Extraction techniques, comparative

Experimental comparisons may suffer from a lack of optimal conditions for all methods considered or may be based on biased evaluation. It is frequently noticed that results quoted by the preferred extraction technique compare extremely favourably with existing extraction technology. Also, lack of prospects of using CRMs is not helpful for comparisons. However, it appears that for a given infrastructure (R D vs. plant laboratory) and need (routine vs. occasional operations), and depending on the mix of polymeric matrices to be handled, some preferences may clearly be expressed. 

Supercritical fluid extraction (SFE) has also been used for the extraction of MMHg from sediments. ° Lorenzo et al. ° compared manual, microwave assisted techniques and SFE for the extraction of Hg from aquatic sediments. Higher recoveries were obtained with microwave extraction techniques compared to manual extraction techniques and SFE. 

Table 1. Radiocarbon dates from the plasma extraction technique compared to previously determined radiocarbon ages for charcoal and TlRl wood...

This procedure was compared with sequential extractive techniques employing alkaline hydrolysis of dried plant tissue followed by extraction of the acidified mixture with ethyl acetate. Fractions were individually evaluated for phytotoxic properties. Selected fractions from those showing a positive response were analyzed by gas-liquid chromatography. Structural identification and characterization of the individual components in these selected fractions were accomplished by gas chromatography-mass spectrometry. 

Polymer/additive analysis then usually proceeds by separation of polymer and additives (cf. Scheme 2.12) using one out of many solvent extraction techniques (cf. Chapter 3). After extraction the residue is pressed into a thin film to verify that all extractables have been removed. UV spectroscopy is used for verification of the presence of components with a chromophoric moiety (phenolic antioxidants and/or UV absorbers) and IR spectroscopy to verify the absence of IR bands extraneous to the polymer. The XRF results before and after extraction are compared, especially when the elemental analysis does not comply with the preliminary indications of the nature of the additive package. This may occur for example in PA6/PA6.6 blends where... 

Some typical applications in SFE of polymer/additive analysis are illustrated below. Hunt et al. [333] found that supercritical extraction of DIOP and Topanol CA from ground PVC increased with temperature up to 90 °C at 45 MPa, then levelled off, presumably as solubility became the limiting factor. The extraction of DOP and DBP plasticisers from PVC by scC02 at 52 MPa increased from 50 to 80 °C, when extraction was almost complete in 25 min [336]. At 70 °C the amount extracted increased from 79 to 95 % for pressures from 22 to 60 MPa. SFE has the potential to shorten extraction times for traces (<20ppm) of additives (DBP and DOP) in flexible PVC formulations with similar or even better extraction efficiencies compared with traditional LSE techniques [384]. Marin et al. [336] have used off-line SFE-GC to determine the detection limits for DBP and DOP in flexible PVC. The method developed was compared with Soxhlet liquid extraction. At such low additive concentrations a maximum efficiency in the extractive process and an adequate separative system are needed to avoid interferences with other components that are present at high concentrations in the PVC formulations, such as DINP. Results obtained... 

It is not uncommon that extraction techniques are unfairly compared. Appropriate interlaboratory studies are few. Soxhlet and sonication extraction (EPA methods 3540 and 3550, respectively) were compared in an interlaboratory study (129 participants) for PCBs in soil. Results from laboratories using Soxhlet extraction were significantly more accurate than those obtained using sonication, especially at higher concentrations, but with equal precision [196]. This is rationalised by the observation that the Soxhlet procedure presents the sample with fresh solvent so that the extraction solvent is never saturated, unlike the sonication procedure. Sonication is very sensitive to the solvent polarity, nonpolar solvents producing considerably less accurate results than polar solvents. It is not as sensitive to clean-up procedures as... 

Desrosiers [23] has dared ranking extracting methods as follows (in order of preference) SFE, US, hot block or MAE, Soxhlet (to be phased out as quickly as possible). Munteanu [556] has evaluated extraction techniques for additives from polymers prior to chromatographic analysis (up to 1990). The analytical extraction of additives from polymers has recently critically been reviewed with emphasis on SFE, MAE and ASE [92]. Dean [272] compared modem extraction techniques, with focus on environmental analysis. 

Kirschner et al. [358] have observed a lower percent finish-on-yarn (FOY) for SFE as compared to solvent extraction of various fibre/textile matrices. This is rationalised as organic solvents tend to extract components from a matrix more vigorously than scCC>2 and thus remove more of the oligomer and organic components present in the fibre. SFE is a potentially softer extraction technique since it removes less of the polymer from the fibre matrix than liquid solvent extraction. 

Hinman et al. [492] have compared SFE and ASE in the extraction of antioxidants from LDPE. Comparable extraction yields were obtained with both techniques. However, sample clean-up was necessary after ASE , while with SFE the extract could be analysed directly without any post-extraction clean-up. Supercritical fluid extraction of 15 polymer additives (AOs, UVAs, process lubricants, flame retardants and antistatic agents) from eight PS formulations was compared to dissolu-tion/precipitation extractions [557], Additive recoveries were comparable. Numerous additional comparisons can be found under the specific headings of the extraction techniques (Sections 3.3 and 3.4). 

In recent years, extraction methods for PhACs have usually been based on liquid partitioning with ultrasonic extraction (USE) [43-47], microwave-assisted extraction (MAE) [48], or the more advanced PLE [49-52]. When compared to the other extraction techniques, PLE provides good recoveries, saves time and organic solvent, which makes it become currently a preferred technique for PhAC analyses. 

