Analytical method multi-analyte

Wrong species identification likely if species identification is based solely on specific retention time in a single (low-resolving) separation method. Multi-dimensional analytical concepts employing different separation mechanisms are recommended. 

Analytical benefits of ICP-MS are (i) rapid multi-element analysis (ii) rapid semiquantitative analysis which includes interpretation of spectra (iii) low detection limits (iv) isotopic analysis including isotopic ratio and isotopic dilution analysis (v) wide linear dynamic range (> 10 ) (vi) spectral simplicity. ICP-MS shares analytical applications with plasma AES and AAS methods, multi-element capabilities with ICP-AES, and analytical speed with ICP-AES. On the other hand, ICP-MS is unique in isotopic measurement capabilities and in rapid semiquantitative analysis. The major disadvantage of ICP-MS is the spectral interference caused by diatomic molecular ions. 

Gros M, Petrovic M, Barcelo D (2006) Development of a multi-residue analytical method based on liquid chromatography-tandem mass spectrometry (LC-MS-MS) for screening and trace level determination of pharmaceuticals in surface and wastewaters. Talanta 70 (4) 678-690... 

The set of possible dependent properties and independent predictor variables, i.e. the number of possible applications of predictive modelling, is virtually boundless. A major application is in analytical chemistry, specifically the development and application of quantitative predictive calibration models, e.g. for the simultaneous determination of the concentrations of various analytes in a multi-component mixture where one may choose from a large arsenal of spectroscopic methods (e.g. UV, IR, NIR, XRF, NMR). The emerging field of process analysis,... 

Table 3.6 presents examples for environmental and biological natural matrix CRMs from BCR, NIST and NRCC certified for elements using the above described analytical multi-method approaches. 

How critically interdependent matrix and analytical methods can be is illustrated in the example of the analysis of a soil sample. Table 7.1 shows the method dependent certified values for some common trace elements. The soil had been subjected to a multi-national, multi-laboratory comparison on a number of occasions (Houba et al. 1995) which provided extensive data. The data was subjected to a rigorous statistical program, developed for the USEPA by Kadafar (1982). This process allowed the calculation of certified values for a wide range of inorganic analytes. Uniquely, for the soil there are certified values for four very different sample preparation methods, as follows ... 

Owing to the complexity of multi-residue methods for products of animal origin, it is not possible to outline a simple scheme however, readers should refer to methods described in two references for detailed guidance (Analytical Methods for Pesticides in Foodstuffs, Dutch method collection and European Norm EN 1528. ) There is no multi-method specifically designed for body fluids and tissues. The latter matrix can be partly covered by methods for products of animal origin. However, an approach published by Frenzel et al may be helpful (method principle whole blood is hemolyzed and then deproteinized. After extraction of the supernatant, the a.i. is determined by GC/MS. The LOQ is in the range 30-200 ag depending on the a.i.). 

The BBA publishes reviews of analytical methods for existing a.i. References and a table of a.i. which can be determined using the standard multi-method S19 or its new modular version are presented on the World Wide Web. ... 

Other considerations could include availability of reagent(s) or equipment, method for routine analyses vs limited samples, and confirmatory method vs multi-residues. Plan for method validation and/or analytical quality control. 

The scope of the multi-residue method is extended permanently by testing and then including further active substances that can be determined by GC. Acidic analytes (such as phenoxyacetic acids or RCOOH metabolites) are included into the homogeneous partitioning by acidifying the raw extracts to a pH below the pKs value of the carboxylic acids. To include these analytes in the GC determination scheme they have to be derivatized with diazomethane, diazoethane, trimethylsilyldiazomethane, acidic esterification or benzylation, or by silanizing the COOH moiety. 

Non-NADA methods may be designed to detect multiple residues and they may be designed for use in multiple species. In order to validate these multi-residue methods, modifications to the validation protocol relative to single analyte methods are made. Additional laboratories will participate in the method trial, but the number of samples... 

The Guidance Document on Residue Analytical Methods requests the applicant to assess a standard multi-residue method by using standard steps. These steps are extraction with acetone or ethyl acetate, cleanup by gel permeation chromatography (GPC) and/or silica gel chromatography and final determination by GC. 

