Sampling extractive

An on-line concentration, isolation, and Hquid chromatographic separation method for the analysis of trace organics in natural waters has been described (63). Concentration and isolation are accompHshed with two precolumns connected in series the first acts as a filter for removal of interferences the second actually concentrates target solutes. The technique is appHcable even if no selective sorbent is available for the specific analyte of interest. Detection limits of less than 0.1 ppb were achieved for polar herbicides (qv) in the chlorotriazine and phenylurea classes. A novel method for deterrnination of tetracyclines in animal tissues and fluids was developed with sample extraction and cleanup based on tendency of tetracyclines to chelate with divalent metal ions (64). The metal chelate affinity precolumn was connected on-line to reversed-phase hplc column, and detection limits for several different tetracyclines in a variety of matrices were in the 10—50 ppb range. 

Spectrophotometric deterrnination at 550 nm is relatively insensitive and is useful for the deterrnination of vitamin B 2 in high potency products such as premixes. Thin-layer chromatography and open-column chromatography have been appHed to both the direct assay of cobalamins and to the fractionation and removal of interfering substances from sample extracts prior to microbiological or radioassay. Atomic absorption spectrophotometry of cobalt has been proposed for the deterrnination of vitamin B 2 in dry feeds. Chemical methods based on the estimation of cyanide or the presence of 5,6-dimethylben2irnida2ole in the vitamin B 2 molecule have not been widely used. 

Composite Samples Obtained hy Multiple Sample Extractions. 19-8... 

Theoiy related to material characteristics states that a minimum quantity of sample is predicated as that amount required to achieve a specified limit of error in the sample-taking process. Theoiy of sampling in its apphcation acknowledges sample preparation and testing as additional contributions to total error, but these error sources are placed outside consideration of sampling accuracy in theoiy of sample extraction. 

The theoiy enables a reasonable estimate of sample quantity needed to attain specified accuracy of a composition variable. The result is an ideal quantity—not realized in practice. Actual quantities for practical estimation are larger by an appropriate multiple to account for the reality that material is incompletely mixed when stored in stockpiles or carried on conveyors. Sample quantity to accommodate incompletely mixed sohds can be specified through evaluating variance by autocorrelation of data derived with a series of stockpile samples, or from multiple sample extractions taken from a moving stream (Gy, Pitard). 

The alternative method of sample extrac tion is termed the ctoss-sti eam samphng method, or ci o.s.s-belt when used in conjunc tiou with a belt conveyor. Sample extraction typically take place with a belt conveyor in motion. However, with a rotary table-feeder conveyor, extractions are made with the table stopped. A cutter can perform extractions by this means from a machined flat surface with neghgible... 

Cross-stream samphng from flat surfaces with material handled on a hnear conveyor or rotary table is best carried out with the conveyor stopped. Sample extraction is then performed by linear traverse. 

In Fig. 19-5, the conveyor belt is radially profiled at the point of sample extraction with contouring idlers set to match the path of the cutter moving from its driveshaft rotation axis. Cutter edges are posi-... 

Composite Samples Obtained by Multiple Sample Extractions Material flow streams are sampled in practice by combining extractions taken at successive time intei vals into a composite sample. Multiple increment collection to obtain representative composite sampfes for specified bulk-material flows is performed according to a... 

Calculation of Sample Extraction Increments Sample quantities taken in an extraction increment are calculated in accord with the mechanical sampler employed. The following three examples illustrate calculations for three commonly used sampling methods. 

Microwave extraction realized at 120 °C for 30 min with Hexane -Acetone (3 2 V/V) as the extraction solvent was identified as the most effective extraction procedure for isolation of TPH from biotic matrices. The aim of this research is to develop a silica gel and alumina fractionation procedure for plant sample extraction. Column chromatography with two solvents (chloroform and hexane dichloromethane) as a mobile phase were used for clean-up of extract. In this research the efficiency of recovery received from chloroform as a mobile phase. 

Spatial and temporal transfer of sample extract with minimum and/or known effects on sample integrity... 

