Recent certification of reference materials by the Community Bureau of Reference for,in particular,environmental analysis

Reference materials are necessary to improve or to maintain a high quality of analysis. To avoid bias as far as possible, the BCR certifies reference materials on the basis of results of different methods used by different laboratories. A proper selection of good methods and laboratories makes it possible to obtain excellent agreement and narrow confidence intervals. Neutron activation techniques are suited for many key elements; their results are in good agreement with those of other techniques.     

Preconcentration of environmental trace elements on organic support for neutron activation and high resolution photon spectrometry

In this paper, six methods of preconcentration on ion exchange or chelating filters and resins for neutron activation with X-ray and gamma spectrometry are described. These techniques are applied to the determination of trace elements in natural waters. The analysis of water samples from the lake of Geneva by these different methods gave results in good agreement among themselves and also when compared with those obtained by other techniques, with a very reasonable blank and good sensitivity for most determined elements.     

Analytical chemistry — a personal perspective

As the demands placed on the analytical chemist continue to grow, he must develop increasingly sophisticated analytical methodologies to meet them. The polarographic techniques are a good illustration of how techniques can be adapted to meet a variety of situations.     

Correlation between different clean-up methods and analytical techniques performances to detect Ochratoxin A in wine

Three different clean-up methods and two analytical techniques were compared to determine Ochratoxin A (OTA) in wines. The first clean-up used a MycoSep column, the second an immunoaffinity column (IAC) and the third consisted in a liquid-liquid extraction (LLE) using dichloromethane in acid conditions. Meanwhile, two different OTA determination techniques were also evaluated: a HPLC analysis using a fluorescence detector and an enzyme-linked immunosorbent assays (ELISA) method.Correlations between clean-up methods and analytical techniques to determine OTA in wine were made evaluating linearity, accuracy and precision.Both the two first clean-up methods (solid-phase extraction, SPE) showed a good linear fit (r² = about 0.9999), followed by LLE. The use of immunoaffinity columns showed the best recoveries, even if also the SPE with MycoSep showed good recoveries while the LLE recoveries were the worst ones. The HPLC analysis showed good precision and accuracy, while ELISA method, even with a sufficient linearity, generally underestimated OTA content in wines.     

A comparison of two micro-beam X-ray emission techniques for actinide elemental distribution in microscopic particles originating from the hydrogen bombs involved in the Palomares (Spain) and Thule (Greenland) accidents

In order to validate and to gain confidence in two micro-beam techniques: particle induced X-ray emission with nuclear microprobe technique (μ-PIXE) and synchrotron radiation induced X-ray fluorescence in a confocal alignment (confocal SR μ-XRF) for characterization of microscopic particles containing actinide elements (mixed plutonium and uranium) a comparative study has been performed. Inter-comparison of the two techniques is essential as the X-ray production cross-sections for U and Pu are different for protons and photons and not well defined in the open literature, especially for Pu.The particles studied consisted of nuclear weapons material, and originate either in the so called Palomares accident in Spain, 1966 or in the Thule accident in Greenland, 1968. In the determination of the average Pu/U mass ratios (not corrected by self-absorption) in the analysed microscopic particles the results from both techniques show a very good agreement. In addition, the suitability of both techniques for the analysis with good resolution (down to a few μm) of the Pu/U distribution within the particles has been proved. The set of results obtained through both techniques has allowed gaining important information concerning the characterization of the remaining fissile material in the areas affected by the aircraft accidents. This type of information is essential for long-term impact assessments of contaminated sites.     

Electroplating versus microprecipitation of the actinides in alpha-spectroscopic analysis

The recent challenge of the electroplating (EP) method by microprecipitation (MP) methods for alpha-spectroscopic analysis of actinides led us to a comparison study of the two techniques for application to our laboratory workloads. A baseline study was done using filter papers spiked individually with uranium, plutonium and americium. Water and soil samples collected at various field sites were analyzed for uranium and field-collected air filters were analyzed for plutonium. Applicability and attractiveness of both techniques were found to provide good reproducible recoveries adequate for quantifying uranium isotope activity on air filters and in water and soil. Measurement of americium and plutonium on air filters similarly gave good results. Isotope peak resolution was good for both methods and did not contribute to measurement uncertainly over the range of activities studied. Although expanded matrix investigations may still be needed for more depth, we concluded that microprecipitation can be a time saving alternative to the electroplating technique for alpha-spectroscopy of the actinides.     

