Automated statistical control of activities measured by gamma-ray spectrometry

Statistical tests were performed for reviewing the results of routinely performed measurements. Within the operating procedure for routine spectral analysis the current results were compared with the average values obtained from measurements of samples of the same type collected at the same location. The agreement of the current result with the population of the results was assessed by the u-statistic, where the expected spread of the population of the results is given by their standard deviation and their uncertainties. After checking for reliability, the current result was used for updating the average and the spread of the population. Some examples are presented to illustrate how the average and the spread follow changes in the population of the measurement results.     

Quality assurance and statistical control

In scientific research laboratories it is rarely possible to use quality assurance schemes, developed for large-scale analysis. Instead methods have been developed to control the quality of modest numbers of analytical results by relying on statistical control: Analysis of precision serves to detect analytical errors by comparing thea priori precision of the analytical results with the actual variability observed among replicates or duplicates. The method relies on the chi-square distribution to detect excess variability and is quite sensitive even for 5–10 results. Interference control serves to detect analytical bias by comparing results obtained by two different analytical methods, each relying on a different detection principle and therefore exhibiting different influence from matrix elements; only 5–10 sets of results are required to establish whether a regression line passes through the origo. Calibration control is an essential link in the traceability of results. Only one or two samples of pure solid or aqueous standards with accurately known content need to be analyzed. Verification is carried out by analyzing certified reference materials from BCR, NIST, or others; their limited accuracy of 5–10% make them less suitable for calibration purposes.     

A statistical approach to the choice of channel-width in gamma-ray spectrometry

Equations giving the percentage of extra peak-broadening caused by the finite channel-width in multichannel gamma-ray spectrometry were earlier developed by means of a statistical treatment. Empirical straight-line fits were used for the energy vs. resolution curves. In this paper this treatment is applied, but using instead a semi-empirical second-order equation for NaI(Tl) detectors. The disadvantage of the use of two equations to describe one detector is thus overcome. We present four different ways to estimate the extra peak-broadening as a function of channel-width, depending on the degree of precision required. A statistical consideration giving the precision of each estimate is included. It appears that for many cases no specific detector information is required. For these cases a generally applicable plot is given.     

On the determination of the column dead volume from homologous series

Summary The calculation of the column dead volume from high precision gross retention times of the n-alkanes pentane to heptadecane in an ODS/MeOH system yields values showing an apparently linear decrease with increasing carbon number. This effect is thought to be related to the partial exclusion from pores. If retention data are corrected for exclusion, one uniform dead volume is obtained.     

On the statistical theory of the nematic mesophase

It is shown that dipole-dipole dispersion forces are not sufficient to account for ordering in the nematic mesophase.     

A quick and effective multivariate statistical strategy for imaging mass spectrometry

A new multivariate statistical strategy for analyzing large datasets that are produced by imaging mass spectrometry（IMS） techniques is reported.The strategy divides the whole datacube of the sample into several subsets and analyses them one by one to obtain the results.Instead of analyzing the whole datacube at one time,the strategy makes the analysis easier and decreases the computation time greatly.In this report,the IMS data are produced by the air flow-assisted ionization IMS（AFAI-IMS）.The strategy can be used in combination with most multivariate statistical analysis methods.In this paper,the strategy was combined with the principal component analysis（PCA） and partial least square analysis（PLS）.It was proven to be effective by analyzing the handwriting sample.By using the strategy,the m/z corresponding to the specific lipids in rat brain tissue were distinguished successfully.Moreover the analysis time grew linearly instead of exponentially as the size of sample increased.The strategy developed in this study has enormous potential for searching for the mjz of potential biomarkers quickly and effectively.     

On the intersection of electrochemistry and mass spectrometry

The application of nanopipettes, developed first as a tool for electrochemistry and electrophysiology, as tools for mass spectrometry is considered. Recent examples of advances in electrospray ionization and sampling for mass spectrometry with nanopipettes is discussed. These examples show a scientific intersection that is ripe for further development.     

