The development of fieldable laser-induced breakdown spectrometer: No limits on the horizon

In this review, new trends in the development of fieldable instrumentation based on laser-induced breakdown spectroscopy (LIBS) and its recent applications is presented. Depending on the LIBS configuration we will distinguish between portable, remote and stand-off instruments. Moreover, the development of portable systems gives greater flexibility and also increases the range of LIBS applications. In general, portable instruments are employed in close-contact applications like immovable artworks, contaminated soils and environmental diagnostic, while remote and stand-off instruments are normally used in analytical applications at distances where access to the sample is difficult or hazardous. Although remote and stand-off instruments are both used for chemical analysis at distances, the instrumental configurations are completely different. In remote analysis, an optical fiber is employed to deliver the laser energy a certain distance. This approach has been usually restricted to industrial applications, bulk analysis in water, geological measurements and chemical analysis on nuclear stations. In the case of stand-off applications, the laser beam and the returning plasma light are transmitted in an open-path configuration. In this article we also discuss the instrumental requirements in the design of remote and stand-off instruments.     

Environmental Analysis Using Antibody and Receptor Based Techniques

Abstract

Immunochemical analysis relies on the selective binding of antibodies to defined targets such as environmental compounds. Commercial applications in the environmental field are still restricted to a limited number of immunoassays and a few immunochromatographic applications. The main barrier to a broader exploitation is seen in the generation of a sufficient number of antibodies within an acceptable time period. Recombinant technologies are expected to eventually replace the circumstantial approach to obtain new Abs by new immunizations. Examples for recombinant singlechain fragments (scFv) and antigen binding fragments (Fab) directed against herbicidal s-triazines are given. If antibodies are replaced by receptors and other functional ligands, biological effects monitoring becomes available. As an example an enzyme-linked receptor assay (ELRA) for endocrine disruptors providing estrogen equivalents is presented. Finally, the concept of bioresponse-linked instrumental analysis is introduced for the tight coupling of effect monitoring to chemical analysis. In the first step, analyte binding by functional biomolecules is recorded to provide binding equivalents. The second step is targeted at chemical analysis of bioeffective analytes bound to the functional biomolecules.     

Analytical Standards and Methods for the Determination of Polynuclear Aromatic Hydrocarbons in Environmental Samplest

Abstract

Standard reference materials (SRM's) have been produced, certified, and issued by the United States National Bureau of Standards (NBS) since 1905. NBS currently issues more than 1000 SRM's of various types, including nuclear materials, rubber, clinical and environmental trace metal standards. The most recent addition to this group is a series of environmental trace organic materials with certified concentrations of selected polynuclear aromatic hydrocarbons (PAH), phenols, and N-heterocyclic compounds. Until recently, trace organic SRM's were non-existent due to the lack of analytical methodology necessary for certification. Details concerning the analytical methods developed and used for certification of the concentrations of several PAH in SRM's 1580 (Organics in Shale Oil), 1644 (Generator Columns for PAH in water), 1647 (PAH in Acetonitrile), and 1649 (Urban Particulate Matter) are given along with some suggested uses for these SRM's.     

An Overview of Analytical Chemistry in Australia

ABSTRACT

A brief overview of analytical chemistry research in Australia is presented and reference is made to the work of several research groups. Topics covered include the development of a longitudinally modulated cryogenic system for comprehensive gas chromatography, mixed-mode capillary electrochromatography for manipulation of separation selectivity of inorganic ions, new developments in chemical metrology, discontinuous flow analysis and its applications, the design and applications of an orthogonal acceleration time-of-flight mass spectrometer, and the use of chemiluminescence in a range of analytical techniques.     

Nickel catalysis: six membered heterocycle syntheses

Abstract

The investigation of methods for the chemical synthesis is a growing area of interest due to increasing environmental issues. The use of catalysts in organic reactions has gained extensive interest. Metal and nonmetal catalysts provide a new improved alternative to traditional methods in modern synthetic chemistry. The aim of present review is to focus on the applications of nickel for the synthesis of six membered heterocylces.     

