Preparation and validation of fully synthetic standard gas mixtures with atmospheric isotopic composition for global CO2 and CH4 monitoring.

We report the preparation and validation of the first fully synthetic gaseous reference standards of CO2 and CH4 in a whole air matrix with an isotopic distribution matching that is in the ambient atmosphere. The mixtures are accurately representative of the ambient atmosphere and were prepared gravimetrically. The isotopic distribution of the CO2 was matched to the abundance in the ambient atmosphere by blending (12)C-enriched CO2 with (13)C-enriched CO2 in order to avoid measurement biases introduced by measurement instrumentation detecting only certain isotopologues. The reference standards developed here have been compared with standards developed by the National Institute of Standards and Technology and standards from the WMO scale. They demonstrate excellent comparability.

Gaseous reference standards of formaldehyde from trioxane.

We have developed a dynamic reference standard of gaseous formaldehyde based on diffusion of the sublimate of trioxane and thermal conversion to formaldehyde in the gas phase. We have also produced a gravimetric standard for formaldehyde in a nitrogen matrix, also by thermal conversion of the sublimate of trioxane. Analysis of the gravimetric standard with respect to the dynamic standard has confirmed the comparability of the static and dynamic gravimetric values.

A new definition for the mole based on the Avogadro constant: a journey from physics to chemistry.

The mole is the most recent addition to the set of base units that form the International System of Units, although its pre-cursor the 'gram-molecule', had been in use by both physicists and chemists for more than 120 years. A proposal has been published recently to establish a new definition for the mole based on a fixed value for the Avogadro constant. This would introduce consistent relative uncertainties for the molar and the atomic masses while making no change to the system of relative atomic masses ('atomic weights'). Although the proposal would have little impact on the measurement uncertainty of practical work, it has stimulated considerable debate about the mole and the nature of the quantity amount of substance. In this paper, the rationale for the new definition is explained against the background of changes in the way the quantity amount of substance has been used, from its first use during the early development of thermodynamics through to the use of the 'number of gram-molecules' at the end of the nineteenth century.

Microfabricated planar glass gas chromatography with photoionization detection.

We report the development of a microfabricated gas chromatography system suitable for the separation of volatile organic compounds (VOCs) and compatible with use as a portable measurement device. Hydrofluoric acid etching of 95x95mm Schott B270 wafers has been used to give symmetrical hemi-spherical channels within a glass substrate. Two matching glass plates were subsequently cold bonded with the channels aligned; the flatness of the glass surfaces resulted in strong bonding through van der Waals forces. The device comprised gas fluidic interconnections, injection zone and 7.5 and 1.4m long, 320microm internal diameter capillaries. Optical microscopy confirmed the capillaries to have fully circular channel profiles. Direct column heating and cooling could be achieved using a combination of resistive heaters and Peltier devices. The low thermal conductivity of glass allowed for multiple uniform temperature zones to be achieved within a single glass chip. Temperature control over the range 10-200 degrees C was achieved with peak power demand of approximately 25W. The 7.5m capillary column was static coated with a 2microm film of non-polar dimethylpolysiloxane stationary phase. A standard FID and a modified lightweight 100mW photoionization detector (PID) were coupled to the column and performance tested with gas mixtures of monoaromatic and monoterpene species at the parts per million concentration level. The low power GC-PID device showed good performance for a small set of VOCs and sub ng detection sensitivity to monoaromatics.

A practical method to fabricate gold substrates for surface-enhanced Raman spectroscopy.

We describe a practical method of fabricating surface-enhanced Raman spectroscopy (SERS) substrates based on dip-coating poly-L-lysine derivatized microscope slides in a gold colloidal suspension. The use of only commercially available starting materials in this preparation is particularly advantageous, aimed at both reducing time and the inconsistency associated with surface modification of substrates. The success of colloid deposition has been demonstrated by scanning electron microscopy (SEM) and the corresponding SERS response (giving performance comparable to the corresponding traditional colloidal SERS substrates). Reproducibility was evaluated by conducting replicate measurements across six different locations on the substrate and assessing the extent of the variability (standard deviation values of spectral parameters: peak width and height), in response to either Rhodamine 6G or Isoniazid. Of particular interest is the observation of how some peaks in a given spectrum are more susceptible to data variability than others. For example, in a Rhodamine 6G SERS spectrum, spectral parameters of the peak at 775 cm(-1) were shown to have a relative standard deviation (RSD) % of <10%, while the peak at 1573 cm(-1) has a RSD of >or=10%. This observation is best explained by taking into account spectral variations that arise from the effect of a chemisorption process and the local nature of chemical enhancement mechanisms, which affects the enhancement of some spectral peaks but not others (analogous to resonant Raman phenomenon).

