Flame-ionization detection

The FID method possesses high sensitivity, uses smaller samples than TG, can routinely detect decomposition rates of 0.01%/min, and can detect rates down to 0.001 %/min if desired. The lowered limit of detection is of the order of 1 x 10 A fig of carbon per minute. However, as found in previous work on the thermal stability of polymers (97), it is hardly feasible to utilize this high sensitivity because of the heating blank obtained even with a well-cleaned system (burnout with air at 550°C). The high sensitivity of the detector makes it possible to obtain meaningful thermal data curves with as little as a few micrograms of material. Vapor-pressure measurements can be made below the level of 1 mTorr (96). 

A FID curve of polyvinyl chloride polymer formulation yielded four peaks corresponding to a pesticide (79°), a plasticizer (179°), a stabilizer (275°), and the polyvinyl chloride (438°). 

Trace amounts of organic carbon compounds in water can also be determined by this technique (99). The sample is heated in a nitrogen carrier gas in two stages to determine volatile (150°C) and nonvolatile (150-550°Q organic carbon. The water evaporated in the first stage changes the detector response 

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The special problems for vaUdation presented by chiral separations can be even more burdensome for gc because most methods of detection (eg, flame ionization detection or electron capture detection) in gc destroy the sample. Even when nondestmctive detection (eg, thermal conductivity) is used, individual peak collection is generally more difficult than in Ic or tic. Thus, off-line chiroptical analysis is not usually an option. Eortunately, gc can be readily coupled to a mass spectrometer and is routinely used to vaUdate a chiral separation. 

Reference methods for criteria (19) and hazardous (20) poUutants estabHshed by the US EPA include sulfur dioxide [7446-09-5] by the West-Gaeke method carbon monoxide [630-08-0] by nondispersive infrared analysis ozone [10028-15-6] and nitrogen dioxide [10102-44-0] by chemiluminescence (qv) and hydrocarbons by gas chromatography coupled with flame-ionization detection. Gas chromatography coupled with a suitable detector can also be used to measure ambient concentrations of vinyl chloride monomer [75-01-4], halogenated hydrocarbons and aromatics, and polyacrylonitrile [25014-41-9] (21-22) (see Chromatography Trace and residue analysis). 

Analytical Techniques. Sorbic acid and potassium sorbate are assayed titrimetricaHy (51). The quantitative analysis of sorbic acid in food or beverages, which may require solvent extraction or steam distillation (52,53), employs various techniques. The two classical methods are both spectrophotometric (54—56). In the ultraviolet method, the prepared sample is acidified and the sorbic acid is measured at 250 260 nm. In the colorimetric method, the sorbic acid in the prepared sample is oxidized and then reacts with thiobarbituric acid the complex is measured at - 530 nm. Chromatographic techniques are also used for the analysis of sorbic acid. High pressure Hquid chromatography with ultraviolet detection is used to separate and quantify sorbic acid from other ultraviolet-absorbing species (57—59). Sorbic acid in food extracts is deterrnined by gas chromatography with flame ionization detection (60—62). 

The flame ionization detector is capable of measuring only gaseous hydrocarbons, in other words, hydrocarbons that have a low boiling point. Emission gases can, however, also contain hydrocarbons in liquid form at ambient temperature and pressure. Therefore, analyzers based on flame ionization detection are generally equipped with heating elements to keep rhe sampling line and the detector at about 200 °C. 

Figure 12.7 Cliromatograms of a polycarbonate sample (a) microcolumn SEC ti ace (b) capillary GC ti ace of inti oduced fractions. SEC conditions fused-silica (30 cm X 250 mm i.d.) packed with PL-GEL (50 A pore size, 5 mm particle diameter) eluent, THE at aElow rate of 2.0ml/min injection size, 200 NL UV detection at 254 nm x represents the polymer additive fraction ti ansfeired to EC system (ca. 6 p-L). GC conditions DB-1 column (15m X 0.25 mm i.d., 0.25 pm film thickness) deactivated fused-silica uncoated inlet (5 m X 0.32 mm i.d.) temperature program, 100 °C for 8 min, rising to 350 °C at a rate of 12°C/min flame ionization detection. Peak identification is as follows 1, 2,4-rert-butylphenol 2, nonylphenol isomers 3, di(4-tert-butylphenyl) carbonate 4, Tinuvin 329 5, solvent impurity 6, Ii gaphos 168 (oxidized). Reprinted with permission from Ref. (14).

