Strategies for constructing the calibration set for a near infrared spectroscopic quantitation method

Three strategies for the construction of calibration sets have been tried, with the objective to develop and to validate a NIR quantitation method.The first two approaches consist of the use of two types of samples, named: samples of laboratory obtained by mixing the ingredients that compose the drug, and doped samples obtained by under- and over-dosed production samples. In order to improve the prediction results, production samples have been added to each calibration model. The ensuing models were validated with a view to determine their fitness for purpose. However, spectral differences between the laboratory samples and doped samples resulted in spurious predictions in quantifying samples of one type using the model developed from samples of the other.Such differences were studied in depth and a third procedure has been proposed, based on a calibration model constructed with an unique type of sample (laboratory sample) for later to correct it with a few doped samples. This corrected model has a good predictive ability on production samples.     

Comparison of radionuclides levels from the Chernobyl reactor accident and from global fallout

Studies on radioactive fallout from atmospheric nuclear weapons tests have been carried out at this laboratory since the mid-fifties. The data thus generated on the levels and composition of radioactive fallout in India has been published periodically. Consequent to the Chernobyl reactor accident in the USSR in April 1986, similar studies were carried out. A number of fairly active samples were collected from commercial aircraft which had flown over the USSR soon after the accident. Even though the levels of fallout from the Chernobyl reactor accident observed in India were not significant from a health hazard view point, the studies provided detailed information on differences in the composition of fallout from the accident and long term radiation exposures likely to accrue from the Chernobyl fallout as opposed to global fallout from atmospheric nuclear weapons tests. This paper presents the results and their interpretation on the above aspects.     

Comparative analysis of volatile components from Clematis species growing in China

The volatile components between stems and roots and also among five Clematis species from China were studied and analyzed by gas chromatography-mass spectrometry (GC-MS) combined with alternative moving window factor analysis (AMWFA), a new chemometric resolution method. Identification of the compounds was also assisted by comparison of temperature-programmed retention indices (PTRIs) on HP-5MS with authentic samples included in our own laboratory database under construction. A total of 153 different compounds accounting for 86.6-96.5% were identified and significant qualitative and quantitative differences were observed among the samples. The major volatile components in different essential oils from Clematis species were n-hexadecanoic acid and (Z,Z)-9,12-octadecadienoic acid. Our work further demonstrated chemometric resolution techniques upon the two-dimensional data and PTRIs can provide a complementary and convenient method for fast and accurate analysis of complex essential oils.     

Interlaboratory comparison of pesticide recovery from water using solid-phase extraction disks and gas chromatography

An interlaboratory study was conducted to assess the suitability of C18 solid-phase extraction disks to retain and ship different pesticides from water samples. Surface and deionized water samples were fortified with various pesticides and extracted using C18 disks. Pesticides were eluted from disks and analyzed in-house, or disks were sent to another laboratory where they were eluted and analyzed. Along with the disks, a standard pesticide solution in methanol was also shipped to be used for fortification, extraction, and analysis. The highest recovery from deionized or surface water using shipped disks was obtained for cyanazine (>97%), followed by metalaxyl (>96%), and atrazine (>92%). Although <40% of the bifenthrin, chlorpyrifos, and chlorothalonil fortified in surface water was recovered from shipped disks, recoveries from deionized water were >70%. From in-house eluted disks, bifenthrin and chlorpyrifos were recovered at 118 and 105%, whereas chlorothalonil showed 71% recovery, indicating that poor recovery from surface water was due to loss during shipping rather than low retention by the C18 disks. There was no consistent relationship between recovery from C18 disk and physicochemical properties for the pesticides included in this study. For most of the 13 pesticides tested, there were no differences in recovery between in-house extracted disks and shipped disks, indicating the suitability of disks to concentrate and transport pesticides extracted from water samples.     

Proficiency testing in food microbiology: experience from implementation of ISO/IEC 17043 and ISO/TS 22117

The proficiency testing (PT) scheme ??AQUA?? for food microbiology was organised by the Istituto Zooprofilattico Sperimentale delle Venezie (IZSVe) according to ISO/IEC 17043 and ISO/TS 22117. This paper describes the IZSVe experience on the application of the above-mentioned standards for the PTs, with focus on the Enterobacteriaceae enumeration one. Freeze-dried food matrices contaminated with American Type Culture Collection bacterial strains were used as test samples for each microbiological PT organised by IZSVe. The sample homogeneity and stability were verified prior to distribution to participants and throughout the PT, respectively. The participating laboratories analysed samples using their routine methods, and results were transmitted to IZSVe. Data and methods used by each participating laboratory were analysed in order to evaluate the laboratory performance. With reference to the Enterobacteriaceae PT, the test samples were homogeneous and stable. In addition, most laboratory results were obtained using equivalent test methods. Statistical approaches applied to analyse data generated from all participating laboratories revealed similar outcomes as no significant outlying count and only 5?% of unacceptable results were observed. Finally, the z-score, with the standard deviation that does not vary from round toround, was applied to compare and to evaluate the performance of each laboratory over time highlighting possible persistent trends over several rounds.     