Developments in accurate and traceable chemical measurements.

In recent years there has been considerable interest in the application of the principles of measurement science to chemistry. This has led to the recognition of 'metrology in chemistry' as an area of relevance to analytical chemistry research. This tutorial review describes the benefits to chemistry of the implementation of the principles of measurement science and explains how they are able to improve the reliability and accuracy of chemical measurements.

Systematic error arising from 'Sequential' Standard Addition Calibrations: quantification and correction.

Calibrations involving the sequential addition of aliquots of a standard solution to a solution of unknown analyte content may exhibit a systematic error. We show that this systematic error is related to the ratio of the mass fractions in the standard and unknown solutions. This relationship is consistent with experimental results from the determination of lead in aqueous solution by anodic stripping voltammetry using 'Sequential' Standard Addition Calibration (S-SAC). The magnitude of this systematic error has been described mathematically and a correction calculated. These mathematical relationships form the basis for a proposal for best practice in the use of S-SAC.

Electromagnetic modelling of Raman enhancement from nanoscale substrates: a route to estimation of the magnitude of the chemical enhancement mechanism in SERS.

Despite widespread use for more than two decades, the SERS phenomenon has defied accurate physical and chemical explanation. The relative contributions from electronic and chemical mechanisms are difficult to quantify and are often not reproduced under nominally similar experimental conditions. This work has used electromagnetic modelling to predict the Raman enhancement expected from three configurations: metal nanoparticles, structured metal surfaces, and sharp metal tips interacting with metal surfaces. In each case, parameters such as artefact size, artefact separation and incident radiation wavelength have been varied and the resulting electromagnetic field modelled. This has yielded an electromagnetic description of these configurations with predictions of the maximum expected Raman enhancement, and hence a prediction of the optimum substrate configuration for the SERS process. When combined with experimental observations of the dependence of Raman enhancement with changing ionic strength, the modelling results have allowed a novel estimate of the size of the chemical enhancement mechanism to be produced.

Analysis of natural gas by gas chromatography reduction of correlated uncertainties by normalisation.

The results of gas chromatographic analysis of natural gas mixtures reveal strong correlations (Pearson correlation coefficient of >0.96) between the uncertainty of each component and variations in the ambient pressure. Although correction for ambient pressure variations can reduce this variability, normalisation of the results of each analysis using the assumption that the sum of all component amount fractions is unity provides significantly greater reductions in the uncertainty of each measured component. We show that the uncertainty in normalised components can be estimated approximately using the correlation coefficient as a measure of the correlation present in the measurements, or exactly using a full calculation of the variance/covariance (V/C) structure of the data.

High accuracy method for the application of isotope dilution to gas chromatography/mass spectrometric analysis of gases.

A new isotope dilution mass spectrometry (IDMS) method for high-accuracy quantitative analysis of gases has been developed and validated by the analysis of standard mixtures of carbon dioxide in nitrogen. The method does not require certified isotopic reference materials and does not require direct measurements of the highly enriched spike. The relative uncertainty of the method is shown to be 0.2%. Reproduced with the permission of Her Majesty's Stationery Office.

Use of the international system of units (SI) in isotope ratio mass spectrometry.

In this communication, we show how the established principles of the International System of Units (SI) can be used to develop a basis for stable, comparable and coherent measurements of isotope ratios by mass spectrometry. We show that there are no important differences in the traceability of quantities that represent ratios of the abundance of isotopes and those that represent fractions. However, it is important to distinguish between results expressed in 'absolute' terms and those expressed relative to stated references such as those expressed in terms of the commonly used quantity 'delta'.