Part I: Advances in GCâMS and GCâMSâMS. Environmental Applications
Outline
Chapter 1 Gas ChromatographyâMass Spectrometry Techniques for Multiresidue Pesticide Analysis in Agricultural Commodities
Chapter 2 Microextraction Techniques Coupled to Advanced GCâMS Techniques for Analysis of Environmental Samples
Chapter 3 Determination of Pesticide Residues in Environmental and Food Samples Using Gas ChromatographyâTriple Quadrupole Mass Spectrometry
Chapter 4 Environmental Odor Pollution
Chapter 5 Injection Port Derivatization for GC/MSâMS
Chapter 6 High-Throughput Analysis of PPCPs, PCDD/Fs, and PCBs in Biological Matrices Using GCâMS/MS
Chapter 7 GCâMS Applied to the Monitoring of Pesticides in Milk and Blackberries and PAHs in Processed Meats of Colombia
Chapter 8 Applications and Strategies Based on Gas ChromatographyâLow-Resolution Mass Spectrometry (GCâLRMS) for the Determination of Residues and Organic Contaminants in Environmental Samples
Chapter 9 Determination of Pyrethroid Insecticides in Environmental Samples by GCâMS and GCâMSâMS
Chapter 10 GCâMSâMS for the Analysis of Phytoestrogens in the Environment
Chapter 1
Gas ChromatographyâMass Spectrometry Techniques for Multiresidue Pesticide Analysis in Agricultural Commodities
Jon W. Wong, Douglas G. Hayward and Kai Zhang, U.S. Food and Drug Administration, Center for Food Safety and Applied Nutrition, Office of Regulatory Science, College Park, Maryland, USA
Abstract
Multiresidue methods are the most common approaches to analyze pesticide residues because the pesticide application on an agricultural commodity is usually not known. Since there are hundreds of pesticides available, it is essentially impractical to apply individual single residue analysis for every pesticide in various types of food products. The challenge is to process a sample using a single procedure or a limited number of procedures that can identify and quantitate as many pesticides with varying physical and chemical properties as possible that could potentially be present in a wide variety of agricultural matrices. Over the past 20 years, capillary gas chromatographyâmass spectrometry (GCâMS) has played a major role in the analysis of pesticides in foods. Despite the increasing popularity of liquid chromatographyâmass spectrometry (LCâMS), GCâMS is still widely used because of its affordability, ruggedness, and effectiveness in multiresidue pesticide procedures. GCâMS is primarily used to analyze a variety of thermally stable and volatile or semivolatile pesticides as well as other industrial contaminants such as PCBs, dioxins, brominated flame retardants, and related persistent organic pollutants in diverse food matrices that currently cannot be analyzed by conventional LCâMS methods. This chapter will attempt to account the past and present use and the future of multiresidue procedures that utilize a variety of GCâMS systems and platforms for the analysis of pesticide residues in foods and related agricultural products.
Keywords
Multiresidue pesticide methods; Gas chromatographyâmass spectrometry; Quadrupole ion trap; Quadrupole mass filter; Triple quadrupole mass spectrometry; Time-of-flight mass spectrometry
1 Gas Chromatography
Gas chromatography was developed in the 1950s when James and Martin [1] reported the separation of organic and fatty acids from mixtures using nitrogen as the carrier gas and 10% steric acid in silicone/diatomaceous earth as the stationary phase [2]. Since its development, tremendous advancements and improvements in the hardware, software, and consumables have established GC as an important analytical tool in the isolation of chemical constituents from complex matrices prevalent in the food, flavor and fragrances, petroleum and chemicals, environmental, and biological and medical disciplines [3]. Fused silica capillary columns of diverse stationary phases and column dimensions have since replaced packed columns due to their superior separation efficiency and resolution. The pneumatics and microfluidic devices, built into current GCs, allow for precise control of gas flows that provides not only reliable chromatographic retention times [4] but also introduce a variety of sample injection and maintenance techniques such as large volume or programmed temperature vaporization (PVT) injection [5], column backflushing [6], and advanced GC procedures such as multidimensional (GC Ă GC), low pressure, and fast capillary gas chromatography [7â10] techniques. The integration and use of the computer in todayâs GC aids in the optimization of instrumental conditions, enables for efficient acquisition and storage of chromatographic (and mass spectra) data, and provides the speed to quantitatively and qualitatively process the data using various software algorithms and programs. The combination of these technological advances has made it possible to couple sampling devices such as headspace, thermal desorption, solid-phase microextraction, stir bar sorptive extraction as well as automated sample preparation workstations, to allow for increased sample throughput and further diversity of GC and gas chromatographyâmass spectrometry (GCâMS) applications.