Two commercial partial extraction techniques improve anomaly contrast in B horizon soil samples compared to aqua regia-ICPMS for Cu and Au. However, whereas the MMIsm and Bio LeachSM Cu profiles are similar, the MMIsm Au signal is much larger than that for Bio LeachSM. Analysis of samples at different depths down the B soil horizon profile indicates that the geochemical response from these methods is depth dependant. 

The next step is to chemically extract the lipids from the visible residue, powdered shard, or soil. A number of novel and conventional sample extraction techniques have been compared by Stern et al. (2000). There are two main methods routinely employed, but the exact conditions may vary between different laboratories. 

David and Seilier [1] compared the efficiencies of various extraction techniques including supercritical fluid [2], high pressure solvent and Soxhlet extraction for the removal of organophosphorus hydraulic fluids from soil. High pressure solvent extraction was at temperatures up to 200°C and pressures up to 170 bar was the favoured technique. Extraction efficiencies were similar in all three methods, but the favoured method was more rapid and cheaper to operate. 

Klenke et al. [5] described a technique for extraction of humic and fulvic acids from stream sediments and outlined methods for their determination. By means of flame atomic absorption spectrometry, the levels of environmentally important heavy metals (cadmium, copper, chromium, cobalt, nickel and lead) in the fulvic and humic acid extracts were compared with those in the original sediment samples. The pattern distribution of the respective metals in the two cases showed very close agreement, suggesting that the combined extract of humic and fulvic acids could be used as an indicator of the level of heavy metal pollution in flowing waters. 

According to Coimbra et solvents play a central role in the majority of chemical and pharmaceutical industrial processes. The most used method to obtain artemisinin (1) from A. annua is through the use of organic solvents such as toluene, hexane, cyclohexane, ethanol, chloroform and petroleum ether. Rodrigues et al described a low-cost and industrial scaled procedure that enables artemisinin (1) enhanced yields by using inexpensive and easy steps. Serial extraction techniques allowed a reduction of 65% in solvent consumption. Moreover, the use of ethanol for compound extraction is safer when compared to other solvents. Flash column pre-purification employing silicon dioxide (Zeosil ) as stationary phase provided an enriched artemisinin (1) fraction that precipitated in hexane/ethyl acetate (85/15, v/v) solution. These results indicate the feasibility of producing artemisinin (1) at final cost lowered by almost threefold when compared to classical procedures. 

To illustrate the advantage of this technique, compared either to direct chromatographic analysis of the water system or of an organic solvent extract, we may consider the circumstance of hexane as a hypothetical contaminant. This compound is distributed to the extent of 96% into the gas phase. The implications... 

Extraction of stevia sweeteners from dried leaves can be accomplished with acetonitrile in the presence of calcium carbonate solution (116) or with boiling water adjusted to pH 9.0 (107). Ahmed and Dobberstein (117) extracted stevioside and rebaudioside A and C from dried leaves of S. rebaudiana in a micro-Soxhlet apparatus. They observed that chloroform/methanol provided the best results, compared to chloroform or to chloroform/methanol/water. Extraction of stevioside, rebaudioside A and C, and dulcoside A can also be performed by subcritical fluid extraction using C02 and methanol as a modifier. Such an extraction technique has been gaining popularity as an analytical tool because it is rapid, simple, and less expensive in terms of solvent cost (110). Beverages, tabletop sweeteners, beverages containing pulp, and candies are prepared as indicated in Sec. I.C (110,115,118). 

Diuron from soil Diuron spiked Tama soil was the extraction example used in the six vessel multi-vessel extractor. As is illustrated in Table III, the average recovery for these samples was 97.3% and the relative standard deviation was 6.6%. When these results are compared to those obtained with the classical extraction techniques, equivalent recoveries were achieved. However, the precision associated with the classical extraction was typically 20%. Acceptable recovery ranges in classical residue analysis are from 70 to 125%. Comparing these precisions with those obtained with a one vessel SFE device, the... 

As an extraction technique, SFE proved to give comparable recoveries to those of Soxhlet extraction. In all cases, SFE dramatically shortened extraction times and minimized most environmental hazards, solvent concentration steps, and waste disposal costs. A summary of this comparison is included as Table XII and is a projected cost comparison of SFE to Soxhlet extraction, based on our experiences with the SFE system used in these studies (Isco SFE System 1200). The projected cost per extraction was determined to be 15.85(SFE) vs. 22.60(Soxhlet). 

Hubert et al. [101] state that accelerated solvent extraction compared to alternatives such as Soxhlet extraction, steam distillation, microwave extraction, ultrasonic extraction and, in some cases, supercritical fluid extraction is an exceptionally effective extraction technique. Hubert et al. [ 101 ] studied the effect of operating variables such as choice of solvent and temperature on the solvent extraction of a range of accelerated persistent organic pollutants in soil, including chlorobenzenes, HCH isomers, DDX, polychlorobiphenyl cogeners and polycyclic aromatic hydrocarbons. Temperatures ofbetween 20 and 180 °C were studied. The optimum extraction conditions use two extraction steps at 80 and 140 °C with static cycles (extraction time 35 minutes) using toluene as a solvent and at a pressure of 15 MPa. 

It is also possible to display the results for one product with all the categories in one graph (Figure 18.10). This way of presenting results is very useful for comparing two different products (here extraction techniques). 

Table 19.9 compares various solvent extraction techniques with regard to the duration and the amount of the solvent used (per 1 sample), and Figure 19.7 presents basic information on the main groups of solvent-free techniques in the context of sample preparation for analysis. 

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