Semivolatile Samples

As stated, the distinction between semivolatile and volatile samples is somewhat arbitrary. For this chapter, semivolatile samples are defined as those compounds with vapor pressures too low to be directly detected by IMS. Because most ionization sources used with IMS require neutral vapor samples to be submitted to the ionizing radiation, semivolatiles must be converted to the vapor state before detection. Volatilization is typically accomplished by increasing the temperature of the introduction platform through thermal desorption or heated chromatographic inlets and in some cases by changing the chemical form of the compound through simple chemical treatment of the sample (e.g., using an alkaline solution to convert acidic amines into volatile free base). Chemical conversion and heat can be combined to enhance vaporization. 

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Water may be found in the crude either in an emulsified form or in large droplets. The quantity is generally limited by pipeline companies and by refiners, and steps are normally taken at the wellhead to reduce the water content as low as possible. However, after a spill, water can be introduced by climatic conditions, and the relevant tests (ASTM D96, D954, D1796 IP, 2004) are regarded as important in crude oil analyses. Prior to analyses, it is often necessary to separate the water from a crude oil sample, and this is usually carried out by one of the procedures described in the preliminary distillation of crude petroleum (IP 24). Overall, there are several methods that can be employed for organic semivolatile sample preparation and cleanup procedures (Table 6.4). 

Table 6.4. Organic Semivolatile Sample Preparation and Cleanup Procedures in SW-846...

Because IMS is a method that separates gas phase ions through collisions with a buffer gas, all analytes must be transported from the sample matrix and converted to a gas phase ion before ion mobility separation and detection can be performed. Thus, the type of introduction method largely depends on the physical characteristics of the analyte. The remainder of this chapter is divided into four sections based on the characteristics of the sample vapor, semivolatile, aqueous, and solid. While these categories are somewhat arbitrary with significant sample overlap, it is useful to think of volatile samples as those compounds that exist or partially exist as vapors under ambient temperature and pressure semivolatile samples as those compounds that can be volatilized but have vapor pressures too low to detect by IMS under ambient temperature and pressure aqueous samples as those compounds that are not volatile but can be dissolved in water and solid samples as compounds not in a solution. Table 3.1 lists a number of example analytes according to the categories discussed in this chapter. 

APCI is best suited to relatively polar, semivolatile samples. 

LC - MS type LC flow range Detection limit Solvent type range Nonvolatile thermally labile samples Semivolatile samples Molecular mass range... 

Dynamic headspace GC/MS. The distillation of volatile and semivolatile compounds into a continuously flowing stream of carrier gas and into a device for trapping sample components. Contents of the trap are then introduced onto a gas chromatographic column. This is followed by mass spectrometric analysis of compounds eluting from the gas chromatograph. 

Semivolatile Organics Sampling EPA Method 0010 as contained in Test Methods for Evaluating Solid Waste, 3d ed., Report No. 

SW-846, is used to measure emissions of semivolatile principal organic constituents. Method 0010 is designed to determine destruction and removal efficiency (DRE) of POHCs from incineration systems. The method involves a modification of the EPA Method 5 sampling train and may be used to determine particulate emission rates from stationary sources. The method is applied to semivolatile compounds, including polychlorinated biphenyls (PCBs), chlorinated dibenzodioxins and dibenzofurans, polycyclic organic matter, and other semivolatile organic compounds. 

Gaseous and particulate pollutants are withdrawn isoldnetically from an emission source and collected in a multicomponent sampling train. Principal components of the train include a high-efficiency glass- or quartz-fiber filter and a packed bed of porous polymeric adsorbent resin (typically XAD-2 or polyurethane foam for PCBs). The filter is used to collect organic-laden particulate materials and the porous polymeric resin to adsorb semivolatile organic species (com-... 

A second sampling program in Southern California sampled for polychlorinated dioxins and polychlorinated dibenzofurans at seven locations (9). Because of the semivolatile nature of these compounds, a tandem sampler was used with a glass fiber filter to collect the particulate-associated compo-... 

Frequently, column problems are caused by the samples that are being analyzed. This type of problem is more likely to occur on capillary columns because of their low capacity for contamination. Contamination results when the sample contains nonvolatile or even semivolatile materials such as salts, sugars, proteins, and so on. Column contamination is more frequently observed with splitless injection because larger amounts of material are being injected on the column. 

The symptoms of column contamination include irregular peak shape, loss of resolution, loss of retention, irregular or noisy baseline, and ghost peaks from semivolatile materials of a previous run or from sample decomposition. Some of these problems can be the result of a contaminated injector. 