Trace Analysis in Industrial Research

Abstract

Public concern and legislative regulations governing environmental pollution have had a dramatic effect on chemists involved in industrial research. The need to establish both the presence and amounts of trace levels of pollutants in industrial products and wastes has become imperative. Since time and cost become important considerations in such analytical determinations, it is apparent that sensitive, rapid and reliable methods of trace analysis are required. Many experimental techniques have been employed to this end and active research programs exist to develop new techniques to make such analysis more efficient.

Techniques capable of determining many elements in a single examination of a sample are of particular interest. No single 'black box' approach is, or is likely to become, feasible for all species of interest. Nonetheless, certain multielement approaches provide adequate information on some species and also provide important guidelines on the determination of other species by more specialized techniques. Problems encountered and progress achieved by the application of various spectroscopic, chromatographic, electrochemical and chemical methods to the trace analysis of industrial materials will be discussed.     

The Application of Perdeuterated Polycyclic Aromatic Hydrocarbons (PAH) as Internal Standards for the Liquid Chromatographic Determination of PAH in a Petroleum Crude Oil and Other Complex Mixtures

Abstract

A sequential liquid chromatographic (LC) procedure for the determination of polycyclic aromatic hydrocarbons (PAH) in a petroleum crude oil and other complex mixtures is described. The procedure includes normal-phase LC on an aminosilane column to isolate fractions containing isomeric PAH and reversed-phase LC on a polymeric C₁₈ column to separate the individual PAH isomers. Appropriate perdeuterated PAH are added to the sample so that each isomeric fraction will contain one internal standard. The perdeuterated PAH are excellent internal standards for this sequential LC procedure. Perdeuterated PAH have normal-phase and reversed-phase LC retention characteristics similar to those of the parent PAH. In the normal-phase LC separation, the perdeuterated PAH elute in the same fraction as the parent PAH. In the reversed-phase LC separation, the perdeuterated PAH elute first and are generally resolved from the parent PAH. The optimized spectrofluorometric detection of each PAH analyte is accomplished by programming appropriate sets of excitation and emission wavelengths to correspond with the elation time of each analyte on the polymeric C₁₈ column. The analytical results obtained from this procedure for the analysis of a shale oil sample [Standard Reference Material (SRM) 1580] and a petroleum crude oil (SRM 1582) are compared to values obtained by gas chromatography - mass spectrometry.     

Microcolumn Liquid Chromatography Combined with Computer-Assisted Retention Prediction System for Polycyclic Aromatic Hydrocarbons in Extract from Diesel Particulate Matter

Abstract

Recent advances in column and instrument technology have made the development of d new generation of high-resolution microcolumn liquid chromatography possible. In addition to offering reduced solvent consumption, this chromatographic technique also yields higher mass sensitivities than those in conventional systems. In this study, the applicability of this technique to the analysis of polycyclic aromatic hydrocarbons (PAH) is investigated. PAH in the extract from diesel particulate matter were analyzed to demonstrate the utility of this approach combined with the computer-assisted retention prediction. The technique proposed in this study makes very clean and high cost-performance environmental analysis possible.     

Fate of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) on soil following accelerant-based fire and liquid decontamination

In the event of alleged use of organophosphorus nerve agents, all kinds of environmental samples can be received for analysis. These might include decontaminated and charred matter collected from the site of a suspected chemical attack. In other scenarios, such matter might be sampled to confirm the site of a chemical weapon test or clandestine laboratory decontaminated and burned to prevent discovery. To provide an analytical capability for these contingencies, we present a preliminary investigation of the effect of accelerant-based fire and liquid decontamination on soil contaminated with the nerve agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). The objectives were (a) to determine if VX or its degradation products were detectable in soil after an accelerant-based fire promoted by aviation fuel, including following decontamination with Decontamination Solution 2 (DS2) or aqueous sodium hypochlorite, (b) to develop analytical methods to support forensic analysis of accelerant-soaked, decontaminated and charred soil and (c) to inform the design of future experiments of this type to improve analytical fidelity. Our results show for the first time that modern analytical techniques can be used to identify residual VX and its degradation products in contaminated soil after an accelerant-based fire and after chemical decontamination and then fire. Comparison of the gas chromatography–mass spectrometry (GC-MS) profiles of VX and its impurities/degradation products from contaminated burnt soil, and burnt soil spiked with VX, indicated that the fire resulted in the production of diethyl methylphosphonate and O,S-diethyl methylphosphonothiolate (by an unknown mechanism). Other products identified were indicative of chemical decontamination, and some of these provided evidence of the decontaminant used, for example, ethyl 2-methoxyethyl methylphosphonate and bis(2-methoxyethyl) methylphosphonate following decontamination with DS2. Sample preparation procedures and analytical methods suitable for investigating accelerant and decontaminant-soaked soil samples are presented. VX and its degradation products and/or impurities were detected under all the conditions studied, demonstrating that accelerant-based fire and liquid-based decontamination and then fire are unlikely to prevent the retrieval of evidence of chemical warfare agent (CWA) testing. This is the first published study of the effects of an accelerant-based fire on a CWA in environmental samples. The results will inform defence and security-based organisations worldwide and support the verification activities of the Organisation for the Prohibition of Chemical Weapons (OPCW), winner of the 2013 Nobel Peace Prize for its extensive efforts to eliminate chemical weapons.     

