Residue analysis method

The MDCs are estimated from an S/N of the diphenyl ether peaks of at least of 3 in the recovery test. With fortification levels between 0.2 and 0.5mgkg recoveries of bifenox from brown rice matrices ranged from 85 to 102% with the limit of detection (LOD) and limit of quantitation (LOQ) being 0.010 mg kg according to the analytical method of the Notification of the Ministry of the Environment, Japan. By the residue analysis method described in Section 2.2.2(3), recoveries of chlornitrofen and CNP-NH2 from brown rice and vegetables with fortification levels of 0.04-0.10 mg kg ranged from 82 to 98%. The LOD for each sample was 0.005 mg kg for chlornitrofen and CNP-NH2. ... 

The sample extraction procedures are similar to those for the Multi-residue analysis method (see Section 3.3.1). 

Residue Analysis Methods. Among the methods routinely used for residue analysis are determination of weight loss, extraction of the residue and quantitation of the extract by either gas chromatography or liquid scintillation counting, and measurement of the increase in void space within a fiber with time, or meniscus regression method. 

While each of these methods has its own advantages and disadvantages all of the residue analysis methods are more rapid than effluent analysis methods. 

Extraction and Quantification of the Residue. When gas chro-matography is used as the method of quantification, extraction provides the most information of any of the residue analysis methods since both qualitative and quantitative information can be obtained. In this way any changes in ratios or the presence of degradation products in the residue can also be detected. 

This method is, however, the most time consuming of the residue analysis methods. Other disadvantages are that the method is destructive as once the pheromone has been extracted from the device, it is useless. Since examination of the residue at various time periods is necessary to establish a release rate this necessitates a large sample size. 

Major Disadvantages Of Residue Analysis. In the foregoing discussion several advantages and disadvantages of the various methods have been discussed, but the most severe limitation of the residue analysis methods has not been touched upon. That disadvantage is that none of these methods provide any direct information about either the quality or quantity of the material actually released. If volatile degradation products are produced, this information would not be detected nor would the ratio of components actually released be directly measurable. Since the material released is the active ingredient of any controlled release system, this lack of information is a serious drawback to dependence on residue analysis for release rate determinations. 

The detailed residue analysis method must be reported including the sample extraction procedure and clean-up. The method of detection must be simple and feasible, and the instrumentation and its operating conditions are to be acceptable for residue laboratories. Secondly, the recovery, RSD (relative standard deviation), and sensitivity (limit of detection and minimum concentration of detection) of the analytical method should meet the requirements of the Residues Experiment Guideline of Pesticide Registration. 

Guidelines of Safety Application of Pesticides, Good Agriculture Practices, Pre-Harvest Interval, ICAMA, Residue Data Requirements, Field Trials, Residue Analysis Method... 

Several chemical methods have been devised for identifying the N terminal ammo acid They all take advantage of the fact that the N terminal ammo group is free and can act as a nucleophile The a ammo groups of all the other ammo acids are part of amide linkages are not free and are much less nucleophilic Sanger s method for N terminal residue analysis involves treating a peptide with 1 fluoro 2 4 dimtrobenzene which is very reactive toward nucleophilic aromatic substitution (Chapter 23)... 

When Sanger s method for N terminal residue analysis was discussed you may have wondered why it was not done sequentially Simply start at the N terminus and work steadily back to the C terminus identifying one ammo acid after another The idea is fine but It just doesn t work well m practice at least with 1 fluoro 2 4 dimtrobenzene... 

A major advance was devised by Pehr Edman (University of Lund Sweden) that has become the standard method for N terminal residue analysis The Edman degrada tion IS based on the chemistry shown m Figure 27 12 A peptide reacts with phenyl iso thiocyanate to give a phenylthwcarbamoyl (PTC) denvative as shown m the first step This PTC derivative is then treated with an acid m an anhydrous medium (Edman used mtromethane saturated with hydrogen chloride) to cleave the amide bond between the N terminal ammo acid and the remainder of the peptide No other peptide bonds are cleaved m this step as amide bond hydrolysis requires water When the PTC derivative IS treated with acid m an anhydrous medium the sulfur atom of the C=S unit acts as... 

