New Raman spectrometer using a digital micromirror device and a photomultiplier tube detector for rapid on-line industrial analysis. Part II: Choice of analytical methods

In this paper, the performances of four improved analytical methods (backward stepwise selection of peak intensities, sum of characteristic peaks of a component, moving window partial least squares, and genetic algorithms) using wavelength selection for the analysis of xylene mixtures by Raman spectroscopy are tested for further use on the new "digital micromirror device associated with a photomultiplier tube" Raman spectrometer. It is shown that the errors of prediction using only a few selected points (from 4 to 49 depending on the method) are almost the same as when using the whole spectral range (1050 points). Compared to the last two methods, the "backward stepwise selection of peak intensities" and "sum of characteristic peaks of a component" methods are robust under industrial conditions and appear to be well suited for chemical quantitative analysis with the new Raman spectrometer, which allows the measurements of the total intensity to be made simultaneously for a number of pre-selected frequencies. Results show that the errors of prediction can be near to or even lower than 2%.     

Analysis of thorium and its progeny by gamma ray spectrometry and alpha track methods

Samples originating from an EU sponsored intercomparison exercise were analysed by gamma ray spectrometry (a thorium solution sample, a zircon sand sample and a thorium ore sample). An alpha track method was also used to analyse the solution sample. The detection efficiency calibration for the gamma ray spectrometry measurements on the solid samples was established using an in-house standard of thorium nitrate. A GESPECOR Monte Carlo simulation program was utilised in the analysis of the solution sample. The in-house thorium nitrate standard was also used to prepare standards for the alpha track method. The relative differences between the 232Th activity concentration values determined in these intercomparison samples and values supplied by the NPL, UK, were found to be less than 5% when determined by the gamma ray spectrometry method and less than 8% when determined by the alpha track method.     

Current research activity in the measurement of thorium and the identification of future research needs

A pre-requisite in the setting and enforcement of regulatory limits for exposure to thorium in the workplace is that thorium and its progeny can be accurately measured. Literature surveys have shown that the majority of thorium measurements were performed using either a radiochemical technique, such as alpha or gamma spectroscopy, or ICP-MS. For many methods. there was a separation step to isolate and pre-concentrate thorium from the sample matrix. Thorium was most commonly measured in geological matrices and industrial materials. A survey of current research activity was performed through distribution of a questionnaire to laboratories and national centres. From the rcsponses, four areas of current activity were identified: (i) development of methods for low level thorium determination, (ii) biological monitoring and metabolism of thorium, (iii) environmental monitoring for thorium, and (iv) health risks from X ray contract media. Two key areas for priority research were identified by the thorium Thematic Network: namely sample preparation methods and for traceable standards and reference materials for thorium analysis.     

The methods of identification,analysis, and removal of endocrine disrupting compounds (EDCs) in water

The information regarding endocrine disrupting compounds (EDCs) was reviewed, including the definition and characteristics, the recent research trends concerning identification and analytical methods, and the applicable removal processes. EDCs include various types of natural and synthetic chemical compounds presenting the mimicking or inhibition of the reproductive action of the endocrine system in animals and humans. The ubiquitous presence with trace level concentrations and the wide diversity are the reported characteristics of EDCs. Biologically based assays seem to be a promising method for the identification of EDCs. On the other hand, mass-based analytical methods show excellent sensitivity and precision for their quantification. Several extraction techniques for the instrumental analysis have been developed since they are crucial in determining overall analytical performances. Conventional treatment techniques, including coagulation, precipitation, and activated sludge processes, may not be highly effective in removing EDCs, while the advanced treatment options, such as granular activated carbon (GAC), membrane, and advanced oxidation processes (AOPs), have shown satisfactory results. The oxidative degradation of some EDCs was associated with aromatic moieties in their structure. Further studies on EDCs need to be conducted, such as source reduction, limiting exposure to vulnerable populations, treatment or remediation of contaminated sites, and the detailed understanding of transport mechanisms in the environment.     