The best way to test the practicability of the multi-residue approach is to start with the GC determination step. Most often the inability to vaporize the intact compound means that it is not possible to include a new pesticide in the multi-residue scheme. In the case of common moiety methods, a decomposition step is needed to produce the common analyte. Often for that step, modification of the reaction conditions (such as pH and temperature) are necessary, which would lead to a significant deviation from standard multi-residue procedures. 

The other two CEN standards, for the determination of dithiocarbamate/thiuram disulfide residues and for the quantitation of bromide, are also separated into parts, but, in contrast to the multi-residue methods, complete methods are presented in each different part. Owing to this different approach and the reduced number of analytes, it was possible to validate these methods fully. 

For multi-analyte and/or multi-matrix methods, it is not possible to validate a method for all combinations of analyte, concentration and type of sample matrix that may be encountered in subsequent use of the method. On the other hand, the standards EN1528 andEN 12393 consist of a range of old multi-residue methods. The working principles of these methods are accepted not only in Europe, but all over the world. Most often these methods are based on extractions with acetone, acetonitrile, ethyl acetate or n-hexane. Subsequent cleanup steps are based on solvent partition steps and size exclusion or adsorption chromatography on Florisil, silica gel or alumina. Each solvent and each cleanup step has been successfully applied to hundreds of pesticides and tested in countless method validation studies. The selectivity and sensitivity of GC combined with electron capture, nitrogen-phosphorus, flame photometric or mass spectrometric detectors for a large number of pesticides are acceptable. 

In contrast to multi-analyte/multi-matrix methods, a more or less complete validation of methods with limited scope is possible. For this reason, TC 275 decided that... 

To reduce the effort, another validation procedure is used for extension of the German multi-residue method to a new analyte. Actually, more than 200 pesticides can be analyzed officially with this method, which is the up-to-date version of the better known method DFG SI9. A typical validation is performed by at least three laboratories, which conduct fortification experiments at the same three levels with at least four representative matrices. These representative matrices are commodities with high water content (e.g., tomato), fruits with high acid content (e.g., lemon), dry crops (e.g., cereals) and commodities with high fat content (e.g., avocado). 

If analytical methods are validated in inter-laboratory validation studies, documentation should follow the requirements of the harmonized protocol of lUPAC. " However, multi-matrix/multi-residue methods are applicable to hundreds of pesticides in dozens of commodities and have to be validated at several concentration levels. Any complete documentation of validation results is impossible in that case. Some performance characteristics, e.g., the specificity of analyte detection, an appropriate calibration range and sufficient detection sensitivity, are prerequisites for the determination of acceptable trueness and precision and their publication is less important. The LOD and LOQ depend on special instmmentation, analysts involved, time, batches of chemicals, etc., and cannot easily be reproduced. Therefore, these characteristics are less important. A practical, frequently applied alternative is the publication only of trueness (most often in terms of recovery) and precision for each analyte at each level. No consensus seems to exist as to whether these analyte-parameter sets should be documented, e.g., separately for each commodity or accumulated for all experiments done with the same analyte. In the latter case, the applicability of methods with regard to commodities can be documented in separate tables without performance characteristics. 

Analytical methods for representative anilides are reported in this article. In addition, they are also applicable as multi-residue methods. 

Using multi-analytical methods, most of the anilides, including naproanilide, propanil and mefenacet, show recoveries of >70% from 0.5mgkg fortified tomato. According to the official analytical method of the Ministry of Environment, Japan, the recovery of clomeprop fortified at 0.4mgkg in brown rice is >90% (personal data). 

Thus, organic solvent extraction methods for the extraction of pesticides from water samples can be replaced by the SPE method using Ci8 and PS-2. Ethobenzanid, clomeprop, naproanilide and their acidic metabolites are determined by a multi-residue analytical method using Cig or PS-2 cartridge extraction after acidification of the water samples with hydrochloric acid or other acidic media, followed by HPLC or LC/MS detection. 

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... 

Multi-residue analytical method for the determination of acetochlor, alachlor, and metolachlor in aqueous samples... 

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