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.     

Characterization and forensic analysis of soil samples using laser-induced breakdown spectroscopy (LIBS)

A method for the quantitative elemental analysis of surface soil samples using laser-induced breakdown spectroscopy (LIBS) was developed and applied to the analysis of bulk soil samples for discrimination between specimens. The use of a 266 nm laser for LIBS analysis is reported for the first time in forensic soil analysis. Optimization of the LIBS method is discussed, and the results compared favorably to a laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) method previously developed. Precision for both methods was <10% for most elements. LIBS limits of detection were <33 ppm and bias <40% for most elements. In a proof of principle study, the LIBS method successfully discriminated samples from two different sites in Dade County, FL. Analysis of variance, Tukey’s post hoc test and Student’s t test resulted in 100% discrimination with no type I or type II errors. Principal components analysis (PCA) resulted in clear groupings of the two sites. A correct classification rate of 99.4% was obtained with linear discriminant analysis using leave-one-out validation. Similar results were obtained when the same samples were analyzed by LA-ICP-MS, showing that LIBS can provide similar information to LA-ICP-MS. In a forensic sampling/spatial heterogeneity study, the variation between sites, between sub-plots, between samples and within samples was examined on three similar Dade sites. The closer the sampling locations, the closer the grouping on a PCA plot and the higher the misclassification rate. These results underscore the importance of careful sampling for geographic site characterization.     

Regulatory compliance vs. NEXUS quality for laboratory tests

In the U.S., all clinical laboratory testing is regulated by the Clinical Laboratory Improvement Amendments (CLIA) (). The CLIA link test quality and adherence to a body of testing regulations intended to ensure accurate, reliable, and timely patient test results. The goal of the CLIA legislation was to ensure a minimum, fundamental level of quality. In the context of “NEXUS,” quality must “go beyond getting the ‘right’ answer on the ‘right’ patient that can be interpreted against ‘right’ reference values. CLIA regulations with specific minimum, performance requirements, or safeguards, are designed to prevent testing errors. The US Institute of Medicine found that testing processes fail as a result of human error, lack of documentation, and lack of test management. In the latest (2004) interpretations of CLIA regulations, the minimum quality control requirement continues to be analyzing at least two external, liquid quality control materials per test per day. In 1995, we proposed that the responsibility for achieving quality test results shifts from the sole purview of the laboratory director to an “alliance” of laboratory professionals, manufacturers, and regulators. The EQC (equivalent quality control) concept as proposed is a positive step in achieving this alliance. With the obvious lack of scientific and statistical robustness, EQC falls far short of ensuring quality. Achieving the “NEXUS Vision” for quality laboratory testing will not come solely from laboratory professionals. The NEXUS is about how to ensure the full-quality assessment of the testing process – pre-analytical, analytical, and post-analytical.Presented at the 10th Conference Quality in the Spotlight, March 2005, Antwerp, Belgium.     

Prompt gamma activation analysis and time of flight neutron diffraction on ‘black boxes’ in the ‘Ancient Charm’ project

The aim of the ‘Ancient Charm’ project is combining neutron tomography, prompt gamma activation analysis, time of flight neutron diffraction and neutron resonance transmission to generate elemental, and phase compositions of complex museum objects in 3D. To develop a protocol for such investigations, complex test samples were constructed and then analyzed by each method. The ‘black boxes’ are sealed iron and aluminum walled cubes, containing 2D or 3D arrangements of materials relevant for the compositions of archaeological samples. The experimental results obtained from bulk PGAA at BNC and TOF-ND at ISIS on two selected boxes are reported.     

Generic division of ‘quantity’ and related terms

In the slow evolution of the International vocabulary of metrology (VIM), the first concept of ‘quantity’ has now been divided generically into ‘ordinal quantity’ and a coordinate primitive without definition and term. An analysis of the concepts by their characteristics is made, and the nature of inheritance is discussed in response to a recent communication in this journal. A completion of the initiated generic division of ‘quantity’ is suggested, and a neoterm for the sister of ‘ordinal quantity’ is offered on the basis of two proposals.     