Figure 12.9 Typical pyrolysis chromatogram of fraction from a styrene-acTylonitiile copolymer sample obtained from a miciocolumn SEC system 1, acrylonitrile 2, styrene. Conditions 5 % Phenylmetliylsilicone (0.33 p.m df) column (50 m X 0.2 mm i.d.) oven temperature, 50 to 240 °C at 10 °C/min carrier, gas, helium at 60 cm/s flame-ionization detection at 320 °C make-up gas, nitrogen at a rate of 20 mL/min. P indicates tlie point at which pyrolysis was made. Reprinted from Analytical Chemistry, 61, H. J. Cortes et ai, Multidimensional cliromatography using on-line microcolumn liquid cliromatography and pyrolysis gas cliromatography for polymer characterization , pp. 961-965, copyright 1989, with permission from tlie American Chemical Society.

An on-line supercritical fluid chromatography-capillary gas chromatography (SFC-GC) technique has been demonstrated for the direct transfer of SFC fractions from a packed column SFC system to a GC system. This technique has been applied in the analysis of industrial samples such as aviation fuel (24). This type of coupled technique is sometimes more advantageous than the traditional LC-GC coupled technique since SFC is compatible with GC, because most supercritical fluids decompress into gases at GC conditions and are not detected by flame-ionization detection. The use of solvent evaporation techniques are not necessary. SFC, in the same way as LC, can be used to preseparate a sample into classes of compounds where the individual components can then be analyzed and quantified by GC. The supercritical fluid sample effluent is decompressed through a restrictor directly into a capillary GC injection port. In addition, this technique allows selective or multi-step heart-cutting of various sample peaks as they elute from the supercritical fluid... 

Figure 12.20 SFC-GC analysis of a sample of aviation fuel (a) SFC separation into two peaks (b and c) coixesponding GC ttaces of the respective peaks (flame-ionization detection used throughout). Reprinted from Journal of High Resolution Chromatography, 10, J. M. Levy et ah, On-line multidimensional supercritical fluid chromatography/capillary gas chromatography , pp. 337-341, 1987, with permission from Wiley-VCH.

Sodium dodecyl sulfate present in hydrophilic ointments has been determined by TLC on silica gel with flame ionization detection, which was considered better than the colorimetric method. TLC is preferred to HPLC in this case due to the low sensitivity of the refractive index detector that makes difficult the analysis of small amounts of sodium dodecyl sulfate [284]. 

The primary method for detecting methyl parathion and metabolites in biological tissues is gas chromatography (GC) coupled with electron capture (BCD), flame photometric (FPD), or flame ionization detection (FID). Sample preparation for methyl parathion analysis routinely involves extraction with an organic solvent (e g., acetone or benzene), centrifugation, concentration, and re suspension in a suitable solvent prior to GC analysis. For low concentrations of methyl parathion, further cleanup procedures, such as column chromatography on silica gel or Florisil are required. 

ECD = electron capture detector FID = flame ionization detection GC = gas chromatography HECD = Hall electrolytic conductivity detector HRGC = high-resolution gas chromatography HSD = halogen-specific detector H2SO4 = sulfuric acid MS = mass spectrometry NR = not reported PID = photoionization detection UV = ultraviolet detection... 

The current methodology to determine residues of alachlor, acetochlor, propachlor, and butachlor in crops and animal products was developed over the last two decades by researchers at the Monsanto Company. These herbicides degrade rapidly in plants and animals to numerous metabolites that can be hydrolyzed to common aniline moieties. Little to no parent herbicide is found as intact residue in crops and animal products therefore, the residue methodology focuses on the determination of the common moieties that are derived from the parent herbicides and their metabolites. Initially, gas chromatography (GC) with flame ionization detection, nitrogen-phosphorus... 

Niki and Kuwatsuka reported a method involving trifluoroacetylation of the amino derivatives of chlornitrofen, nitrofen and chlomethoxyfen. A 1-mL volume of 10 M NaOH solution was added to 50 g of soil and the mixture was extracted with 100 mL of benzene. After separation and drying over anhydrous Na2S04, the benzene solution was trifluoroacetylated by adding successively 1 mL of 0.1% trifluoroacetic anhydride in benzene and 1 mL of 0.1% triethylamine in benzene. The mixture was shaken for 30 s and diluted to 10 mL with benzene. To remove the excess of trifluoroacetic anhydride, about 2 mL of water were added to the mixture and shaken for 30 s. The benzene layer was dried over anhydrous Na2S04 and injected for gas chromatography/flame ionization detection (GC/FID). 