The EC Thematic Network on the Analysis of Thorium and its isotopes in Workplace Materials

Accurate measurements of workplace exposure to 232Th and its progeny are required to estimate internal radiation doses received by persons working with thorium-containing materials. However, a small intercomparison carried out in the mid-nineteen nineties raised doubts about the reliability of results obtained by methods available for measurement of thorium. An EC-funded thematic network was therefore established to bring together experts in the field of thorium analysis in order to coordinate research activity and identify best analytical practice. requirements for reference materials. etc. This network has now successfully completed its work programme. which included a survey to determine future research needs; a series of intercomparisons to test the performance of methods for measuring thorium in workplace materials, and a workshop held to promote best practice and transfer information to regulatory authorities and industry. Results of the work have been used to make various recommendations concerning future needs in this field.     

Basic methods for analytical chemical safety monitoring in the destruction of chemical weapons

Basic methods were examined for analytical chemical monitoring at chemical weapons facilities. The database for this monitoring is found in a separate section 1-KhO of the State Register of Measurement Methods, which is part of the Federal Information Foundation for the Assurance of Measurement Uniformity. These monitoring methods are based on analysis of the project design documentation of chemical weapon destruction facilities and have emerged from investigations in chemical weapon disarmament over the past 11 years, in particular, at the Inversiya Technology Center.     

Improving risk assessment methods for process plant

This paper considers the usefulness of risk assessment in the analysis of hazards due to chemical process plant and similar installations. Risk assessment is first defined as a technique in which the probabilities and consequences of all possible accidents are quantified. The outputs from such an analysis may take the form of ‘frequency versus magnitude’ graphs, contours of constant risk or overall average rates of death or injury. The applications of the technique include siting and layout studies, comparison of alternative designs, ordering priorities for remedial action and setting insurance rates. Criticisms of the method include: inaccuracy (mainly in the probabilities); incompleteness; difficulty of checking final results; inadequate criteria for evaluating the results; and complexity and laboriousness of the method. Each of these criticisms is considered in the paper, and it is concluded that, while they all have some merit, the problems they represent can be overcome. Moreover, risk assessment is the only method available for dealing with the inherently probabilistic nature of the problems. Finally, priorities for future improvements in the methods are identified; these include achieving a consensus regarding the prediction of consequences and probabilities, developing labour-saving analytical techniques, and testing the final results against the actual experience of accidents.     

The use of global uncertainty methods for the evaluation of combustion mechanisms

Complex chemical mechanisms are increasingly used within models describing a range of important chemical processes. Parameters describing the rates of chemical steps and thermodynamics may be highly uncertain, influencing the uncertainty in final model predictions. Local sensitivity analysis is traditionally employed within commercial modelling packages but may not be appropriate for highly uncertain data within non-linear models. There is a need for global uncertainty techniques such as Morris and Monte Carlo methods that can be applied efficiently for computationally expensive models. This paper presents the development of such techniques, along with application to a kinetic mechanism describing the influence of fuel trace elements such as sulphur-containing compounds, on the formation of nitrogen oxide in combustion devices. The analysis evaluates the parameters from within the current sulphur scheme that drive uncertainties in predicted relative changes in nitrogen oxide concentrations when sulphur compounds are added to the fuel. The overall performance of the mechanism is evaluated in comparison with available experimental profiles and the level of agreement between different methods for importance ranking of the rate parameters is highlighted. The use of fitted model representations is also discussed as an alternative method for determining importance ranking, and highlights non-linear interactions between parameters. Finally, possible improvements to the chemical scheme are tested within a Monte Carlo framework under lean flame conditions, where the current mechanism performs the least well with respect to experimental results.     

The distribution of uranium and thorium in samples taken from different polluted marine environment

Concentrations of uranium and thorium in seawater, sediment and some marine species taken from along the coastal areas of Malaysia were determined spectrophotometrically. The uranium and thorium concentrations in seawater were found to vary ranging from 1.80 to 4.1 and 0.14 to 0.88 microg/L, respectively. The concentration of uranium in sediment samples was reported to range from 3.00 to 6.60 microg/g while those of thorium were slightly lower ranging from 0.01 to 0.68 microg/g. The uptake of uranium and thorium in marine species was found to be rather low. Similar variations in total alpha activities in samples were also observed with the total alpha activities relatively lower than the beta activities in most samples.     

Thorium in the workplace: results from a European-based measurement comparison project

A Series of comparisons were conducted to test the capabilities of a range of metrological techniques and analytical laboratories engaged in the assay of thorium in the workplace. The results of these exercises are presented together with the decision criteria used to determine whether results are significantly different from the true value. The discussion highlights those aspects which warrant closer and further attention.     