Monitoring Method for Airborne Polycyclic Aromatic Hydrocarbons

Abstract

This paper describes a method for the determination of airborne polycyclic aromatic hydrocarbons (PAH), which has been employed in routine analysis of a large number of samples. The method is in principle based on well known techniques, but some improvements have been made in order to reduce the analysis time and the cost without lowering the quality of the analytical results. Recovery studies have been made for some important steps of the procedure, and the reproducibility of the sampler has been tested. The method has proved to be suitable for monitoring of PAH in highly polluted as well as pristine areas.     

Super-resolution and Raman chemical imaging: from multiple low resolution images to a high resolution image

Imaging in Raman spectroscopy is a valuable tool for analytical chemistry. Although molecular characterization at micron level is achieved for many applications, it usually fails producing chemical images of micron size samples as expected in chemical, environmental and biological analysis. The aim of the work is to introduce the potential of super-resolution in vibrational spectroscopic imaging. This original chemometrics approach uses several low resolution images of the same sample in order to retrieve a higher resolution chemical image. It is thus possible to overcome in a certain way some physical and instrumentals limitations. To illustrate the methodology, sub-micronic details of a Si/Au sample are retrieved from low resolution images with different super-resolution algorithms. The better results are obtained with Iterative L2/Bilateral Total Variation regularization method. The use of a regularization procedure gives also better results since its first property is to preserve edges during the reconstruction of the super-resolved image. This concept of chemical image data processing should open new analytical opportunities.     

Quantitative analysis of polycyclic aromatic hydrocarbons using high-performance liquid chromatography-photodiode array-high-resolution mass spectrometric detection platform coupled to electrospray and atmospheric pressure photoionization sources

Polycyclic aromatic hydrocarbons (PAHs) are common pollutants present in atmospheric aerosols and other environmental mixtures. They are of particular air quality and human health concerns as many of them are carcinogenic toxins. They also affect absorption of solar radiation by aerosols, therefore contributing to the radiative forcing of climate. For environmental chemistry studies, it is advantageous to quantify PAH components using the same analytical technics that are commonly applied to characterize a broad range of polar analytes present in the same environmental mixtures. Liquid chromatography coupled with photodiode array and high-resolution mass spectrometric detection (LC-PDA-HRMS) is a method of choice for comprehensive characterization of chemical composition and quantification of light absorption properties of individual organic compounds present in the environmental samples. However, quantification of non-polar PAHs by this method is poorly established because of their imperfect ionization in electrospray ionization (ESI) technique. This tutorial article provides a comprehensive evaluation of the quantitative analysis of 16 priority pollutant PAHs in a standard reference material using the LC–MS platform coupled with the ESI source. Results are further corroborated by the quantitation experiments using an atmospheric pressure photoionization (APPI) method, which is more sensitive for the PAH detection. The basic concepts and step-by-step practical guidance for the PAHs quantitative characterization are offered based on the systematic experiments, which include (1) Evaluation effects of different acidification levels by formic acid on the (+)ESI-MS detection of PAHs. (2) Comparison of detection limits in ESI+ versus APPI+ experiments. (3) Investigation of the PAH fragmentation patterns in MS² experiments at different collision energies. (4) Calculation of wavelength dependent mass absorption coefficient (MAC_λ) of the standard mixture and its individual PAHs using LC-PDA data. (5) Assessment of the minimal injected mass required for accurate quantification of MAC_λ of the standard mixture and of a multi-component environmental sample.     

