD 20899. Summarized in Table VII, these SRM s range from "pure compounds" in aqueous and organic solvents to "natural" matrices such as shale oil and urban and diesel particulate materials. 

If the sample and standard have essentially the same matrices (e.g., air particulates or river sediments), one can go through the total measurement process with both the sample and the standard in order to (a) check the accuracy of the measurement process used (compare the concentration values obtained for the standard with the certified values) and (b) obtain some confidence about the accuracy of the concentration measurements on the unknown sample since both have gone through the same chemical measurement process (except sample collection). It is not recommended, however, that pure standards be used to standardize the total chemical measurement process for natural matrix type samples chemical concentrations in the natural matrices could be seriously misread, especially since the pure PAH probably would be totally extracted in a given solvent, whereas the PAH in the matrix material probably would not be. All the parameters and matrix effects. Including extraction efficiencies, are carefully checked in the certification process leading to SRM s. 

The theory and development of a solvent-extraction scheme for polynuclear aromatic hydrocarbons (PAHs) is described. The use of y-cyclodextrin (CDx) as an aqueous phase modifier makes this scheme unique since it allows for the extraction of PAHs from ether to the aqueous phase. Generally, the extraction of PAHS into water is not feasible due to the low solubility of these compounds in aqueous media. Water-soluble cyclodextrins, which act as hosts in the formation of inclusion complexes, promote this type of extraction by partitioning PAHs into the aqueous phase through the formation of complexes. The stereoselective nature of CDx inclusion-complex formation enhances the separation of different sized PAH molecules present in a mixture. For example, perylene is extracted into the aqueous phase from an organic phase anthracene-perylene mixture in the presence of CDx modifier. Extraction results for a variety of PAHs are presented, and the potential of this method for separation of more complex mixtures is discussed. 

The data were collected using fluorescence measurements, which allow both identification and quantitation of the fluorophore in solvent extraction. Important experimental considerations such as solvent choice, temperature, and concentrations of the modifier and the analytes are discussed. The utility of this method as a means of simplifying complex PAH mixtures is also evaluated. In addition, the coupling of cyclodextrin-modified solvent extraction with luminescence measurements for qualitative evaluation of components in mixtures will be discussed briefly. 

Cyclodextrin-modified solvent extraction has been used to extract several PAHs from ether to an aqueous phase. Data evaluation shows that the degree of extraction is related to the size of the potential guest molecule and that the method successfully separates simple binary mixtures in which one component does not complex strongly with CDx. The most useful application of cyclodextrin-modified solvent extraction is for the simplification of complex mixtures. The combined use of CDx modifier and data-analysis techniques may simplify the qualitative analysis of PAH mixtures. 

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