Universal and selective detectors, linked to GC or LC systems, have remained the predominant choice of analysts for the past two decades for the determination of pesticide residues in food. Although the introduction of bench-top mass spectrometers has enabled analysts to produce more unequivocal residue data for most pesticides, in many laboratories the use of selective detection methods, such as flame photometric detection (FPD), electron capture detection (BCD) and alkali flame ionization detection (AFID) or nitrogen-phosphorus detection (NPD), continues. Many of the new technologies associated with the on-going development of instrumental methods are discussed. However, the main objective of this section is to describe modern techniques that have been demonstrated to be of use to the pesticide residue analyst. 

GC, utilizing flame ionization detection (FID), has been used to measure diisopropyl methylphosphonate in meat, grain, or milk (Caton et al. 1994). Sample preparation steps include homogenization, filtration, dialysis, and extraction on a solid sorbent. Two common solid phase extractants, Tenax GC and octadecylsilane bonded silica gel (C18 Silica), were compared by Caton et al. (1994). They reported 70% recovery when using Tenax GC and 85% recovery when using C18 Silica. Sensitivity was not reported. Equilibrium experiments indicate that 8-10 mg of Tenax GC are required to achieve maximum recovery of each g of diisopropyl methylphosphonate (Caton et al. 1994). By extrapolating these... 

FID = flame ionization detection GC = gas chromatography HPLC = high performance liquid chromatography ITMS = ion trap mass spectrometry MS = mass spectrometry PNMR = proton nuclear magnetic resonance TLC = thin-layer chromatography... 

Determination of caffeine in soft drinks was undertaken using the aerosol alkali flame ionization detector.24 Soft drinks studied were Coke, Diet Coke, Pepsi, Diet Pepsi, Dr. Pepper, and Mountain Dew. A sample clean-up and concentration procedure is employed followed by GC separation with alkali flame ionization detection. Results showed that Coke, Diet Coke, Pepsi, Diet Pepsi, Dr. Pepper, and Mountain Dew contained 41 2, 52 2, 43 4, 35 9, 46 6, and 60 15 mg caffeine per 355-ml serving. These values compared favorably with levels reported in the literature. 

Conte, E.D. and Barry, E.F., Gas chromatographic determination of caffeine in beverages by alkali aerosol flame ionization detection, Microchem. J., 48,372,1993. 

FID = flame ionization detection GC = gas chromatography MS = mass spectrometry... 

The reaction mixture is sampled after each reaction cycle and analyzed for purity, reaction progress, and the presence and amount of by-products (if any) formed. Analysis is by gas chromatography (HP 5890 Series II Phenomenex Zebron ZB-1 capillary column, Phenomenex Cat. No. 7HK-G001-36) with flame ionization detection in order to quantify the by-product impurities. The quantity of the byproducts is determined using an external standard calibration method. 

Acrylonitrile in both biological and environmental samples is most commonly determined by gas chromatography with a nitrogen-phosphorus detector (GC/NPD) (Page 1985), gas chromatography/flame ionization detection (GC/FID) (EPA 1982a), or gas chromatography/mass spectroscopy (GC/MS) (Anderson and Harland 1980). Infrared spectroscopy (Jacobs and Syrjala... 

Gas chromatography can also be used with other detection systems, e.g. electron-capture detection (GC-ECD) and flame-ionization detection (GC-FID). The optimization will have been carried out during validation studies. The peak separation criterion is the same as that given for LC above. Once again, cochromatography can be used for confirmation. 

PDMS = polydimethylsiloxane. PA = polyacrylate. CW = Carbowax. DVB = divinylbenzene. FID = flame ionization detection. NPD = nitrogen-phosphorus detection. TSD = thermionic-specific detection. LOQ = limit of quantitation. LOD = limit of detection. TCA = trichloroacetic acid. PICI-MS = positive ion chemical mass spectrometry. SIM = selected ion monitoring. 

A method for detecting compounds that have UV absorbance is the use of thin-layer plates that contain a fluorescence dye or indicator. Plates are developed and then placed under UV light. Compounds on the plate may show up as bright or dark spots depending on their interaction with the UV light and the fluorescence produced by the fluorescence indicator [9], It has been reported that flame ionization detection can also be used however, this is not a standard method [10]. 

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