Natural and artificial photo-aging of non-stabilized and pigmented, hindered-amine stabilized propylene-ethylene copolymers

This paper describes the chemical evolution of two propylene-ethylene copolymer formulations, non-stabilized and carbon black filled - HALS stabilized, exposed to a range of natural and artificially accelerated weathering techniques, commonly used in the field of material testing. With the non-stabilized formulation, a fairly good representation of weathering in outdoor conditions was demonstrated with any of the accelerated exposures through the recognition of similar chemical changes at the molecular level. In contrast, the additives in the stabilized matrix induced very different chemical evolutions depending on the weathering techniques employed. This variability has been used to critically characterize those techniques on a scientific basis.     

The role of graphene‐based sorbents in modern sample preparation techniques

The application of graphene‐based sorbents in sample preparation techniques has increased significantly since 2011. These materials have good physicochemical properties to be used as sorbent and have shown excellent results in different sample preparation techniques. Graphene and its precursor graphene oxide have been considered to be good candidates to improve the extraction and concentration of different classes of target compounds (e.g., parabens, polycyclic aromatic hydrocarbon, pyrethroids, triazines, and so on) present in complex matrices. Its applications have been employed during the analysis of different matrices (e.g., environmental, biological and food). In this review, we highlight the most important characteristics of graphene‐based material, their properties, synthesis routes, and the most important applications in both off‐line and on‐line sample preparation techniques. The discussion of the off‐line approaches includes methods derived from conventional solid‐phase extraction focusing on the miniaturized magnetic and dispersive modes. The modes of microextraction techniques called stir bar sorptive extraction, solid phase microextraction, and microextraction by packed sorbent are discussed. The on‐line approaches focus on the use of graphene‐based material mainly in on‐line solid phase extraction, its variation called in‐tube solid‐phase microextraction, and on‐line microdialysis systems.     

An international intercalibration for methylmercury in biological tissue

An intercalibration exercise between 13 laboratories from seven countries was conducted for comparing the methylmercury measurement techniques for marine biological tissues. Analyses have been conducted on two sets of samples: a fish muscle and a mussel soft tissue. Most of the participating laboratories performed six replicate analyses, allowing statistical comparisons. Various analytical techniques have been used, including cold vapour atomic absorption spectrophotometry (CVAA), electron capture gas liquid chromatography (GCEC), neutron activation (NAA), and inductively coupled plasma–isotopic dilution mass spectrometry (ICPIDMS). All of these methods offer similar results. They allow us to define consensus values which seem good estimates of the real concentrations. In addition the results show, for most of the participating laboratories, good accuracy and precision in the determination.     

Design and preparation of bioactive glasses with hierarchical pore networks

Hierarchically giant-, macro-, and meso-porous 3D bioactive glass scaffolds with good bone-forming bioactivity in vitro were synthesized by using a combination of sol-gel, double polymers templating, and rapid prototyping techniques.     

Determination of trace and minor elements in coal: A comparison between instrumental photon and thermal neutron activation analysis

Instrumental photon and neutron activation techniques have been compared through the determination of sixteen major, minor and trace constituents in two British Columbian coals and a standard coal. Between the two techniques, the results generally agreed to within one standard deviation with replicate precision being maintained, for both techniques, below twenty percent at worst and down to five percent or better for several elements. Almost all of the elements having environmental, industrial or economic significance in fossil fuels can be determined with good sensitivity by either of these two methods, both of which share the advantages of being non-destructive and multi-element in nature and sufficiently accurate as demonstrated in this paper.     

Chromatographic analysis of unsaponifiable compounds of olive oils and fat-containing foods

The analysis of the "minor components" present in food lipids is usually hampered by the large diversity of compounds found in this fraction. High-purity degree reagents and solvents, good collection techniques and highly sensitive analysis are required in order to accurately identify and quantify these components. Chromatographic techniques have proven to be particularly suitable for these determinations, especially capillary gas chromatography. This study reports several analytical cases of the main classes of components of the unsaponifiable matter obtained from olive oils or food matrices.     

Determination of nanocrystal sizes: a comparison of TEM, SAXS, and XRD studies of highly monodisperse CoPt3 particles

One of the most fundamental tasks in nanoscience is the accurate determination of particle sizes. Various methods have been developed to elucidate the mean particle diameter and the standard deviation for an ensemble of nanocrystals. However, good agreement between the results from different methods is not always encountered in the literature. In this study, we investigate colloidally prepared, highly monodisperse CoPt3 nanoparticles by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and powder X-ray diffraction (XRD). The results are compared in order to examine to which extent agreement is obtained by the different techniques when applied to small nanocrystals in the size range below 10 nm. In particular, the applicability of the simple Scherrer formula for size determination from the broadening of XRD reflections is checked. When the different techniques are correctly applied, the results from all methods are in good agreement.     