Elements, Principles and the Narrative of Affinity

In the 18th century, the concept of ‘affinity’, ‘principle’ and ‘element’ dominated chemical discourse, both inside and outside the laboratory. Although much work has been done on these terms and the methodological commitments which guided their usage, most studies over the past two centuries have concentrated on their application as relevant to Lavoisier's oxygen theory and the new nomenclature. Kim's affinity challenges this historiographical trajectory by looking at several French chemists in the light of their private thoughts, public disputations and communal networks. In doing so, she tells a complex story which points to the methodological and practical importance of industrial and medical chemistry. The following review highlights the advantages and snares of such an approach and makes a few historiographical points along the way. This revised version was published online in August 2006 with corrections to the Cover Date.     

Complementarity and the temporal Uncertainty principle. Insight into the dichotomous formulations of the Curtin-Hammett principle. A new formulation

By the temporal Uncertainty principle, chemical systems may be described in terms of ‘kinetic’ or ‘thermodynamic’ complementary formulations, based on rate or equilibrium constants, and free energy changes respectively. Thereby, the paradox of the dichotomous formulations of the Curtin-Hammett principle is resolved. A new formulation of the principle is suggested, and a fundamental conflict with transition state theory is indicated.     

Double pulse laser-induced breakdown spectroscopy of explosives: Initial study towards improved discrimination

Detecting trace explosive residues at standoff distances in real-time is a difficult problem. One method ideally suited for real-time standoff detection is laser-induced breakdown spectroscopy (LIBS). However, atmospheric oxygen and nitrogen contributes to the LIBS signal from the oxygen- and nitrogen-containing explosive compounds, complicating the discrimination of explosives from other organic materials. While bathing the sample in an inert gas will remove atmospheric oxygen and nitrogen interference, it cannot practically be applied for standoff LIBS. Alternatively, we have investigated the potential of double pulse LIBS to improve the discrimination of explosives by diminishing the contribution of atmospheric oxygen and nitrogen to the LIBS signal. These initial studies compare the close-contact (< 1 m) LIBS spectra of explosives using single pulse LIBS in argon with double pulse LIBS in atmosphere. We have demonstrated improved discrimination of an explosive and an organic interferent using double pulse LIBS to reduce the air entrained in the analytical plasma.     

Metrology and protometrology: the ordinal question

Laboratory medicine provides results for quantities as well as for properties having no magnitude. The terminology of the latter is less well established and sources are contradictory. Two recent papers on “protometrology” published in this journal offer an opportunity to discuss the necessary concept systems. The delineations of “metrology” versus “protometrology”, “observation” versus “measurement”, and the generic division of “property” are examined with emphasis on avoiding conflict with the International Vocabulary of Metrology. It is suggested that having “examination” as a top generic concept coupled with systematic modifiers for division, especially ‘nominal’ and ‘ordinal’, is a preferable terminological solution.

Spectral Interferences in Light Element Analysis

 Interferences (overlaps) occurring when lines of other elements affect either peak or background measurements can cause errors in quantitative WD analysis, but may be minimised by suitable choices of analysis conditions such as spectrometer crystal, background offsets, and pulse-height analyser settings. Computer spectrum-simulation is much more effective than reference to wavelength tables for investigating interferences. The ‘Virtual WDS’ simulation program developed by the present authors, hitherto applied only to ‘ordinary’ elements (Z ≥ 11), has been extended to light elements for which evaporated multilayers are used in place of true crystals. ‘Virtual WDS’ utilises experimentally recorded light-element K spectra and L and M spectra of heavier elements in the same wavelength range. It is impractical to record all high-order peaks, so computed line profiles are used, with widths and intensities interpolated from a limited set of observations. The relative positions of first and higher order peaks are affected significantly by the refractive index of the multilayer, requiring modification of the Bragg equation. Suppression of high orders by pulse-height analysis is less effective than for ‘normal’ wavelengths, owing to the breadth of the pulse-height distribution for low X-ray energies. Simulation using a Gaussian expression aids optimisation of threshold and window-width settings.     