In general, CE is simple, rapid, and low cost because it needs neither laborious treatment of the samples nor long times of analysis. However, its high detection limit is a major limitation of CE. CE is often poorly reproducible. Enzymatic assay is more suitable for quantifying one organic acid in honey samples because it is specific, precise, and accurate. GC is more suitable for analyzing volatile or semivolatile chemicals. HPLC is versatile and reproducible. However, common HPLC detectors such as UV-VIS are not very sensitive for organic aliphatic acids. 

There are basically three methods of liquid sampling in GC direct sampling, solid-phase extraction and liquid extraction. The traditional method of treating liquid samples prior to GC injection is liquid-liquid extraction (LLE), but several alternative methods, which reduce or eliminate the use of solvents, are preferred nowadays, such as static and dynamic headspace (DHS) for volatile compounds and supercritical fluid extraction (SFE) and solid-phase extraction (SPE) for semivolatiles. The method chosen depends on concentration and nature of the substances of interest that are present in the liquid. Direct sampling is used when the substances to be assayed are major components of the liquid. The other two extraction procedures are used when the pertinent solutes are present in very low concentration. Modem automated on-line SPE-GC-MS is configured either for at-column conditions or rapid large-volume injection (RLVI). 

S. Hamm, J. Bleton, J. Connan, A. Tchapla, A chemical investigation by headspace SPME and GC MS of volatile and semivolatile terpenes in various olibanum samples, Phytochemistry, 66, 1499 1514(2005). 

Our focus in this chapter is on the analysis of organic analytes in sample matrices that are organic and/or inorganic in nature. These organic analytes can be subclassified into volatile, semivolatile, or nonvolatile. The matrix can be gas (or volatile samples), solid, or liquid. Both the anticipated concentration of the analyte and the type of sample dictate the instrumentation that can be used, as well as the sample preparation technique required. 

A gaseous sample is passed through a solid material, such as silica gel or polyurethane foam (PUF), in a tube. A glass fiber filter is often put in front of the solid support to capture particle-phase constituents, while the vapor-phase compounds are captured on the solid support. This is used for semivolatile analytes, such as polycyclic aromatic hydrocarbons and pesticides. The solid support is then usually extracted in the lab with a solvent (see techniques described later in this chapter), and then the techniques used for liquid samples are followed. 

Samples containing heavy oil, along with the volatile components can severely contaminate pnrge-and-trap instrumentation, and caution is advised when interpreting the data. For such samples it may be advisable to use a separatory funnel for the water extraction method for semivolatiles (EPA 3520). In this method, the sample is ponred into a funnel-shaped piece of glassware, solvent is added, and the mixtnre is shaken vigorously. After layer separation, the extract (i.e., the solvent layer) is removed. Altered, dried with a desiccant, and concentrated. Multiple extractions on the same sample may increase overall recovery. 

Another commonly nsed water extraction method for semivolatiles involves continuous liquid-liquid extraction (EPA 3520). In this method, the sample... 

For the separation of samples from contaminated soil, there are also several possible methods, depending on whether the contaminant is volatile or semivolatile ... 

Soxhlet extraction (EPA SW-846 3540) is a very efficient extraction process that is commonly used for semivolatile petroleum constituents. In the method, the solvent is heated and refluxed (recirculated) through the soil sample continuously for 16 hours, or overnight. This method generates a relatively large volume of extract that needs to be concentrated. Thus, it is more appropriate for semivolatile constituents than for volatile constituents. Sonication extraction (EPA SW-846 3550) can also be used for semivolatile compounds, and as the name suggests, involves the use of sound waves to enhance analyte transfer from sample to solvent. Sonication is a faster technique than Soxhlet extraction and can require less solvent. 

Supercritical fluid extraction (EPA 3540, for total recoverable petroleum hydrocarbons EPA 3561 for polynuclear aromatic hydrocarbons) is applicable to the extraction of semivolatile constituents. Supercritical fluid extraction involves heating and pressuring a mobile phase to supercritical conditions (where the solvent has the properties of a gas and a liquid). The supercritical fluid is passed through the soil sample, and the analytes are concentrated on a sorbent or trapped cryogenically. The analytes are eluted with a solvent and analyzed using conventional techniques. Carbon dioxide is the most popular mobile phase. 

Extraction of semivolatile analytes collected using modified Method 5 (Method 0010) sampling train Accelerated solvent extraction (ASE) (3545A in update IVB) Ultrasonic extraction... 

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