This reaction forms the basis of one method of terminal residue analysis A peptide is treated with excess hydrazine in order to cleave all the peptide linkages One of the terminal amino acids is cleaved as the free amino acid and identified all the other ammo acid residues are converted to acyl hydrazides Which amino acid is identified by hydrazmolysis the N terminus or the C terminus ... 

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). 

Trace Mercury. There are a number and variety of methods and instmments to determine trace quantities of both inorganic and organic mercury ia natural or synthetic substances (19) (see also Trace and residue analysis). Literature describiag numerous techniques and trace element analysis of a myriad of mercury-containing substances is available (20). Only the most commonly used methods are mentioned hereia. 

Nickel also is deterrnined by a volumetric method employing ethylenediaminetetraacetic acid as a titrant. Inductively coupled plasma (ICP) is preferred to determine very low nickel values (see Trace AND RESIDUE ANALYSIS). The classical gravimetric method employing dimethylglyoxime to precipitate nickel as a red complex is used as a precise analytical technique (122). A colorimetric method employing dimethylglyoxime also is available. The classical method of electro deposition is a commonly employed technique to separate nickel in the presence of other metals, notably copper (qv). It is also used to estabhsh caUbration criteria for the spectrophotometric methods. X-ray diffraction often is used to identify nickel in crystalline form. 

Chemical Properties. Elemental analysis, impurity content, and stoichiometry are determined by chemical or iastmmental analysis. The use of iastmmental analytical methods (qv) is increasing because these ate usually faster, can be automated, and can be used to determine very small concentrations of elements (see Trace AND RESIDUE ANALYSIS). Atomic absorption spectroscopy and x-ray fluorescence methods are the most useful iastmmental techniques ia determining chemical compositions of inorganic pigments. Chemical analysis of principal components is carried out to determine pigment stoichiometry. Analysis of trace elements is important. The presence of undesirable elements, such as heavy metals, even in small amounts, can make the pigment unusable for environmental reasons. 

The distribution of impurities over a flat sihcon surface can be measured by autoradiography or by scanning the surface using any of the methods appropriate for trace impurity detection (see Trace and residue analysis). Depth measurements can be made by combining any of the above measurements with the repeated removal of thin layers of sihcon, either by wet etching, plasma etching, or sputtering. Care must be taken, however, to ensure that the material removal method does not contaminate the sihcon surface. 

From a toxicological and physiological point of view, the determination of very small amounts of tellurium is becoming increasingly important. Interest is environmental and human health has promoted development in analytical techniques and methods for the trace and ultra trace levels (see Trace AND RESIDUE ANALYSIS). 

Method of analysis proposed for residue monitoring Method ... 

Egan H. 1969. lUPAC Commission on the development, improvement, and standardization of methods of pesticide residue analysis. J AOAC 52 306-309. 

Koen JG, Huber JF. 1970. A rapid method for residue analysis by column liquid chromatography with polarographic detection Application to the determination of parathion and methyl parathion on crops. Anal Chim Acta 51 303-307. 

An enzyme immunoassay technique has been employed for measuring endosulfan and its degradation products (i.e., endosulfan diol, endosulfan sulfate, endosulfan ether, and endosulfan lactone) in water at 3 ppb (Chau and Terry 1972 Musial et al. 1976). However, this technique is not currently in use in environmental residue analysis. Further research into this technique could produce a rapid, rehable, and sensitive method for identifying contaminated areas posing a risk to human health. No additional methods for detecting endosulfan in environmental media appear to be necessary at this time. However, methods for the determination of endosulfan degradation products are needed. 

Shibata Y, Oyama M, Sato H, et al. 1998. Simultaneous cleanup method for multi pesticide residue analysis by GC and HPLC. J Food Hyg Soc Jpn 39(4) 241-250. 

W.G. Fong, Regulatory aspects pesticide registration, risk assessment and tolerance, residue analysis, and monitoring, in Pesticide Residues in Foods Methods, Techniques, and Regulations, ed. W.G. Fong, H.A. Moye, J.N. Seiber, and J.R Toth, WUey, New York, Chapt. 7 (1999). 

To avoid different interpretations, a list of analytical techniques, regarded as commonly available, is given in the guidance document SANCO/825/00. Other techniques may also be powerful tools in residue analysis the acceptance of these additional techniques as part of enforcement methods will be discussed at appropriate intervals by governmental experts. Therefore, whilst not wishing to prevent... 

---