A semi-automated approach for processing and extracting low-level plutonium from soil

A semi-automated approach for processing and extracting plutonium from large soil samples has been developed and implemented in our laboratory. The system approach was designed around basic plutonium techniques already published in the literature. The technique was carried out using modular work stations for the major analytical steps, namely; soil leaching, plutonium extraction and phase evaporation. This allowed the laboratory to operate in a batch mode which improved sample flow and significantly reduced analysis cost and time. The method has been validated and is routinely used in our laboratory. Chemical yield, accuracy and precision were comparable to those obtained from manual procedures. The system was designed with built-in flexibility to accommodate revised or similar procedures and to complement most existing laboratory equipment and resources.     

Provenance study of obsidian samples by using portable and conventional X ray fluorescence spectrometers. Performance comparison of both instrumentations

The potentiality of portable instrumentation lies on the possibility of the in situ determinations. Sampling, packaging and transport of samples from the site to the laboratory are avoided and the analysis becomes non destructive at all. However, detection limits for light elements are, in most cases, a limitation for quantification purposes. In this work a comparison between the results obtained with an X ray fluorescence spectrometer laboratory based and a portable instrument is performed. A set of 76 obsidian archaeological specimens from northwest Patagonia, Argentina was used to carry out the study. Samples were collected in the area of the middle and high basin of the Limay River. The analytical information obtained with both instrumentations was complemented with Principal Component Analysis in order to define groups and identify provenance sources. The information from both instruments allows arriving to the same conclusion about sample provenance and mobility of hunter-gatherer groups. Three groups of sources were identified in both cases matching with the geographical information. Also, same sets of outlier samples or not associated to these sources were found. Artifact samples were associated mainly to the closest sources, but some of them are related to sources located more than three hundred kilometers, evidencing the large mobility of the hunter-gatherers by the obsidian interchange. No significant differences between concentrations values obtained by laboratory based instrument and portable one were found.     

Isolation of Glycolipids from Blood Elements

Abstract

Several chromatographic e.g. HPTLC, HPLC, etc. methods have been published in the literature for the separation, after sufficient pretreatment, of derivatized or non-derivatized glycolipid samples.

Our task is the extraction, isolation and separation of the glycolipids from different blood elements, followed by suitable fractionation methods, giving the lipid classes in sufficient purity and quantity for HPLC, HPTLC and OPTLC measurements and possibly further biochemical use.

We show the differences between the procedures commonly used and that developed in our laboratory.

The advantage of our method, which employs 3 cm long Brownlee Labs HPLC cartridges, is that it can be automated, it gives class fractionation of the lipid samples and as it is hardware compatible with HPLC equipment it can be used directly in a coupled column system for on line separation in the individual class. The development of this column coupling method for the fractionation of a given lipid class from the total lipid extract on an analytical column is under development.     

Solid phase versus solvent extraction of pesticides from water

The average recovery for 12 pesticides spiked into 100 ml of water at 0.1 ppb was 90% when cartridges containing 100 mg of C-18 bonded porous silica were used for adsorption. Flow rates of up to 200 bed volumes per minute were employed for the adsorption step. Quantitative desorption of the pesticides was accomplished with less than 100l of solvent, thus eliminating the need for a solvent reduction step. The pesticides from samples of surface waters were adsorbed onto C-18 bonded porous silica at the sampling site and the cartridges containing the bonded phase were returned to the laboratory for elution and analysis. The analytical results obtained from use of this procedure agreed with those obtained for duplicate samples of the water that were processed in the laboratory using standard solvent extraction procedures.     