Optimization of the Hewlett-Packard particle-beam liquid chromatography-mass spectrometry interface by statistical experimental design

Optimization of both sensitivity and ionization softness for the Hewlett-Packard particle-beam liquid chromatography-mass spectrometry interface has been achieved by using a statistical experimental design with response surface modeling. Conditions for both optimized sensitivity and ionization softness were found to occur at 55-lb/in.² nebulizer flow, 35°C desolvation chamber temperature with approximately 45% organic modifier in the presence of 0.02-F ammonium acetate and a liquid chromatography flow rate of 0.2 mL/min.     

Differentiation of vegetable oils by mass spectrometry combined with statistical analysis

The main triacylglycerol (TAG) composition of different plant oils (almond, avocado, corn germ, grape seed, linseed, mustard seed, olive, peanut, pumpkin seed, sesame seed, soybean, sunflower, walnut and wheat germ) were analyzed using two different mass spectrometric techniques: HPLC/APCI-MS (high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry) and MALDI-TOFMS (matrix-assisted laser desorption/ionization time-of-flight mass spectrometry).Linear discriminant analysis (LDA) as a multivariate mathematical statistical method was successfully used to distinguish different plant oils based on their relative TAG composition. With LDA analysis of either APCI-MS or MALDI-MS data, the classification among the almond, avocado, grape seed, linseed, mustard seed, olive, sesame seed and soybean oil samples was 100% correct. In both cases only 6 different oil samples from a total of 73 were not classified correctly.     

On the statistical behaviour of molecular vibronic energy levels

Electronic spectra of polyatomic molecules often exhibit a high density of complicated energy levels, making a detailed analysis of the individual levels unfavourable. In these cases, statistical tests provide an appropriate means for analysing the spectra. Fluctuation measures are presented and evaluated for calculated and experimental molecular spectra as examples. The results are compared with the predictions of random matrix theory.     

Evaluation of statistical control charts for on-line radiation monitoring

Statistical control charts are presented for the evaluation of time series radiation counter data from flow cells used for monitoring of low levels of ⁹⁹TcO₄⁻ in environmental solutions. Control chart methods consisted of the 3-sigma (3σ) chart, the cumulative sum (CUSUM) chart, and the exponentially weighted moving average (EWMA) chart. Each method involves a control limit based on the detector background which constitutes the detection limit. Both the CUSUM and EWMA charts are suitable to detect and estimate sample concentration requiring less solution volume than when using a 3σ control chart. Data presented here indicate that the overall accuracy and precision of the CUSUM method is the best.     

Calibration in solid-sample spectrometry: statistical routine or a complex of problems?

The analytical calibration in atomic spectrometry similar to other indirect analytical methods has been for many years basically a routine procedure. While the calibration is based on the use of the solution standards, it is only a chemometrical routine in which the by IUPAC recommended complex procedure could be used. In the last two decades the solid-sampling methods have been spread out, their interactivity is connected with their use in analysis of the non-oxide ceramics as well as samples of the environmental relevancy (e.g. sediments, sludge, dust sediments, etc.). This wide use of the solid sampling methods has pointed to more specific problems, as lack of suitable CRM-s, homogeneity problems and with those connected problems of the useable sample amounts. Some of the mentioned problems as well as their elimination possibilities are the aim of this work.     

Multivariate statistical identification of human bladder carcinomas using ambient ionization imaging mass spectrometry

Diagnosis of human bladder cancer in untreated tissue sections is achieved by using imaging data from desorption electrospray ionization mass spectrometry (DESI-MS) combined with multivariate statistical analysis. We use the distinctive DESI-MS glycerophospholipid (GP) mass spectral profiles to visually characterize and formally classify twenty pairs (40 tissue samples) of human cancerous and adjacent normal bladder tissue samples. The individual ion images derived from the acquired profiles correlate with standard histological hematoxylin and eosin (H&E)-stained serial sections. The profiles allow us to classify the disease status of the tissue samples with high accuracy as judged by reference histological data. To achieve this, the data from the twenty pairs were divided into a training set and a validation set. Spectra from the tumor and normal regions of each of the tissue sections in the training set were used for orthogonal projection to latent structures (O-PLS) treated partial least-square discriminate analysis (PLS-DA). This predictive model was then validated by using the validation set and showed a 5% error rate for classification and a misclassification rate of 12%. It was also used to create synthetic images of the tissue sections showing pixel-by-pixel disease classification of the tissue and these data agreed well with the independent classification that uses histological data by a certified pathologist. This represents the first application of multivariate statistical methods for classification by ambient ionization although these methods have been applied previously to other MS imaging methods. The results are encouraging in terms of the development of a method that could be utilized in a clinical setting through visualization and diagnosis of intact tissue.     

