Analysis GC-ECD

Blood Thermally decarboxylated subjected to static headspace analysis GC/ECD (for metabolite trichloroacetic acid) 2 ppb 101-109 Ziglio et al. 1984... 

Olive oil Oil dissolved in hexane, then transferred to SPE column. Eluted with acetonitrile. Residue after drying cleaned up using Florisil. Hexane/benzene/ethyl acetate used to elute fraction for analysis. GC/ECD No data 101 Di Muccio et al. 1991... 

AgN03 = silver nitrate CICN = cyanogen chloride CN" = cyanide ion CNATC = cyanides not amenable to chlorination (Rosentreter and Skogerboe 1992) AAS = atomic absorption spectroscopy EPA = Environmental Protection Agency FIA = flow injection analysis GC/ECD = gas chromatograph/electron capture detector HCN = hydrogen cyanide NaOH = sodium hydroxide NIOSH = National Institute for Occupational Safety and Health... 

Blood, plasma, and serum Sample in sealed vial subjected to static head-space analysis GC/ECD 100 ppb NR Ramsey and Flanagan 1982... 

Figure 15.1 Separation of pesticides from butter by using LC-GC-ECD. Peak identification is as follows 1, HCB 2, lindane 5, aldrin 7, o,p -DDE 10, endrin 11, o,p -DDT 13, p,p -DDT peaks 3, 4, 6, 8, 9, 12, 14, 15 and 16 were not identified. Adapted from Journal of High Resolution Chromatography, 13, R. Barcarolo, Coupled EC-GC a new method for the on-line analysis of organchlorine pesticide residues in fat , pp. 465-469, 1990, with permission from Wiley-VCH.

Analysis of methyl parathion in sediments, soils, foods, and plant and animal tissues poses problems with extraction from the sample matrix, cleanup of samples, and selective detection. Sediments and soils have been analyzed primarily by GC/ECD or GC/FPD. Food, plant, and animal tissues have been analyzed primarily by GC/thermionic detector or GC/FPD, the recommended methods of the Association of Official Analytical Chemists (AOAC). Various extraction and cleanup methods (AOAC 1984 Belisle and Swineford 1988 Capriel et al. 1986 Kadoum 1968) and separation and detection techniques (Alak and Vo-Dinh 1987 Betowski and Jones 1988 Clark et al. 1985 Gillespie and Walters 1986 Koen and Huber 1970 Stan 1989 Stan and Mrowetz 1983 Udaya and Nanda 1981) have been used in an attempt to simplify sample preparation and improve sensitivity, reliability, and selectivity. A detection limit in the low-ppb range and recoveries of 100% were achieved in soil and plant and animal tissue by Kadoum (1968). GC/ECD analysis following extraction, cleanup, and partitioning with a hexane-acetonitrile system was used. 

HPLC has been recommended as a cleanup and fiactionation procedure for food samples prior to analysis by GC/ECD (Gillespie and Walters 1986). The advantages over the AOAC-recommended Florisil colunrn are that it is faster, requires less solvent, and gives better resolution. HPLC coupled with various detectors MS, MS/MS, UV/electrochemical detector, or UV/polarographic detection has been tested as a rapid, simplified separation and detection system to replace GC (Betowski and Jones 1988 Clark et al. 1985 Koen and Huber 1970). Recoveries, detection limits, and precisions were generally good, but further work is needed before the techniques are adopted for general use. 

GC/MS has been employed by Demeter et al. (1978) to quantitatively detect low-ppb levels of a- and P-endosulfan in human serum, urine, and liver. This technique could not separate a- and P-isomers, and limited sensitivity confined its use to toxicological analysis following exposures to high levels of endosulfan. More recently, Le Bel and Williams (1986) and Williams et al. (1988) employed GC/MS to confirm qualitatively the presence of a-endosulfan in adipose tissue previously analyzed quantitatively by GC/ECD. These studies indicate that GC/MS is not as sensitive as GC/ECD. Mariani et al. (1995) have used GC in conjunction with negative ion chemical ionization mass spectrometry to determine alpha- and beta-endosulfan in plasma and brain samples with limits of detection reported to be 5 ppb in each matrix. Details of commonly used analytical methods for several types of biological media are presented in Table 6-1. 

GC/ECD or a halogen-specific detector (HSD) (Method 8080) is the technique recommended by EPA s Office of Solid Waste and Emergency Response for determining a- and [3-endosulfan and endosulfan sulfate in water and waste water at low-ppb levels (EPA 1986a). At these low concentrations, identification of endosulfan residues can be hampered by the presence of a variety of other pesticides. Consequently, sample clean-up on a Florisil column is usually required prior to analysis (EPA 1986a). 

A procedure has been developed for the analysis of a- and (3-endosulfan and endosulfan sulfate in fish, water, and sediments (Chau and Terry 1972 Musial et al. 1976). This procedure involves the acetylation of endosulfan residues into their diacetates and subsequent quantification by GC/ECD. Detection limits of low-ppb levels of endosulfan were reported. This approach is rapid and simple, and minimum sample preparation is required (Chau and Terry 1972 Musial et al. 1976). 