不同部位人体气味的分析研究

运用SPME-GC/MS法对同一个体腋窝部、手部和足部的人体气味样品进行了采样分析,通过比较3个部位人体气味样品色谱图中共有成分相对峰面积比和非共有成分,结合使用相似度法对3个部位的人体气味进行了比较分析,三者具有较高的相似度,但仍存在一些细微的差别。     

Surface analysis of particulates from laboratory hood exhaust manifold

Particulate samples collected from a laboratory ventilation manifold during routine maintenance were analyzed to determine if particulate composition had changed as a result of changes in the laboratory's atmosphere. This ventilation manifold exhausts more than 100 fume hoods. The particulate samples were analyzed using static secondary ion mass spectrometry (SIMS). The negative SIMS spectra showed abundant Cl^?, NO₃^?, and HSO₄^?, consistent with the use of mineral acids in the laboratory. Cluster anions containing primarily Zn (but also other transition metals) were detected, which signaled corrosion of the manifold's galvanized steel by the volatilized acids. The most abundant ions in the cation SIMS spectra were derived from cyclohexylamine (CHA), which had been used as an antiscaling agent in the facility's boiler. Steam from the boiler, which contained CHA, was used to humidify the building air; this practice stopped in 1997. The abundances of the CHA‐derived ions were significantly lower in the samples collected in 2004 and 2006 than in the 1992 samples, indicating that the CHA is being slowly depleted. Changes in the relative abundances suggest exponential depletion from the manifold with rate constants that are on the order of 0.01 to 0.04 month^?1. Published in 2007 John Wiley & Sons, Ltd.     

Application of Raman microscopy to the characterization of different verdigris variants obtained using recipes from old treatises

Verdigris is an historical pigment of synthetic origin widely used in the artistic scope, from the antiquity to beginning of 19th century. It is a greenish or green-bluish colored product resulting from corrosion of pure copper and alloys caused by the action of different chemical reagents. The preparation recipes are numerous and appear in old texts, such as: treatises of art and texts of alchemy, as well as in books of secrets, natural history and those concerning medicines. A comparative study of these recipes shows significant differences depending on the initial components and the methodology applied in the synthesis of the pigment. Consequently, typical verdigris pigments very likely correspond to a variety of chemical compositions and, in addition, it might contain certain amounts of unknown by-products. To confirm such hypothesis, four different preparation recipes of verdigris have been carefully reproduced in our laboratory, and characterized by Raman microscopy. Our experiments allowed us to establish interesting differences among the studied samples. Some differences are mostly related to the ingredients used in the elaboration of the so-called raw verdigris. In other cases, the observed variations are consequence of the recrystallization treatment of the pigment. In general, all spectra reveal the existence of common component, namely, the copper(II) acetate (hydrated or anhydrous). However, other minority components have been detected in our samples, for instance, copper oxides, copper chlorides, and ammonic salts. In some cases, these compounds allow us to deduce the type of recipe used in the elaboration of the pigment.     

An inter-laboratory comparative study into sample preparation for both reproducible and repeatable forensic 2H isotope analysis of human hair by continuous flow isotope ratio mass spectrometry

Stable isotope analysis of organic materials for their hydrogen ((2)H), carbon ((13)C), nitrogen ((15)N) or oxygen ((18)O) isotopic composition using continuous flow isotope ratio mass spectrometry (CF-IRMS) is an increasingly used tool in forensic chemical analysis. (2)H isotopic analysis can present a huge challenge, especially when dealing with exhibits comprising exchangeable hydrogen such as human scalp hair. However, to yield forensic data that are fit for purpose, analysis of the (2)H isotopic composition of the same homogeneous human hair sample by any laboratory worldwide must yield the same isotopic composition within analytical uncertainty. This paper presents longitudinal (2)H isotope data for four human hair samples of different provenance, measured by three different laboratories whose sample preparation was based on a two-stage H exchange equilibration method. Although each laboratory employed varying means to comply with the generic features of the sample preparation protocol such as the (2)H isotopic composition of exchange waters or drying down of samples prior to analysis, within each laboratory the Principle of Identical Treatment (P.I.T.) was applied for each individual experiment. Despite the variation in materials and procedures employed by the three laboratories, repeatable and reproducible 'true' (2)H isotope values (δ(2)H(hair,true)) were determined by each laboratory for each of the four stock samples of human scalp hair. The between-laboratory differences for obtained δ(2)H(hair,true) values ranged from 0.1 to 2.5 ‰. With an overall 95% confidence interval of ±2.8 ‰, these differences were not significantly different, which suggests that the general method of two-stage exchange equilibration carried out at ambient temperature is suitable for accurately and reproducibly determining 'true' δ(2)H-values for hair and other proteins provided that certain key conditions are met.     

Multivariate analysis of laser-induced breakdown spectroscopy chemical signatures for geomaterial classification

A large suite of natural carbonate, fluorite and silicate geological materials was studied using laser-induced breakdown spectroscopy (LIBS). Both single- and double-pulse LIBS spectra were acquired using close-contact benchtop and standoff (25 m) LIBS systems. Principal components analysis (PCA) and partial least squares discriminant analysis (PLS-DA) were used to identify the distinguishing characteristics of the geological samples and to classify the materials. Excellent discrimination was achieved with all sample types using PLS-DA and several techniques for improving sample classification were identified. The laboratory double-pulse LIBS system did not provide any advantage for sample classification over the single-pulse LIBS system, except in the case of the soil samples. The standoff LIBS system provided comparable results to the laboratory systems. This work also demonstrates how PCA can be used to identify spectral differences between similar sample types based on minor impurities.     