Chemical amplification — A novel approach to ultratrace analysis

The lowest concentration that can be estimated with 100% error in chemical analysis by instrumental technique is referred to as detection limit. It is equal to the ratio of twice the background signal to the magnitude of analytical signal corresponding to a concentration of unity. Detection limit (dl) could be improved if the analytical signal alone could be selectively amplified without affecting the background. It is shown that this could be achieved by chemical amplification. Atomic amplification of two or three orders of magnitude could be obtained by combining two chemical amplifications in series. It is demonstrated that by using heteropoly acid formation as the first amplification reaction and determining molybdenum in the heteropoly acid by catalyticdc polarographic wave, a detection limit for the hetero atom of less than a ppb can be obtained. It is pointed out that the approach of selectively amplifying analytical signals by tandem chemical amplification reactions makes it possible to perform ultratrace analysis (ppb level) with classical instrumental analytical techniques which havedl at ppm level.     

Absolute quantification of the G protein-coupled receptor rhodopsin by LC/MS/MS using proteolysis product peptides and synthetic peptide standards

Methods for the absolute quantification of a membrane protein are described using isotopically labeled or unlabeled synthetic peptides as standards. Synthetic peptides are designed to mimic peptides that are cleaved from target analyte proteins by proteolytic or chemical digestion, and the peptides selected serve as standards for quantification by LC/MS/MS on a triple quadrupole mass spectrometer. The technique is complementary to relative quantification techniques in widespread use by providing absolute quantitation of selected targets with greater sensitivity, dynamic range, and precision. Proteins that are found to be of interest by global proteome searches can be selected as targets for quantitation by the present method. This method has a much shorter analytical cycle time (minutes versus hours for the global proteome experiments), making it well suited for high-throughput environments. The present approach using synthetic peptides as standards, in conjunction with proteolytic or chemical cleavage of target proteins, allows mass spectrometry to be used as a highly selective detector for providing absolute quantification of proteins for which no standards are available. We demonstrate that quantification is simple and reliable for the integral membrane protein rhodopsin with reasonable recoveries for replicate experiments using low-micromolar solutions of rhodopsin from rod outer segments.     

Knowledge representation for the selection of methods in analytical chemistry

Expert systems are gaining rapidly in importance in several areas of science, and in chemistry in particular. One of the most important factors that determines the success of an expert system is the representation of the knowledge. To understand better the suitability of the different knowledge representation techniques for the selection of methods in analytical chemistry, a test knowledge base was developed for the high-performance liquid chromatographic analysis of pharmaceutical compounds. This knowledge base has been used to study which features of knowledge representation are necessary to describe analytical chemical knowledge in a natural and efficient way. It is concluded that no single representation method is optimal. A combination of production rules and frame structures seems to be much more suitable. The possibility of consulting external databases and programs is also a very important aspect.     

Establishing sensitivity requirements for environmental analyses from project data quality objectives.

This article proposes a simple strategy for establishing sensitivity requirements (quantitation limits) for environmental chemical analyses when the primary data quality objective is to determine if a contaminant of concern is greater or less than an action level (e.g., an environmental "cleanup goal," regulatory limit, or risk-based decision limit). The approach assumes that the contaminant concentrations are normally distributed with constant variance (i.e., the variance is not significantly dependent upon concentration near the action level). When the total or "field" portion of the measurement uncertainty can be estimated, the relative uncertainty at the laboratory's quantitation limit can be used to determine requirements for analytical sensitivity. If only the laboratory component of the total uncertainty is known, the approach can be used to identify analytical methods or laboratories that will not satisfy objectives for sensitivity (e.g., when selecting methodology during project planning).     

Nuclear data used in the analysis of thorium in the workplace

The analysis of thorium in the workplace can be achieved using a variety of metrological techniques. The uncertainty on the final measured values will include components that arise from the uncertainties in the nuclear data that are used. These data include half-lives, branching ratios and gamma ray emission probabilities. It is important that a common, consistent and reliable data set is used in order to minimise the potential differences between analytical results. With particular reference to the problems associated with thorium analysis, some of the various sources of nuclear data are discussed and a recommended set of data is proposed.     