The role of metrology in making chemistry sustainable

Sustainable development is the new design of an old concept, now emerging from the acute endangering of our habitat. Coined by the Brundlandt Commission in 1987, sustainable development was defined as ‘Development that meets the needs of the present without compromising the ability of future generations to meet their own needs’ (World commission on Environment and Development, Our Common Future, Oxford University Press, Oxford, 1987). It appeared on the world stage during the UNO Earth Summit in Rio, 1992. Sustainability became the key term of the ‘Agenda 21’ (United Nations Conference for Education and Development, Earth Summit, Agenda 21, The United Nations Programme of action for Sustainable Development, United Nations, New York, 1992). The ‘Agenda 21’ is adopted by 178 states, although to date not all signatories have ratified the Agenda. Sustainable solutions should aim to harmonize ecological equilibrium, economic stability, and social harmony. But in the course of the years, the interpretation of the concept became more and more complicated and its context is becoming fuzzy. Extended version of a presentation given during a Baltic University Programme's international workshop on ‘Sustainable Chemistry and Biochemistry’ at St. Marienthal, Germany, February 15–17, 2005     

A comparison of laser ablation inductively coupled plasma mass spectrometry,micro X-ray fluorescence spectroscopy,and laser induced breakdown spectroscopy for the discrimination of automotive glass

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), micro X-ray fluorescence spectroscopy (μXRF), and laser induced breakdown spectroscopy (LIBS) are compared in terms of discrimination power for a glass sample set consisting of 41 fragments. Excellent discrimination results (> 99% discrimination) were obtained for each of the methods. In addition, all three analytical methods produced very similar discrimination results in terms of the number of pairs found to be indistinguishable. The small number of indistinguishable pairs that were identified all originated from the same vehicle. The results also show a strong correlation between the data generated from the use of µXRF and LA-ICP-MS, when comparing µXRF strontium intensities to LA-ICP-MS strontium concentrations. A 266 nm laser was utilized for all LIBS analyses, which provided excellent precision (< 10% RSD for all elements and < 10% RSD for all ratios, N = 5). The paper also presents a thorough data analysis review for forensic glass examinations by LIBS and suggests several element ratios that provide accurate discrimination results related to the LIBS system used for this study. Different combinations of 10 ratios were used for discrimination, all of which assisted with eliminating Type I errors (false exclusions) and reducing Type II errors (false inclusions). The results demonstrate that the LIBS experimental setup described, when combined with a comprehensive data analysis protocol, provides comparable discrimination when compared to LA-ICP-MS and μXRF for the application of forensic glass examinations. Given the many advantages that LIBS offers, most notably reduced complexity and reduced cost of the instrumentation, LIBS is a viable alternative to LA-ICP-MS and μXRF for use in the forensic laboratory.     

The third edition of ISO Guide 34: what were the drivers for the revision and what is new?

After the International Laboratory Accreditation Cooperation (ILAC) had taken in 2004, the resolution to conduct accreditation of producers of reference materials according to ISO Guide 34 ‘General requirements for the competence of reference material producers’ in combination with ISO/IEC 17025 ‘General requirements for the competence of testing and calibration laboratories’, ISO/REMCO, the ISO Committee on Reference Materials, decided in 2005 to revise ISO Guide 34 to align it closer with ISO/IEC 17025 and to clarify certain issues for accreditors and producers seeking accreditation without adding new requirements. Moreover, the publication in 2007 of ISO/IEC Guide 99 ‘International vocabulary of metrology—Basic and general concepts and associated terms (VIM)’ triggered additional adaptations of the guide.     

