Duplicate samples

The most useful methods for quality assessment are those that are coordinated by the laboratory and that provide the analyst with immediate feedback about the system s state of statistical control. Internal methods of quality assessment included in this section are the analysis of duplicate samples, the analysis of blanks, the analysis of standard samples, and spike recoveries. 

Analysis of Duplicate Samples An effective method for determining the precision of an analysis is to analyze duplicate samples. In most cases the duplicate samples are taken from a single gross sample (also called a split sample), although in some cases the duplicates must be independently collected gross samples. The results from the duplicate samples, Xi and X2, are evaluated by determining the difference, d, or the relative difference, d) between the samples... 

Agency. A second example of an external method of quality assessment is the voluntary participation of the laboratory in a collaborative test (Chapter 14) sponsored by a professional organization such as the Association of Official Analytical Chemists. Finally, individuals contracting with a laboratory can perform their own external quality assessment by submitting blind duplicate samples and blind standard samples to the laboratory for analysis. If the results for the quality assessment samples are unacceptable, then there is good reason to consider the results suspect for other samples provided by the laboratory. 

With a prescriptive approach to quality assessment, duplicate samples, blanks, standards, and spike recoveries are measured following a specific protocol. The result for each analysis is then compared with a single predetermined limit. If this limit is exceeded, an appropriate corrective action is taken. Prescriptive approaches to quality assurance are common for programs and laboratories subject to federal regulation. For example, the Food and Drug Administration (FDA) specifies quality assurance practices that must be followed by laboratories analyzing products regulated by the FDA. 

If the spike recovery for Bsf is acceptable, or if the result for sample B is below the method s detection limit or outside the range of 0.1 to 10 times the amount of analyte spiked in Bsf, then the duplicate samples Ai and A2 are analyzed. The results for Ai and A2 are discarded if the difference between their values is excessive. If the difference between the results for Ai and A2 is within the accepted limits, then the results for samples Ai and B are compared. Since samples collected from the same sampling site at the same time should be identical in composition, the results are discarded if the difference between their values is unsatisfactory, and accepted if the difference is satisfactory. 

In a performance-based approach to quality assurance, a laboratory is free to use its experience to determine the best way to gather and monitor quality assessment data. The quality assessment methods remain the same (duplicate samples, blanks, standards, and spike recoveries) since they provide the necessary information about precision and bias. What the laboratory can control, however, is the frequency with which quality assessment samples are analyzed, and the conditions indicating when an analytical system is no longer in a state of statistical control. Furthermore, a performance-based approach to quality assessment allows a laboratory to determine if an analytical system is in danger of drifting out of statistical control. Corrective measures are then taken before further problems develop. 

The average range for the 20 duplicate samples is 0.177. Because two replicates were used for each point, the UWL and UCL are... 

Average Range for Duplicate Samples for Different Concentrations of Chromium in Water... 

Using Control Charts for Quality Assurance Control charts play an important role in a performance-based program of quality assurance because they provide an easily interpreted picture of the statistical state of an analytical system. Quality assessment samples such as blanks, standards, and spike recoveries can be monitored with property control charts. A precision control chart can be used to monitor duplicate samples. 

Duplicate samples for the photometer involve duplicate dilutions because this is the critical step for precision for the HPLC the same solution is injected a second time because the injection/detection/inte-gration step is more error-prone than the dilution. 

Beer Samples. The beer samples were examined as part of the American Society of Brewing Chemists (ASBC) and Association of Official Analytical Chemists (AOAC) collaborative studies of NDMA in beer. Duplicate samples were analyzed by the column extraction procedure and the ASBC distillation procedure (35). The AOAC procedure (36) was similar, except that a larger sample (50 vs. 25 g) was examined and sulfamic acid was added to minimize artifactual formation of nitrosamines. Both methods utilize N-nitrosodipropylamine (NDPA) as an internal standard. 

These data are used to accept or reject a set of replicated samples. The replicates are usually duplicate samples. Therefore, the difference between the two values should lie within the critical range. If not, the sample Is rejected and the analyses rerun If possible. Discarding results should only be done after... 

The studies in the Yakima Valley were made on two varieties of apples and those in the Mississippi Valley on five varieties. Duplicate samples of 1500 and 2000 grams of fruit were employed for each analysis at Vincennes and samples of 1000 to 1500 grams at Yakima. 

Duplicate samples were processed onshore after a variety of storage procedures. All samples were analysed for copper and iron by GFA-AS. Only samples filtered (< 1 pm), acidified, and stored frozen gave extractable copper and iron results comparable with those for samples extracted immediately after collection. Cold storage with sample acidification in polyethylene containers appeared less satisfactory. Organic extracts from samples processed onboard are best retained in all-Teflon containers pending complete digestion and analysis onshore. Unless clean (ultra-filtered air) conditions can be ensured onboard, the estuarine water samples are best returned in a filtered, acidified, and frozen condition for onshore processing. 

In summary, WSL uses 8 screened panellists, 60% dilution steps and, where possible, takes duplicate samples it is indicated that the corresponding 95% confidence limits are -33% to +49%. It should, of course, be remembered when comparing dilution values determined by the same set of panellists (e.g. to evaluate the % efficiency of odom control equipment on a particular day) that the standard error is somewhat reduced because the person to person variance need not be considered. 

Treatment of pectin (containing 79. % of galacturonic acid) for 1 h at 121° gave 53.5% of galacturonic acid for a net recovery of 67%. The average of duplicate samples is presented. Amounts relative to myoinositol, the internal standard, in arbitrary units. 

The 5 k actives with percent inhibition of 25 to 40% and that feU into clusters of less than five compounds were treated separately using BCUT diversity analysis, as described in Section 6.2.5. A cell-based selection biased by primary activity from six bins per each of six axes yielded 1258 compounds. The combined selection from filtering, clustering, and diversity totaled 6986 compounds representing 3337 ring scaffolds and was submitted for confirmation assays. Note that the full set of 16 k filtered actives contained 9254 ring hashcodes, so the selected set covers 36.1% of the represented scaffolds. Because of the presence of duplicate samples in the corporate screening collection, 7275 samples were pulled and assayed. 

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