Matrix effect measurement

FIG. 7—Matrix effects measured correction factor and the theoretical correction curves for C/H mass ratio and total oxygen wt. %... 

Sources of Error. pH electrodes are subject to fewer iaterfereaces and other types of error than most potentiometric ionic-activity sensors, ie, ion-selective electrodes (see Electro analytical techniques). However, pH electrodes must be used with an awareness of their particular response characteristics, as weU as the potential sources of error that may affect other components of the measurement system, especially the reference electrode. Several common causes of measurement problems are electrode iaterferences and/or fouling of the pH sensor, sample matrix effects, reference electrode iastabiHty, and improper caHbration of the measurement system (12). 

The usage of the ratio of chai acteristic lines as analytical parameter in the process of formation of the calibration curve provides a significant decrease of the residual error. In Realization of this method simultaneously with the decrease of the matrix effects causes some decrease or even full compensation of the fonu and condition of the measured surface. 

Nuclear reaction analysis (NRA) is used to determine the concentration and depth distribution of light elements in the near sur ce (the first few lm) of solids. Because this method relies on nuclear reactions, it is insensitive to solid state matrix effects. Hence, it is easily made quantitative without reference to standard samples. NRA is isotope specific, making it ideal for isotopic tracer experiments. This characteristic also makes NRA less vulnerable than some other methods to interference effects that may overwhelm signals from low abundance elements. In addition, measurements are rapid and nondestructive. 

The most accurate - and most popular - method of quantifying matrix effects is to analyze the unknown sample with a similar sample of known composition. The relationship between measured intensity and the content of each sample is, usually, defined by the relative sensitivity factor (RSF) ... 

Manganese, D. of - continued with magnesium and zinc, (ti) 334 Mannitol 299, 581 Masking agents 12, 312 Mass action law 16 applications to electrolyte solutions, 23 Matrix effects 733, 794 Maxima in polarography 597 suppression of, 597, 611 Mean deviation 134 relative, 134 standard, 134 Measuring cylinders, 87 flasks, 81... 

Standard additions A method of relating the intensity of signal from an analyte measured in an unknown to the amount of analyte present. This technique is designed to take matrix effects into account. 

If the sample and standard have essentially the same matrices (e.g., air particulates or river sediments), one can go through the total measurement process with both the sample and the standard in order to (a) check the accuracy of the measurement process used (compare the concentration values obtained for the standard with the certified values) and (b) obtain some confidence about the accuracy of the concentration measurements on the unknown sample since both have gone through the same chemical measurement process (except sample collection). It is not recommended, however, that pure standards be used to standardize the total chemical measurement process for natural matrix type samples chemical concentrations in the natural matrices could be seriously misread, especially since the pure PAH probably would be totally extracted in a given solvent, whereas the PAH in the matrix material probably would not be. All the parameters and matrix effects. Including extraction efficiencies, are carefully checked in the certification process leading to SRM s. 

In their broadest application, CRMs are used as controls to verify in a direct comparison the accuracy of the results of a particular measurement parallel with this verification, traceability may be demonstrated. Under conditions demonstrated to be equal for sample and CRM, agreement of results, e.g. as defined above, is proof. Since such possibilities for a direct comparison between samples and a CRM are rare, the user s claims for accuracy and traceability have to be made by inference. Naturally, the use of several CRMs of similar matrix but different analyte content will strengthen the user s inference. Even so, the user stiU has to assess and account for all uncertainties in this comparison of results. These imcertainty calculations must include beyond the common analytical uncertainty budget (i) a component that reflects material matrix effects, (2) a component that reflects differences in the amount of substance determined, (3) the uncertainty of the certified or reference value(s) used, and 4) the uncertainty of the comparison itself AU this information certainly supports the assertion of accuracy in relation to the CRM. However, the requirement of the imbroken chain of comparisons wiU not be formally fulfilled. 

In subsequent experiments, it was found that rearrangement of 2 persisted in solid glasses at temperatures as low as 28 K, where the reaction rates became nearly temperature independent, as expected. The fact that similar kinetics were measured in solution and in low temperature solids indicated that matrix effects were minimal, at least in these intramolecular hydrogen abstractions. 

Measurement caused by concurrent reactions or incomplete reaction processes in the case of chemical principles, and by instrumental deviations and wrong adjustment in the case of physical methods. A frequently encountered reason for the occurrence of systematic deviations is erroneous calibration due to unsuitable calibration standards, matrix effects, or insufficient methodical or theoretical foundation. 

A particular issue that must be considered for all calibration procedures is the possibility of matrix effects on the analyte signal. If such effects are present they may be allowed for in many cases by matrix matching of the standard to the sample. This of course requires an accurate knowledge of the sample matrix. Where this is not available, the method of standard addition is often effective. This involves spiking at least three equal aliquots of the sample with different amounts of the analyte, and then measuring the response for both spiked and unspiked aliquots. A plot of response vs analyte, extrapolated back, will give abscissae intercepts from which the amount of analyte in the sample may be deduced (Figure 2.8). 

Matrix effect is a phrase normally used to describe the effect of some portion of a sample matrix that causes erroneous assay results if care is not taken to avoid the problem or correct for it by some mechanism. The most common matrix effects are those that result in ion suppression and subsequent false negative results. Ion enhancement may lead to false positive results.126 127 Several reports about matrix effects include suggestions on what can cause them and how to avoid them.126-147 While various ways to detect matrix effects have been reported, Matuszewski et al.140 described a clear way to measure the matrix effect (ME) for an analyte, recovery (RE) from the extraction procedure, and overall process efficiency (PE) of a procedure. Their method is to prepare three sets of samples and assay them using the planned HPLC/MS/MS method. The first set is the neat solution standards diluted into the mobile phase before injection to obtain the A results. The second set is the analyte spiked into the blank plasma extract (after extraction) to obtain the B results. The third set is the analyte spiked into the blank plasma before the extraction step (C results) these samples are extracted and assayed along with the two other sets. The three data sets allow for the following calculations ... 

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