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ABSTRACTThis paper presents the results of analytical work which aimed to explore potential sources for the lime mortar used in the Hadrianic fort baths and a third-century repair to Hadrian's [...]

ABSTRACT Extraction of limestone roofing slate from Collyweston was an industry which was considered extinct by the early 1990's, with building repairs relying on wholesale recycling of roofing from demolished [...]

This article describes the approach used to assess the performance of a Fourier transform infrared (FTIR) and principal component regression (PCR) chemometric method when measuring respirable quartz, kaolinite, and coal in samples from a variety of mines from different countries; relative to target assigned values determined using X-ray diffraction (XRD). For comparison, FTIR results using the partial least squares regression (PLSR) method are also available. Bulk dusts from 10 Australian mines were scanned using XRD and grouped into three sets based on the levels of quartz, kaolinite, and feldspar within their crystalline mineral composition. Prediction samples were generated from 5 of these Australian mine dusts, Durrans coal dust, 2 mine dusts from the UK, and a single South African mine dust (71 samples in total) by collecting the aerosolized respirable dust onto 25-mm diameter polyvinylchloride filters using the Safety in Mines Personal Dust Sampler (SIMPEDS) operating at 2.2 l min−1. The predicted values from the FTIR chemometric methods were compared with assigned target values determined using a direct on-aerosol filter XRD analysis method described in Method for the Determination of Hazardous Substances (MDHS) 101. Limits of detection (LOD) and uncertainty values for each analyte were calculated from a linear regression between target and predicted values. The uncertainty was determined using the calibration uncertainty equation for an unweighted regression. FTIR results from PCR and PLSR are very similar. For the PCR method, the LOD for quartz, kaolinite, and coal were 5, 25, and 71 µg, respectively. For quartz, an LOD of 5 µg corresponds to an airborne quartz concentration of 10 µg m−3, assuming a 4-h sampling time and collection flow rate of 2.2 l min−1. The FTIR measurement met the expected performance criteria outlined in ISO 20581 when sampling quartz for more than 4 h using a flow rate of 2.2 l min−1at a concentration of 0.1 mg m−3(100 µg m−3), the current workplace exposure limit in Great Britain. This method met the same performance criteria when measuring exposures at the Australian Workplace Exposure Standard (WES) concentration of 0.05 mg m−3, although in this case a sampling period greater than 8 h was needed.

Exposure to respirable crystalline silica (RCS) is potentially hazardous to the health of thousands of workers in Great Britain. Both X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy can be used to measure RCS to assess exposures. The current method outlined in the Health and Safety Executive’s (HSE) Methods for the Determination of Hazardous Substances (MDHS) guidance series is ‘MDHS 101 Crystalline silica in respirable airborne dust - Direct-on-filter analyses by infrared spectroscopy or x-ray’. This describes a procedure for the determination of time-weighted average concentrations of RCS either as quartz or cristobalite in airborne dust. FTIR is more commonly employed because it is less expensive, potentially portable and relatively easy to use. However, the FTIR analysis of RCS is affected by spectral interference from silicates. Chemometric techniques, known as Partial Least Squares Regression (PLSR) and Principal Component Regression (PCR), are two computational processes that have the capability to remove spectral interference from FTIR spectra and correlate spectral features with constituent concentrations. These two common chemometric processes were tested on artificial mixtures of quartz and kaolinite in coal dust using the same commercially available software package. Calibration, validation and prediction samples were prepared by collecting aerosols of these dusts onto polyvinylchloride (PVC) filters using a Safety in Mines Personal Dust Sampler (SIMPEDS) respirable cyclone. PCR and PLSR analyses were compared when processing the same spectra. Good correlations between the target values, measured using XRD, were obtained for both the PCR and PLSR models e.g. 0.98–0.99 (quartz), 0.98–0.98 (kaolinite) and 0.96–0.97 (coal). The level of agreement between PCR and PLSR was within the 95% confidence value for each analyte. Slight differences observed between predicted PCR and PLSR values were due to the number of optimal principal components applied to each chemometric process. The presence of kaolinite in these samples caused an 18% overestimation of quartz, for the FTIR, when following MDHS 101 without a chemometric method. Chemometric methods are a useful approach to obtain interference-free results for the measurement of RCS from some workplace environments and to provide a multicomponent analysis to better characterise exposures of workers.

This article describes the development of an analytical method to measure respirable crystalline silica (RCS) collected on filters by a miniature sampler placed behind respirators worn by workers to evaluate their ‘true’ exposure. Test samples were prepared by aerosolising a calibration powder (Quin B) and by pipetting aliquots from suspensions of bulk material (NIST 1878a and Quin B) onto filters. Samples of aerosolised RCS collected onto polyvinyl chloride PVC filters were ashed and their residue was suspended in isopropanol and filtered into a 10 mm diameter area onto silver filters. Samples were also collected by the Health and Safety Executive's (HSE) miniature sampler from within the facepiece of a respirator on a breathing manikin during a simulated work activity. Results obtained using Raman spectroscopy were compared with X-ray diffraction (XRD) measurements, which was used as a reference method and a linear relationship was obtained. Raman has similar estimates of uncertainty when compared with the XRD methods over the measurement range from 5 to 50 μg and obtained the lowest limit of detection (LOD) of 0.26 μg when compared with XRD and Fourier Transform Infrared FTIR methods. A significant intercept and slope coefficient greatly influenced the higher LOD for indirect XRD method. The level of precision and low LOD for Raman spectroscopy will potentially enable workplace measurements at lower concentrations below the Workplace Exposure Limit (WEL) than are achieved using current analytical instrumentation. Different inward leakage ratio (ILR) measurement approaches were compared using six aerosolised sandstone dust tests. For the three highest inward leakage ratios the Portacount® obtained higher values than the RCS mass or the miniWRAS ratios, the latter of which reporting both particle number and quartz mass concentration. However, these limited ILR data were insufficient to establish statistical correlations between the measurement methods.

The effect of polyethylene glycol (PEG) having amolecular weight of 1000 and 2000 on shellac stability has been investigated in this research. The shellac was shellac wax free, and the solvent was ethanol 96%. Shellac films were prepared by solventevaporationmethod. The stability of shellac was investigated using insoluble solid test, Fourier Transform Infra Red (FTIR), Thermogravimetry Analyzer (TGA), and Water Vapour Transmission Rate (WVTR). The results showed that stability of shellac decreased after heating at 125oC for 10,30,90,and 180 minutes, and storing for 1 month at 27 oC and 85 relative humidity (RH). PEG improved the stability, and the most stable effect was achieved through PEG1000.