Quality control and statistical analysis of biodistribution of commercial99mTc-IDA derivatives

The results obtained for radiochemical purity of ITLC (SA) and (SG) using different solvent systems and low voltage electrophoresis are presented in the paper. Radiochemical purities obtained for^99mTc-dimethyl IDA (^99mTc-HIDA) and^99mTc-diethyl IDA (^99mTc-EHIDA) are 98.1±0.6% and 98.7±0.5%, respectively. Variable^99mTc hydrolyzate contents, depending on the ionic strength of the eluents and on the time interval between labelling and analysis, have been obtained by Sephadex chromatography. The eluent containing Sn-EHIDA inhibits dissociation of^99mTc-EHIDA due to dilution of the preparation during elution of the column and yielding only a small percent of Sephadex bound fraction, as compared to other investigated eluents. The range of normal^99mTc-IDA biodistribution values in the organs of experimental animals and statistical significance of the difference between these two preparations have also been determined. The results obtained for^99mTc-HIDA and^99mTc-EHIDA in the liver are 33.9±5% and 25.7±4.7%, respectively p<0.01.     

Analysis of sexual assault evidence: statistical classification of condoms by ambient mass spectrometry

Desorption electrospray ionization mass spectrometry (DESI‐MS) and easy ambient sonic‐spray ionization mass spectrometry (EASI‐MS) are employed here in the forensic analysis of chemical compounds found in condoms and relative traces, and their analytical performances are compared. Statistical analysis of data obtained from mass spectra only was applied in order to obtain classification rules for distinguishing ten types of condoms. In particular, two supervised chemometric techniques [linear discriminant analysis (LDA) and soft independent modeling of class analogy (SIMCA)] were carried out on absolute and relative intensity values to test the performances of statistical models in terms of predictive capacity. The achieved classification of samples was excellent because of the high prediction percentages of the method used both for DESI and EASI mass spectrometry analyses, confirming these two as potential ambient ionization techniques for forensic analyses in case of sexual assault crimes. EASI‐MS showed 99% prediction ability for LDA using relative data and 100% prediction ability for SIMCA using both absolute and relative ones, while DESI showed 94% prediction ability for both LDA and SIMCA. The absence of any sample preparation technique gives advantages in terms of sample preservation and reduced contamination, allowing successive analyses to be performed on the same sample by other techniques. Copyright © 2015 John Wiley & Sons, Ltd.     

液相色谱-质谱联用在兴奋剂检测中的应用及进展

液相色谱-质谱联用技术已越来越广泛地应用在兴奋剂的检测中,其中包括对各类小分子兴奋剂和肽类激素等的检测。本文综述了近年来液相色谱-质谱联用在兴奋剂检测中的筛选、确证和定量方面的应用及进展情况,并讨论了相关的检测标准。     

A statistical approach to the choice of channel-width in gamma-ray spectrometry using empirical relations between resolution and gamma-ray energy

The problem of extra peak-broadening caused by the finite channel-width in multichannel gamma-ray spectrometry is discussed, using empirical equations for the relations between resolution and energy for NaI(T1) scintillation detectors and Ge(Li) drift detectors. Relations are derived and graphs designed to estimate the extra peak-broadening at a certain energy, caused by the compromise necessary when using a chosen energy scale in as few channels as possible.     

On-line HPLC combined with multivariate statistical process control for the monitoring of reactions

On-line high performance liquid chromatography is used to monitor a steady state reaction over 35.2 h, with 197 chromatograms recorded as the reaction progresses. For each chromatogram, peaks are detected, baseline corrected, aligned and integrated to provide a peak table consisting of the intensities of 19 peaks, two corresponding to the reactants, one to the product and one to the solvent, the remaining being impurities, by-products or intermediates. D-charts and Q-charts from multivariate statistical process control are applied to the data to determine which samples are out of control and also provide diagnostic insight into why these samples are problematic. The D-chart is best at looking at overall performance issues such as problems with mixing or difficulties with instrument operation, whereas the Q-charts are best at detecting impurities during the reaction.