Pulsed ion beam characterization of CVD diamond surfaces under thin film deposition conditions

Diamond and diamond-like carbon have properties which in principle make them ideally suited to a wide variety of thin-film applications. The widespread use of diamond thin films, however, has been limited for a number of reasons related largely to the lack of understanding and control of the nucleation and growth processes. Real-time, in-situ studies of the surface of the growing diamond film are experimentally difficult because these films are normally grown under a relatively high pressure of hydrogen, and conventional surface analytical methods require an ultrahigh vacuum environment. Pulsed ion beam based analytical methods with differentially pumped ion sources and particle detectors are able to characterize the uppermost atomic layer of a film during growth at ambient pressures in the range 0.7–27 Pa (4–6 orders of magnitude higher than other surface-specific analytical methods). We describe here a system which has been developed for the purpose of determining the hydrogen concentration and bonding sites on diamond surfaces as a function of sample temperature and ambient hydrogen pressure under hot-filament chemical vapor deposition (CVD) growth conditions. It is demonstrated that as the hydrogen partial pressure increases the saturation hydrogen coverage of the surface of a CVD diamond film increases, but that the saturation level depends on the atomic hydrogen concentration and substrate temperature. At the highest temperatures studied (700 °C), it was found that the surface hydrogen concentration did not exceed 1/4 monolayer.     

New iterative reconstruction methods for fan-beam tomography

In this paper, we present a novel class of iterative reconstruction methods for severely angular undersampled or/and limited-view tomographic problems with fan-beam scanning geometry. The proposed algorithms are based on a new analytical transform which generalizes Fourier-slice theorem to divergent-beam scanning geometries. Using a non-rigid coordinate transform, divergent rays can be reorganized into parallel ones. Therefore, one can employ a simpler parallel-beam projection model instead of more complicated divergent-beam geometries. Various existing iterative reconstruction techniques for divergent-beam geometries can be easily adapted to the proposed framework. The significant advantage of this formulation is the possibility of exploiting efficient Fourier-based recovery methods without rebinning of the projections. In case of highly sparse measurements (few-view data), rebinning methods are not suitable due to error-prone angular interpolation involved. In this work, three new methods based on the novel analytical framework for fan-beam geometry are presented: the Gerchberg-Papoulis algorithm, the Neumann decomposition method and its total variation regularized version. Presented numerical experiments demonstrate that the methods can be competitive in reconstructing from few-view noisy tomographic measurements.     

Improved methods for performing multivariate analysis and deriving background spectra in atmospheric open-path FT-IR monitoring

Open-path Fourier transform infrared spectrometry (OP/FT-IR) may improve the temporal and spatial resolution in air pollutant measurements compared to conventional sampling methods. However, a successful OP/FT-IR operation requires an experienced analyst to resolve chemical interference as well as to derive a suitable background spectrum. The present study aims at developing a systematic method of handling the OP/FT-IR derived spectra for the measurement of photochemical oxidants and volatile organic compounds (VOCs) in urban areas. A classical least-squares (CLS) method, the most frequently used regression method in OP/FT-IR, is modified to constrain all the analyzed chemical species concentrations within a physically reasonable range. This new CLS method, named constrained CLS, may save the effort of predetermining the chemical species to be analyzed. A new background spectrum generation method is also introduced to more efficiently handle chemical interferences. Finally, CLS is shown to be prone to propagating errors in the case that a few data points contain a significant amount of error. The LI-norm minimization method reduces this error propagation to considerably increase the stability compared to CLS. The presently developed analysis software based on these approaches is compared with the other conventional CLS method using an artificially made single-beam spectrum as well as a field single-beam spectrum.     

Investigative methods for the characterisation of historic mortars—Part 1: Mineralogical characterisation

The mineralogical characterisation of historic mortars is performed for a number of reasons related to the conservation of traditional structures. The reasons for analysis and the questions posed during the conservation, repair or restoration of an old building determine the analysis methods that will be chosen. A range of mineralogical characterisation methods is available for the study of historic masonry mortars. These include X-ray Diffraction (XRD), Optical Microscopy, Scanning Electron Microscopy (SEM), Thermal and Infra-Red methods. Sample preparation is important; adequate separation of binder from aggregate is required for instrumental as opposed to microscopic investigation methods. An ordered scheme of analysis can be developed and is presented in flowchart form. It is difficult, and perhaps unwise, to analyse a mortar with only one method of characterisation. Corroboration of evidence of identification and quantification for mineralogical composition is best supported by a combination of methods, including chemical analysis methods. All methods of characterisation require qualified and experienced people to cary out the analyses.