Handling of Environmental and Biological Samples via Pre-Column Technologies

Abstract

Sample handling is still a weak point in chromatography and in analytical chemisty in general. One consideration is the automation potential of new procedures. Solid-liquid extraction techniques in combination with pre-column technology are particularly promising in this regards. The construction and geometry of pre-columns both for conventional and narrow-bore HPLC are of major importance, since band broadening should be kept at a minimum for an optimal functioning of the analytical system. The various operations that can be carried out with such a pre-column are trace-enrichment, clean-up of the sample which depends on the type of adsorbents used in the precolumn, i.e., polar or apolar materials, ion exchangers or metal covered surfaces, etc., protection of the analytical column, field sampling and storage of samples and as a substrate for on-column chemical derivatizations. These various operations are demonstrated with practical examples from the fields of environmental and biological analysis. The selectivity can be further enhanced by coupling precolumn technology with selective detection modes such as diode array UV, electrochemical or fluorescence detection. This enables the construction of optimal and integrated analysis sytems which are fully automated and microprocessor controlled. They can also be made compatible with miniaturized LC-technology.     

EU Approach for Environmental Exposure Assessment: Actual Status and Future Needs

Abstract

To estimate the environmental concentration of a chemical substance, as required by the legislation of the European Union in the context of the risk assessment of chemical substances, several mathematical models are proposed. Representative and reliable analytical monitoring data for the different environmental compartments are indeed only seldom available. The proposed models are simple models as for instance multimedia fugacity models. Although the results of these models only provide an imperfect approximation of the concentration in the different compartments, very high uncertainties can lie upon certain input parameters, like the quantities of the substance released during one of its life-stages, its biodegradation rate in the respective compartments or its partition coefficients between those compartments. The improvement of the risk assessment scheme as proposed by the EU-Member States should focus on these input parameters. This might imply further adapting the test methods or even the requested test battery to the physical-chemical properties or even the structure of a substance.     

The Identification of Polynuclear Aromatic Hydrocarbon (PAH) Derivatives in Mutagenic Fractions of Diesel Particulate Extracts

Abstract

The soluble organic fraction (SOF) of particulate matter from diesel exhaust (from point sources, ambient air, etc.) contains hundreds of organic constituents. Normal-phase high pressure liquid chromatography (HPLC) has been used to separate the SOF into sub-fractions suitable for subsequent chemical analysis and bioassays. These fractions consist of non-polar(PAH), moderately polar (transition) and highly polar constituents. The non-polar fractions have been well characterized and consist of PAH and aliphatic hydrocarbons. The specific compounds present in the transition and polar fractions are for the most part unknown. This analytical information has been difficult to obtain since these compounds are highly labile, polar, of low volatility and in very low concentrations when compared to the bulk of material found in the SOF. Mutagenicity tests using the Ames Salmonella typhimurium assay indicate that the transition fraction accounts for most of the mutagenicity when compared to the non-polar (PAH) and polar fractions.

A variety of chromatographic and mass spectrometric techniques are described that have been used to determine the composition of the HPLC fractions. More than one hundred species have been identified in the transition fraction of diesel particulate matter using high resolution gas chromatography (HRGC)/high resolution mass spectrometry (HRMS), HPLC and direct-probe high resolution mass spectrometry. It has been found that the transition fraction contains mostly PAH derivatives consisting of hydroxy, ketone, quinone, carboxaldehyde, acid anhydride and dihydroxy derivatives of PAH. Three nitro-PAH species have been tentatively identified and 1-nitropyrene positively identified in the transition fraction. The 1-nitropyrene was found to account for approximately 45% and 30% of the direct-acting mutagenicity observed for the transition fraction and total extract, respectively. The HPLC separation procedure was shown to give better than 95% recovery of the mass and mutagenic activity. The problem of PAH oxidation during the analytical procedures and possible effect on bioassay results are discussed.     