Exploring STR signal in the single‐ and multicopy number regimes: Deductions from an in silico model of the entire DNA laboratory process

Short tandem repeat (STR) profiling from DNA samples has long been the bedrock of human identification. The laboratory process is composed of multiple procedures that include quantification, sample dilution, PCR, electrophoresis, and fragment analysis. The end product is a short tandem repeat electropherogram comprised of signal from allele, artifacts, and instrument noise. In order to optimize or alter laboratory protocols, a large number of validation samples must be created at significant expense. As a tool to support that process and to enable the exploration of complex scenarios without costly sample creation, a mechanistic stochastic model that incorporates each of the aforementioned processing features is described herein. The model allows rapid in silico simulation of electropherograms from multicontributor samples and enables detailed investigations of involved scenarios. An implementation of the model that is parameterized by extensive laboratory data is publically available. To illustrate its utility, the model was employed in order to evaluate the effects of sample dilutions, injection time, and cycle number on peak height, and the nature of stutter ratios at low template. We verify the model's findings by comparison with experimentally generated data.     

Selective Sorption of Pd(II) from Nitric-Nitrous Acid Solutions Simulating PUREX Raffinates with Polymethylene Monosulfide

Static sorption of Pd(II) from nitric and nitric-nitrous acid solutions, simulating PUREX raffinates, with laboratory and semicommercial samples of polymethylene monosulfide is studied. The selectivity of Pd(II) recovery from the simulated solutions is determined.     

模拟酸雨对冶炼厂土壤中Cd释放行为影响的研究

模拟株洲地区降水酸度及离子组成,用pH3．5、pH4．5、pH5．6的模拟酸雨对株洲冶炼厂土壤样品（S1）进行了Cd动态淋溶试验。结果表明,酸雨加速了土壤中Cd的释放,表现为模拟酸雨pH值越低Cd释放量越大;且在pH3．5、pH4．5的平均释放水平是对照组（pH5．6）的3．97和2．94倍;其释放量与土壤中Cd的原始含量、赋存形态关系密切;淋出液中Cd与Zn呈显著的正相关关系,相关系数均大于0．94;与Pb呈负相关关系,冶炼厂Cd的来源应与工厂Zn的生产关系密切,在pH3．5、pH4．5的模拟酸雨作用下分别是国家饮用水源水质标准值的1037倍、768倍。随着淋溶的进行,酸雨可加速工厂土壤中Cd的释放,对人类存在着直接或潜在的危害性。     

Spectrochemical study for the in situ detection of oil spill residues using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been used to identify the differences or similarities between crude oil and fuel residues. Firstly, a man portable LIBS analyzer was used for the on-site environmental control and analysis of the oil spill from The Prestige. An exhaustive analysis of crude oil and oil spill residues (collected during the field campaign in the Galician Coast) was performed in the laboratory. Characteristics elements in petroleum such as C, H, N, O, Mg, Na, Fe and V were detected. In addition, contributions from Ca, Si and Al in the composition of residues have been found. The use of intensity ratios of line and band emissions in the original fuel (crude oil) and in the aged residues allowed a better characterization of the samples than the simple use of peak intensities. The chemical composition between the crude oil and the fuel residues was found completely different. As well, a statistical method was employed in order to discriminate residues. Although significant differences were observed, no conclusions in terms of age and provenance could be reached due to the unknowledgment in the origin of the samples.     

An inter-laboratory comparison study for the determination of copper and lead from the wastewater of printed circuit board manufacturing industry in Pakistan

This inter-laboratory comparison study was arranged for 28 laboratories from different public and private sector organizations in Pakistan having wastewater testing capabilities aimed at improving the quality and comparability of test results. This national inter-laboratory study was started in December 2003 and completed in July 2004. Laboratories were invited to analyze the wastewater collected from printed circuit board (PCB) industry for lead and copper contamination. The samples fulfill the criteria for homogeneity and stability as done by the reference laboratory. The results obtained from participating laboratories were analyzed in terms of Hampel Test for outliers, while the performance evaluation of the participating laboratories was done on the basis of Z-score. An assigned value derived from the participant's results was compared with a reference value provided by a reference laboratory. Overall >50% of the participating laboratories have shown good performance in this PT-program