Extraction solvents limitations

Extraction Eiltering limits particulate gravimetry to solid particulate analytes that are easily separated from their matrix. Particulate gravimetry can be extended to the analysis of gas-phase analytes, solutes, and poorly filterable solids if the analyte can be extracted from its matrix with a suitable solvent. After extraction, the solvent can be evaporated and the mass of the extracted analyte determined. Alternatively, the analyte can be determined indirectly by measuring the change in a sample s mass after extracting the analyte. Solid-phase extractions, such as those described in Ghapter 7, also may be used. 

The FDA has pubhshed methods for the deterrnination of residual solvents in spice extracts such as oleoresins and has limited the concentrations of those specific solvents that are permitted. Chlorinated hydrocarbons and benzene have been almost completely removed from use as extracting solvents in the United States their use continues overseas where toxicity regulations are less stringent. The presence of pesticides or herbicides in spices is rigidly controHed by the FDA. 

Accelerated solvent extraction (ASE) is a technique which attempts to merge the beneficial solvation properties of SFE with traditional organic solvents. Specifically, the sample is placed in an extraction vessel which can withstand high pressures while being maintained at a constant temperature. Extraction is carried out by pumping the extraction solvent through the samples for a limited time. As an example of the use of ASE, Richter and Covino extracted PCBs from a 10-g fish tissue sample with hexane... 

A disadvantage of supercritical fluids for extraction is that most common fluids used for extraction (carbon dioxide, nitrous oxide, sulfur hexafluoride, etc.) are weak solvents, limiting the polarity and molecular weight range of analytes that can be efficiently extracted. Also, for trace analysis the availability of fluids of adeguate ptirity may be a problem. 

Some guidelines for predicting the results from distributing a sample between two immiscible solvents are summarized in Table 8.3 [67,68]. The efficiency of an extracting solvent, E, depends primarily on the affinity of the solute for the extracting solvent, Kd) the phase ratio, V, and the number of extractions, n. For simple batchwlse extractions K, should be l u ge, as there is a practical limit to the volume of the extracting solvent and the... 

The static ASE mode may lead to incomplete extraction because of the limited volume of solvent used. Dynamic ASE yields faster extractions by continuously providing fresh extraction solvent to the sample, but obviously requires a larger solvent volume than static ASE and is therefore less suited for trace analysis. In practice, a combination of static and dynamic extraction is often considered to be the best choice. 

The use of the Hildebrand solubility parameter approach to aid solvent selection with a few simple experiments, starting from the liquid solvents used in traditional extraction methods, limits the efforts needed in method development. As for other extraction... 

High selectivity (i.e. the ability to separate analytes from matrix interferences) is one of the most powerful aspects of SPE. This highly selective nature of SPE is based on the extraction sorbent chemistry, on the great variety of possible sorbent/solvent combinations to effect highly selective extractions (more limited in LLE where immiscible liquids are needed) and on the choice of SPE operating modes. Consequently, SPE solves many of the most demanding sample preparation problems. 

Water samples are acidified and extracted with solvent (Kawamura and Kaplan 1983 Muir et al. 1981). Clean-up steps may be used (Kawamura and Kaplan 1983). Methylene chloride is often used as the extracting solvent, and it may interfere with the nitrogen-phosphorus detector. In this case, a solvent-exchange step is used (Muir et al. 1981). Analysis by GC/NPD or GC/MS provides specificity (Kawamura and Kaplan 1983 Muir et al. 1981). Accuracy is acceptable (>80%), but precision has not been reported. Detection limits were not reported, but are estimated to be 0.05-0.1 pg/L (Muir et al. 1981). Detection limits at the low ppt level (ng/L) were achieved by concentrating organophosphate esters on XAD-2 resin. The analytes were solvent extracted from the resin and analyzed by GC/NPD and GC/MS. Recovery was acceptable (>70%) and precision was good (<10% RSD) (LeBel et al. 1981). 

Part II extraction solvents for which conditions of use/maximum residue limits, are specified hexane, methanol, propan-2-ol, methyl acetate, ethyl-methylketone, dichloromethane. 

Freon-extractable material is reported as total organic material from which polar components may be removed by treatment with silica gel, and the material remaining, as determined by infrared (IR) spectrometry, is defined as total recoverable petroleum hydrocarbons (TRPHs, or total petroleum hydrocarbons-IR). A number of modifications of these methods exist, but one particular method (EPA 418.1 see also EPA 8000 and 8100) has been one of the most widely used for the determination of total petroleum hydrocarbons in soils. Many states use or permit the use of this method (EPA 418.1) for identification of petroleum products and during remediation of sites. This method is subject to limitations, such as interlaboratory variations and inherent inaccuracies. In addition, methods that use Preon-113 as the extraction solvent are being phased out and the method is being replaced by a more recent method (EPA 1664) in which n-hexane is used as the solvent and the n-hexane extractable material (HEM) is treated with silica gel to yield the total petroleum hydrocarbons. 

In the previous section, the role of solvent extraction was limited to preparing the analyte for subsequent analysis. A large majority of procedures that use solvent extraction in chemical analysis are used in this fashion. However, the extraction itself, or rather the distribution ratio characterizing it, may provide an appropriate measured signal for analysis. Examples of this use of solvent extraction are found in spectroscopy, isotope dilution radiometry, and ion-selective electrodes using liquid membranes. In the latter case, electrochemical determinations are possible by controlling the local concentration of specific ions in a solution by extraction. 

Catalysis in ionic liquids is not limited to biphasic reaction systems. When the reaction mixture is homogeneous, an extraction solvent that is immiscible with the ionic liquid can be used to remove the product. A number of organic solvents display little or only limited miscibility with these liquids. However, this advantage is of limited value in practice, because one major incentive for using ionic liquids is to avoid volatile organic compounds. 

The Joint FAO/WHO Expert Committee on Food Additives (WHO, 1983) withdrew the previously allocated temporary allowable daily intake (ADI) of 0-0.5 mg/kg body weight and recommended that the use of dichloromethane as an extraction solvent be limited, in order to ensure that its residues in food are as low as practicable. 

SOLVENT Choice. Solvent extraction is limited to water immiscible solvents. Solid adsorbents do not have this limitation, so miscible solvents, desirable for subsequent analytical or bioassay purposes, can be used. For example, DMSO is preferred for mutagenicity screening and has been used to elute the adsorbed organic material (211-213, 216, 235, 328). For analytical purposes, acid, base, and neutral eluents can be employed for on-column fractionation of the adsorbed organic solutes (78, 80,196). 

Normally, the concentration of solute in the final extract is limited to the value in equilibrium with the feed, but a countercurrent stream that is richer than the feed is available for enrichment of the extract. This is essentially solvent-free extract as reflux. A flowsketch and nomenclature of such a process are given with Example 14.7. Now there are two operating points, one for above the feed and one for below. These points are located by the following procedure ... 

The working group CEN TC 275/WG 5 searched for performance criteria to be used in mycotoxin analysis and came up with a document reporting the criteria for the selection of methods (26). The criteria deal with limits of detection, minimum performance characteristics, extraction solvents, and applicability. Criteria for analytical methods in mycotoxin analysis are also included in Directive 98/53/EC (18). 

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