‘Verification’ versus ‘validation’: a terminological comparison

The present diversity in the definitions and relations of ‘verification’ and ‘validation’ is impractical for such transdisciplinary concepts. General dictionaries, international special language vocabularies and minor lists show that the respective recent formulations by the International Organization for Standardization (ISO) and the Joint Committee for Guides in Metrology (JCGM) are the most quoted. The characteristics of these concepts are elucidated terminologically, and separate concept systems are made for ISO and JCGM to arrive at a preference for a generic rather than an associative relation.     

Miniaturized Laser-Induced Breakdown Spectroscopy for the in-situ analysis of the Martian surface: Calibration and quantification

We report on our ongoing studies to develop Laser-Induced Breakdown Spectroscopy (LIBS) for planetary surface missions to Mars and other planets and moons, like Jupiter's moon Europa or the Earth's moon. Since instruments for space missions are severely mass restricted, we are developing a light-weight miniaturized close-up LIBS instrument to be installed on a lander or rover for the in-situ geochemical analysis of planetary surface rocks and coarse fines. The total mass of the instrument will be ≈ 1 kg in flight configuration. Here we report on a systematic performance study of a LIBS instrument equipped with a prototype laser of 216 g total mass and an energy of 1.8 mJ. The LIBS measurements with the prototype laser and the comparative measurements with a regular 40 mJ laboratory laser were both performed under Martian atmospheric conditions.     

Ultrahydrophobic aluminium surfaces: properties and EIS measurements of different oxidic and thin-film coated states

Firstly, the contribution summarises important results of the work dedicated to the formation of ultrahydrophobic aluminium surfaces. This treatment comprises sulphuric acid anodisation under intensified temperature and current density conditions (‘SAAi’) as well as subsequent chemical modification (‘C’). The usual sulphuric acid anodisation (‘SAAu’) was included for comparison. These various states were examined by electrochemical impedance spectrometry (EIS) to derive typical EIS-related features, especially for the ultrahydrophobic states compared to the anodised surfaces. Based on well-defined spectra types, modelling yielded results, preferentially with regard to the nano-porosity of the oxidic layers. EIS measurements allowed the conclusion that the original nano-porosity underwent specific changes due to the chemical modification variants employed. The chances of EIS predicting the stability of the ultrahydrophobically modified systems are critically assessed on the background of standardised weathering tests.     

Practical Thermogravimetry

The well-known divergence between the present ‘state of the art’ of thermogravimetry and industrial requirements is discussed. Sources of errors are analyzed and the optimization of measuring conditions is discussed regarding the problems associated with static and dynamic (flow) atmospheres, and interactions between materials and gases or vapors. Recommendations for gas-flow control systems and vapor sources are given. Thermal stability and the kinetics of gas-evolving, reversible, thermal decompositions of solids are discussed. The scope of TG-derived kinetics for practical use is examined. Some new characteristic points of TG curves are proposed and defined, e.g. ‘procedure-independent decomposition temperature’ and ‘augmented decomposition temperature’ (obtained at pseudo-equilibrium conditions). This revised version was published online in August 2006 with corrections to the Cover Date.     

Can the provenance of the conflict minerals columbite and tantalite be ascertained by laser-induced breakdown spectroscopy?

Conflict minerals is a term applied to ores mined in conditions of armed conflict and human rights abuse. Niobium and tantalum are two rare metals whose primary natural occurrence is in the complex oxide minerals columbite and tantalite, the ore of which is commonly referred to as coltan. The illicit export of coltan ore from the Democratic Republic of the Congo is thought to be responsible for financing the ongoing civil conflicts in this region. Determining the chemical composition of an ore is one of the means of ascertaining its provenance. Laser-induced breakdown spectroscopy (LIBS) offers a means of rapidly distinguishing different geographic sources for a mineral because the LIBS plasma emission spectrum provides the complete chemical composition (i.e., “chemical fingerprint”) of any material in real time. To test this idea for columbite–tantalite, three sample sets were analyzed. Partial least squares discriminant analysis (PLSDA) allows correct sample-level geographic discrimination at a success rate exceeding 90%.