Analysis of Polycyclic Aromatics

Abstract

Polycyclic aromatic hydrocarbons (PAH), among them carcinogenic compounds, have been found to be widely distributed in the human environment. The formation of PAH in processes relevant to environmental pollution will be described (pyrolysis or incomplete combustion of aliphatic and aromatic material, formation in higher plants). The application of the following methods to the analysis of PAH mixtures will be discussed: gas chromatography (capillary columns, use. of liquid crystals and inorganic salts such as LiCl or Cacl₂, as stationary phases in packed columns, selective detectors); luminescence spectroscopy (use of phosphorescence in paper and thin-layer chromatography, Shpol'skii spectra, quenchofluorimetry; mass spectroscopy.     

Cloud point extraction as a sample enrichment technique for capillary electrophoresis–An overview

Abstract

Cloud point extraction (CPE) is a simple, inexpensive and green sample enrichment technique for different analytes in different matrices. In this technique surfactant solution is used at concentration above critical micelle concentration to extract the analytes from various matrices. Capillary electrophoresis (CE) and family of related techniques have emerged as powerful analytical techniques for pharmaceutical, biomedical, food and environmental analysis. In this review we have described the applications of CPE coupling with CE.     

Improving the Fluorescence Detectability of Polycyclic Aromatic Hydrocarbons for Evaluation of Workplace Environments of Cement Industries Processing Organic Residues

Abstract

The burning of organic residues and wastes in furnaces of cement industries has been an attractive and lucrative approach to eliminate stocks of these pollutants. There is a potential risk for producing PAH in the workplace of industries burning organic wastes, so that highly sensitive analytical methods are needed for monitoring the air quality of these environments. An official method for determination of PAH is based on liquid chromatography with fluorescence detection at fixed excitation and emission wavelengths. We demonstrate that a suitable choice of these wavelengths, which are changed during the chromatographic run, significantly improves the detectability of PAH in atmosphere and particulate matter collected in cement industries.     

Perspectives of magnetic nature carbon dots in analytical chemistry: From separation to detection and bioimaging

Magnetic nature carbon dots (MNCDs) are fast growing materials with extremely unique physico-chemical properties and physiological ability to extend their applications from separation science to detection and bio-/magnetic resonance imaging applications. Recent studies have revealed that the MNCDs are significantly used as promising agents in analytical chemistry for the separation and identification of trace level target analytes. Further, the MNCDs have been used as probes for bioimaging of cells and magnetic resonance imaging (MRI) of tumors. Due to the lack of comprehensive reviews in this emerging field especially MNCDs applications in analytical chemistry, this review may provide quick guide and reference on the MNCDs-based analytical approaches for the separation and detection of trace level analytes, and bio- and MR- imaging of various cells. In this review article, we will summarize the synthetic approaches for the fabrication of MNCDs. The main part of this proposed review is devoted to the tremendous applications of MNCDs (Fe₃O₄@CDs, metal ion (Fe³⁺, Mn²⁺, Co²⁺ and Gd²⁺)-doped CDs, MnO₂@CDs) in analytical chemistry from separation science to detection and bio- and MR imaging. Finally, we will explore the challenges and future prospects of magneto fluorescent carbon dots in biomedical applications.     

Determination of selected polycyclic aromatic hydrocarbons and oxygenated polycyclic aromatic hydrocarbons in aerosol samples by high-performance liquid chromatography and liquid chromatography–tandem mass spectrometry

Fine and ultrafine particles are probably responsible for numerous health effects, but it is still unclear whether and to what extent the particle itself or organic compounds adsorbed or condensed on the particle are responsible for the effects observed. One important class of particle-bound substances are the polycyclic aromatic hydrocarbons (PAH) and their oxygenated derivatives. To improve the tools used for chemical characterization of particulate matter analytical methods for the determination of PAH and oxygenated PAH in aerosol samples of different origin have been developed and optimized. PAH on high-volume filters and on soot aerosols were analyzed by using accelerated solvent extraction for extraction and high-performance liquid chromatography with fluorescence detection for separation and quantification. Total PAH concentrations were in the range 0.3–9.3 ng m^–3. For analysis of selected oxygenated PAH on high-volume filters a liquid chromatography–tandem mass spectrometric method was developed and optimized. Preliminary investigations showed that oxygenated PAH at pg m^–3 concentrations can be determined.