2 Gas Chromatography with Element Selective Detection for Multiresidue Pesticide Analysis
The first significant work of multiresidue pesticide procedures by Mills [11] applied paper chromatography using a chromogenic reagent (silver nitrate/hydrogen peroxide in 2-phenoxyethanol and acetone) to stain the paper as a means to detect organochlorine pesticides and reported âit is possible to rapidly identify and approximately measure residual of commonly used pesticides in a variety of foods and feeds.â Identification with paper chromatography depended on the number and size of the developed spots and difficulties arose due to streaking and resolving spots of pesticides with similar migration times. In a follow up on his work, Mills et al. [12] replaced paper chromatography with a GC equipped with a Coulson coulometric detector for the separation and detection of 21 organochlorine pesticides, demonstrating one of the first published application of detectors used for GC analysis for pesticides.
Many GC detectors prior to mass spectrometry were of the element selective types, namely, so because detection was dependent on the presence and detection of element heteroatoms in the molecular makeup of the analyte that formed specific ions or emissions when combusted and became ideally suited for pesticide analysis. Commonly used universal GC detectors were the thermal conductivity (TCD) and flame ionization (FID) detectors [13â15] because of their abilities to produce signal responses from the carbonâhydrogen content of the analyte. The TCD signal response is a result of changes in the temperature and electrical resistance when the analyte from the GC effluent comes in contact with a conductivity cell. The FID signal results when the CâH-containing analyte is combusted in a flame jet creating ions which are collected at an electrode to produce the response. The detectors generally used for the GC analysis of pesticides are electron-capture (ECD) [16,17], electrolytic conductivity (ELCD) [18], nitrogenâphosphorus (NPD) [19], and flame photometric [20], which were effective due to their selectivity and sensitivity for halogens (especially chlorine), nitrogen, phosphorus, sulfur, or a conjugated moiety such as an aromatic ring that were present in organochlorine and organophosphorus pesticides that were commonly used at the time [12,21â23]. Some of these detectors have been modified such as the micro-electron-capture (ÎźECD) and pulsed flame photometric [24] and are of still in use today because of their improved selectivity and sensitivity [25,26]. The ELCD and the closely related halogen-specific detector (XSD) [27â29] are currently used to analyze organochlorine pesticides and have been useful to detect phthalimide fungicides such as captan, captafol, and folpet [30,31], notoriously difficult pesticides to analyze by MS because of their thermal instability under GC conditions and the inability to produce stable fragments with MS. As a result of the availability of these different detector types, many multiresidue pesticide procedures based on gas chromatography coupled with element selective detection for the analysis of foods were developed at several regulatory and private laboratories [21,32,33]. Despite the increasing use of GCâMS, the addition of an element selective detector to the GCâMS or a stand alone GC-element selective detector can be used to compliment GCâMS or enhance the GCâMS performance in the detection or confirmation of difficult pesticides in complex food and agriculture-based matrices [24,30,34â38].
3 Capillary GCâMS
Pesticide confirmation with GC-element selective detection is determined by cross-referencing the retention indices or comparing the variations in the retention times of each pesticide using two different columns of stationary phases of varying polarities [26,39,40]. This practice has since been replaced because MS has become the primary detector of use in most laboratories and is more reliable for identification or confirmation. Today, criteria for pesticide presence from a sample are based on MS technology [41â45]. Due to the separation and resolution capabilities of GC, an analyte is isolated as it undergoes fragmentation typically by electron ionization (EI) in the mass spectrometer to generate a spectrum based on mass-to-charge (m/z) ratios. The analyte can be unambiguously identified based on the chromatographic retention time and the unique spectral fragmentation pattern of the mass spectrum in full-sc...