Matrix sample, soil

Group No. of samples Soil Matrix Main inclusions Proposed provenance... 

Purified matrix (water, soil, and tissue) are processed as though they were a sample. This will indicate interferences caused by the reagents used. It will also identify cross-contamination from samples. Frequency should be once per batch of up to 20 samples. 

An example of an extraction and reaction sequence of a soil matrix sample analysis is presented in Figure 1.3. 

Standard Practice for Dissolution of Silicate or Acid Resistant Matrix Samples Standard Test Method for the Analysis of Total and Isotopic Uranium and Total Thorium in Soils by Inductively Coupled Plasma-Mass Spectrometry... 

Samples containing PAHs are obtained from air, soil (and sediment), or water so collection procedures to ensure the validity of the sample obtained are very important. For the sample analyzed to represent the true composition of the environmental matrix, sampling must be quantitative, no artifacts should be formed during sample collection, and all sample treatment and storage before analysis must be free from interferences and losses. 

The type of decomposition of the sample (reactive to use) depends on the nature of the matrix in reactors. Many matrices require HF to break the Si-O bonds of the silicates and HNO3 to oxidize the C. Organic samples (biological, botanical, polymeric pharmaceutical, etc.) and geological samples (soils, sediments, rocks, clays, etc.) are of interest for this type of treatment, since the C and the Si are transformed, by the acids mentioned, to volatile compounds (CO2 and SiF4, respectively) and the... 

It is therefore essential to use controls of exactly the same composition as the samples this could be achieved if a bigger amount of a natural matrix (compost, soil or sediment), than needed for the biodegradation experiments, is collected. One part... 

The so-called matrix — the predominant material of which the sample is composed — is the subject of any analysis. The matrix is frequently water, soil, or sediment. 

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. 

Also consider the use of NIST sediments 1646, 2704, and soils 2709-2711 in exploration geochemistry. These samples were certified largely in view of the demand for samples to support monitoring of toxic elements in environmental samples. However, many of the elements certified overlap either the list of primary ore elements or the list of pathfinder elements. Thus, these samples may legitimately be used in a very different application than the one that prompted certification. The sample matrix is ideal for the alternative application, and so is the suite of certified elements. 

The literature includes a number of mis-matches, the following standing as examples for the many The use of bovine liver and other animal tissues for QC in the analysis of hmnan body fluids should not be considered by analysts. The matrix and the levels of trace elements do not match the levels to be analyzed, which may lead to serious errors. An even more severe mis-use was recently reported by Schuhma-cher et al. (1996) for NIST SRM 1577a Bovine Liver, which was used for QC in the analysis of trace elements in plant materials and soil samples in the vicinity of a municipal waste incinerator. Also recently, Cheung and Wong (1997) described how the quality control for the analysis of trace elements in clams (shellfish) and sediments was performed with the same material NIST SRM 1646, Estuarine sediment. Whilst the selected SRM was appropriate for sediments, its usefulness as a QC tool for clams is difficult to prove see also Chapter 8. This inappropriate use is the more mystifying because a broad selection of suitable shellfish RMs from various producers is available. 

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 ... 

The importance of particle size is directly proportional to the sub-sample size recommended by the analytical method. The larger the sub-sample size the larger the acceptable particle size. For sub-sample sizes of ig or greater a soil sieved through a imm screen is generally acceptable. Therefore if the sample is relatively coarse, e.g up to 2mm particles and the matrix CRM is an uniform sub-micron powder, it may be necessary to use a much larger sample from the material under test than for the CRM. 

These two terms (IDL and IQL) define only the limitations of the instmment. When analyzing real-life samples such as plant or animal tissue or even soil and ground water samples, matrix interference must be taken into consideration in order to define detection limits. This is because these real-life matrices are made up of hundreds (or even thousands) of compounds. These compounds may interfere in several ways in the detection and quantification of the analyte of interest. 

The method for chloroacetanilide soil metabolites in water determines concentrations of ethanesulfonic acid (ESA) and oxanilic acid (OXA) metabolites of alachlor, acetochlor, and metolachlor in surface water and groundwater samples by direct aqueous injection LC/MS/MS. After injection, compounds are separated by reversed-phase HPLC and introduced into the mass spectrometer with a TurboIonSpray atmospheric pressure ionization (API) interface. Using direct aqueous injection without prior SPE and/or concentration minimizes losses and greatly simplifies the analytical procedure. Standard addition experiments can be used to check for matrix effects. With multiple-reaction monitoring in the negative electrospray ionization mode, LC/MS/MS provides superior specificity and sensitivity compared with conventional liquid chromatography/mass spectrometry (LC/MS) or liquid chromatography/ultraviolet detection (LC/UV), and the need for a confirmatory method is eliminated. In summary,... 

Specifically for triazines in water, multi-residue methods incorporating SPE and LC/MS/MS will soon be available that are capable of measuring numerous parent compounds and all their relevant degradates (including the hydroxytriazines) in one analysis. Continued increases in liquid chromatography/atmospheric pressure ionization tandem mass spectrometry (LC/API-MS/MS) sensitivity will lead to methods requiring no aqueous sample preparation at all, and portions of water samples will be injected directly into the LC column. The use of SPE and GC or LC coupled with MS and MS/MS systems will also be applied routinely to the analysis of more complex sample matrices such as soil and crop and animal tissues. However, the analyte(s) must first be removed from the sample matrix, and additional research is needed to develop more efficient extraction procedures. Increased selectivity during extraction also simplifies the sample purification requirements prior to injection. Certainly, miniaturization of all aspects of the analysis (sample extraction, purification, and instrumentation) will continue, and some of this may involve SEE, subcritical and microwave extraction, sonication, others or even combinations of these techniques for the initial isolation of the analyte(s) from the bulk of the sample matrix. 

Sample preparation techniques vary depending on the analyte and the matrix. An advantage of immunoassays is that less sample preparation is often needed prior to analysis. Because the ELISA is conducted in an aqueous system, aqueous samples such as groundwater may be analyzed directly in the immunoassay or following dilution in a buffer solution. For soil, plant material or complex water samples (e.g., sewage effluent), the analyte must be extracted from the matrix. The extraction method must meet performance criteria such as recovery, reproducibility and ruggedness, and ultimately the analyte must be in a solution that is aqueous or in a water-miscible solvent. For chemical analytes such as pesticides, a simple extraction with methanol may be suitable. At the other extreme, multiple extractions, column cleanup and finally solvent exchange may be necessary to extract the analyte into a solution that is free of matrix interference. 

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