Figure 2.16 Clirotnatograms of a pentane extract of a water sample containing 200 ppb of a naphtha fraction (a) sample extracted by using a continuous flow system, where a pressurized bottle was employed as the sample-delivery system (b) batch-extracted sample. Reprinted from Journal of Chromatography, A 330, J. Roeraade, Automated monitoring of organic Race components in water. I. Continuous flow exti action together with on-line capillary gas cliro-matography , pp. 263 - 274, copyrigth 1985, with permission from Elsevier Science.

The experimental conditions are shown in Table 13.1, while Figure 13.9 shows the chromatogram of a soil sample extract spiked with fenpropimorph obtained by this method, plus the chromatogram from the two columns connected in series without column switching. 

For superheated steam, the sample points should be designed and installed to permit correct isokinetic sampling. A modified multiport nozzle design ensures that the velocity of the steam entering the sample nozzle is the same as the velocity of steam in the header. The design incorporates a small, high-quality water delivery tube, used to inject water and remove superheat before sample extraction. 

Sampling Procedure. The sample extraction technique previously described was used in this work (8). However, a heated palladium thimble was also used to separate hydrogen and hydrocarbon fractions of the samples. No exchange occurred during the separation process in agreement with observations of other workers (30). In experiments using NH3 as a minor additive, the ammonia fraction was separated by means of appropriate cold traps. 

Recent Uses of Solid-Surface Luminescence Analysis in Environmental Analysis. Vo-Dinh and coworkers have shown very effectively how solid-surface luminescence techniques can be used for environmentally important samples (17-22). RTF has been used for the screening of ambient air particulate samples (17,18). In addition, RTF has been employed in conjunction with a ranking index to characterize polynuclear aromatic pollutants in environmental samples (19). A unique application of RTF reported recently is a personal dosimeter badge based on molecular diffusion and direct detection by RTF of polynuclear aromatic pollutants (20). The dosimeter is a pen-size device that does not require sample extraction prior to analysis. 

The predominant method of analyzing environmental samples for methyl parathion is by GC. The detection methods most used are FID, FPD, ECD, and mass spectroscopy (MS). HPLC coupled with ultraviolet spectroscopy (UV) or MS has also been used successfiilly. Sample extraction and cleanup varies widely depending on the sample matrix and method of detection. Several analytical methods used to analyze environmental samples for methyl parathion are summarized in Table 7-2. 

Three out of nine groundwater samples extracted from Dobrich in northeastern Bulgaria contained endosulfan (isomers not specified) ranging from 0.020 to 0.025 pg/L in March 1996 (Pulido-Bosch et al. 1999). The suspected source of this pollution was from agricultural practices in the region. 

In the past decade, new sample extraction techniques have been introduced to meet stricter criteria in the areas of food and agriculture, for example, enviromnentally friendly, non-toxic, fast, automated, robust, and cost-efficient techniques. Accelerated solvent extraction (ASE) and pressurized liquid extraction (PEE) are two methods developed for the extraction of chemicals of interest " and provide high yields and efficiency from a wide range of botanical, - animal, and biological samples. ASE and PLE combine solvents at elevated temperatures (40 to 200°C)... 

As with urine, saliva (spumm) is easy to collect. The levels of protein and lipids in saliva or spumm are low (compared to blood samples). These matrices are viscous, which is why extraction efficiency of xenobioties amoimts to only 5 to 9%. By acidifying the samples, extraction efficiencies are improved as the samples are clarified, and proteinaceous material and cellular debris are precipitated and removed. Some xenobioties and their metabohtes are expressed in hair. Hair is an ideal matrix for extraction of analytes to nonpolar phases, especially when the parent xenobioties are extensively metabolized and often nondetectable in other tissues (parent molecules of xenobioties are usually less polar than metabolites). Hair is a popular target for forensic purposes and to monitor drug compliance and abuse. Human milk may be an indicator of exposure of a newborn to compounds to which the mother has been previously exposed. The main components of human milk are water (88%), proteins (3%), lipids (3%), and carbohydrates in the form of lactose (6%). At present, increasing attention is devoted to the determination of xenobioties in breath. This matrix, however, contains only volatile substances, whose analysis is not related to PLC applications. 

---