Contact angle hysteresis on polymer substrates established with various experimental techniques, its interpretation, and quantitative characterization

The effect of contact angle hysteresis (CAH) was studied on various polymer substrates with traditional and new experimental techniques. The new experimental technique presented in the article is based on the slow deformation of the droplet, thus CAH is studied under the constant volume of the drop in contrast to existing techniques when the volume of the drop is changed under the measurement. The energy of hysteresis was calculated in the framework of the improved Extrand approach. The advancing contact angle established with a new technique is in a good agreement with that measured with the needle-syringe method. The receding angles measured with three experimental techniques demonstrated a very significant discrepancy. The force pinning the triple line responsible for hysteresis was calculated.     

Comparison of different extraction techniques for the determination of polychlorinated organic compounds in sediment

The performance of various enhanced extraction techniques, such as accelerated solvent extraction, microwave-assisted extraction, Soxhlet extraction, ultrasonic extraction and fluidized-bed extraction for the determination of polychlorinated organic compounds in dry sediment was investigated in two laboratories. The results of the two laboratories were in good agreement. The extraction yields from the batch extraction methods were lower than those from the dynamic techniques. Accelerated solvent extraction, especially, exhibited higher extraction efficiency than the standard procedure, Soxhlet extraction, whereas the results of fluidized-bed extraction were comparable.     

Preparation and application of hydrophilic monolithic columns

Hydrophilic interaction chromatography (HILIC) has experienced increasing attention in recent years. Much research has been carried out in the area of HILIC separation mechanisms, column techniques and applications. Because of their good permeability, low resistance to mass transfer and easy preparation within capillaries, hydrophilic monolithic columns represent a trend among novel HILIC column techniques. This review attempts to present an overview of the preparation and applications of HILIC monolithic columns carried out in the past decade. The separation mechanism of various hydrophilic monolithic stationary phases is also reviewed.     

Chiral ytterbium complex-catalyzed direct asymmetric aldol-Tishchenko reaction: synthesis of anti-1,3-diols

The asymmetric aldol-Tishchenko reaction of aromatic aldehydes with aliphatic and aromatic ketones has been developed as an efficient strategy for the synthesis of anti-1,3-diols in good yield with high diastereocontrol and good levels of enantioselectivity. This domino-type reaction is catalyzed by a chiral ytterbium complex that promotes both the aldol reaction through enolization of the carbonyl compound and the Evans-Tishchenko reduction of the aldol intermediate. The stereochemistry of the resulting diols is also investigated and finally proved by using CD techniques.     

A comparison of two techniques to determine carbon-14 in environmental samples

We have experience of two methods for the analysis of ¹⁴C in environmental samples and have used this experience to directly compare these two techniques. Nine vegetation samples and a sucrose standard were analyzed using the benzene synthesis and combustion techniques. The results obtained using both methods were in good agreement and show that ¹⁴C data obtained using either technique are comparable. The analytical requirements for the two techniques vary considerably. In choosing a technique, a variety of factors such as sensitivity, sample size, sample type, carbon content and how the results are to be expressed, need to be considered.     

Efficient microwave-assisted synthesis of 3-benzothiazolo and 3-benzothiazolino coumarin derivatives catalyzed by heteropoly acids

Heteropoly acids are reported as efficient catalysts for the microwave-assisted synthesis of 3-benzothiazolo and 3-benzothiazolino coumarin from o-aminothiophenol derivatives with 3-acetly and 3-cyanochromen-2-one in good to excellent isolated yields (73?C95%). This study suggests new techniques for the synthesis of chromene derivatives using an inexpensive and easily available catalyst, a simple procedure, short reaction time, and good to excellent yields of the products.     

An Assessment of Dust Analyses: With Particular Reference to Lead and Certain Other Metals

Abstract

The last few years have shown an increase in the number of publications describing studies on dust as indicators of environmental pollution, especially by trace metals. The techniques of sampling and analysis used in these studies are reviewed, with particular attention to inconsistencies and differences which make data incomparable. The need for work on the development of standard methods is demonstrated. Only by the application of good quality control, reference materials and reliable techniques will an unsatisfactory situation be improved.