Headspace analysis has also been used to determine trichloroethylene in water samples. High accuracy and excellent precision were reported when GC/ECD was used to analyze headspace gases over water (Dietz and Singley 1979). Direct injection of water into a portable GC suitable for field use employed an ultraviolet detector (Motwani et al. 1986). While detection was comparable to the more common methods (low ppb), recovery was very low. Solid waste leachates from sanitary landfills have been analyzed for trichloroethylene and other volatile organic compounds (Schultz and Kjeldsen 1986). Detection limits for the procedure, which involves extraction with pentane followed by GC/MS analysis, are in the low-ppb and low-ppm ranges for concentrated and unconcentrated samples, respectively. Accuracy and precision data were not reported. 

Residue analytical chemistry has extended its scope in recent decades from the simple analysis of chlorinated, lipophilic, nonpolar, persistent insecticides - analyzed in the first Si02 fraction after the all-destroying sulfuric acid cleanup by a gas chro-matography/electron capture detection (GC/ECD) method that was sometimes too sensitive to provide linearity beyond the required final concentration - to the monitoring of polar, even ionic, hydrophilic pesticides with structures giving the chemist no useful feature other than the molecule itself, hopefully to be ionized and fragmented for MS or MS" detection. 

Several methods can be used for the residue analysis of anilides, especially gas chro-matography/mass spectrometry (GC/MS) and liquid chromatography/mass spectrometry (LC/MS). GC/ECD or GC/NPD for the determination of anilides has generally been used except for the unstable metabolites of naproanilide and clomeprop, which are determined by HPLC/UV, HPLC/FL or GC/ECD after derivatization. 

Analytical methods for parent chloroacetanilide herbicides in soil typically involve extraction of the soil with solvent, followed by solid-phase extraction (SPE), and analysis by gas chromatography/electron capture detection (GC/ECD) or gas chromatog-raphy/mass spectrometry (GC/MS). Analytical methods for parent chloroacetanilides in water are similarly based on extraction followed by GC with various detection techniques. Many of the water methods, such as the Environmental Protection Agency (EPA) official methods, are multi-residue methods that include other compound classes in addition to chloroacetanilides. While liquid-liquid partitioning was used initially to extract acetanilides from water samples, SPE using... 

The method using GC/MS with selected ion monitoring (SIM) in the electron ionization (El) mode can determine concentrations of alachlor, acetochlor, and metolachlor and other major corn herbicides in raw and finished surface water and groundwater samples. This GC/MS method eliminates interferences and provides similar sensitivity and superior specificity compared with conventional methods such as GC/ECD or GC/NPD, eliminating the need for a confirmatory method by collection of data on numerous ions simultaneously. If there are interferences with the quantitation ion, a confirmation ion is substituted for quantitation purposes. Deuterated analogs of each analyte may be used as internal standards, which compensate for matrix effects and allow for the correction of losses that occur during the analytical procedure. A known amount of the deuterium-labeled compound, which is an ideal internal standard because its chemical and physical properties are essentially identical with those of the unlabeled compound, is carried through the analytical procedure. SPE is required to concentrate the water samples before analysis to determine concentrations reliably at or below 0.05 qg (ppb) and to recover/extract the various analytes from the water samples into a suitable solvent for GC analysis. 

To determine the residue levels of dinitroaniline herbicides, GC/NPD or GC/ECD is used in general. An aliquot of GC-ready sample solution is injected into the gas chromatograph under the conditions outlined below. Further confirmatory analysis is carried out using gas chromatography/mass spectrometry (GC/MS) in the selected-ion monitoring (SIM) mode. 

The minimum detectable level is estimated with the dinifroaniline signal-to-noise ratios (S/N). With fortification levels between 0.2 and 0.5mgkg the recovery of trifluralin from plant matrices is 70-99% with the LOD/LOQ being 0.005 mg kg according to the analytical method of the Ministry of the Environment, Japan. In multiresidue analysis by GC/NPD, the percent recoveries of pendimethalin from each crop with a fortification level of 0.25 mg kg were brown rice 70, potato 70, cabbage 80, letmce 89, carrot 84, cucumber 64, shiitake 74, apple 76, strawberry 99, and banana 99%. The LOD for each sample was 0.01 mg kg for pendimethalin. In residue analysis by GC/ECD, recoveries of the majority of dinifroaniline herbicides from fortified samples of carrot, melon, and tomato at fortification levels of 0.04—0.10 mg kg ranged from 79 to 92%. The LODs were benfluralin 0.001, pendimethalin 0.002 and trifluralin 0.001 mg kg for the GC/ECD method. ... 

A 100-mL volume of benzene is added to the 20 g of air-dried soil and the mixture is shaken vigorously for 2h. After extraction twice with 100 mL of benzene, the combined extract is filtered through filter paper and the filter cake is washed with an additional 20 mL of benzene. The benzene extracts are dried over anhydrous Na2S04 and concentrated to dryness using a vacuum rotary evaporator. The residue is dissolved in an appropriate volume followed by GC/ECD analysis. For the monitoring of pesticide residues in soil, methanol for bifenox and oxyfluorfen and acetonitrile for nitrofen were recommended as the solvents for efficient extraction. ... 

HPLC-UV, GC-ECD, GC-MS, LC-MS Figure 8 Schematic of general analytical method for soil analysis... 

Qin BH, Yu BB, Zhang Y, Lin XC. Residual analysis of organochlorine pesticides in soil by gas chromatograph-electron capture detector (gc-ecd) and gas chromatograph-negative chemical ionization mass spectrometry (GC-NCI-MS). Environ. Forensics 2009 10 331-335. 

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