Abstract. Measuring the chemical composition of airborne particulate matter (PM) can provide valuable information on the concentration of regulated toxic metals, support modelling approaches for source detection and assist in the identification and validation of abatement techniques. Undertaking these at a high time resolution (1 h or less) enables receptor modelling techniques to be more robustly linked to emission processes. This study describes a comprehensive laboratory and field evaluation of a high time resolution x-ray fluorescence (XRF) instrument (CES XACT 625) for a range of elements (As, Ba, Ca, Cd, Ce, Cl, Cr, Cu, Fe, K, Mn, Mo, Ni, Pb, Pt, S, Sb, Se, Si, Sr, Ti, V and Zn) against alternative techniques: high time resolution mass measurements, high time resolution ion chromatography, aerosol mass spectrometry, and established filter-based, laboratory analysis using inductively coupled plasma mass spectrometry (ICP-MS).

1. Laboratory evaluation was carried out using a novel mass-based calibration technique to independently assess the accuracy of the XRF against laboratory generated aerosols, which resulted in slopes that were not significantly different from unity. This demonstrated that generated particles can serve as an alternative calibration method for this instrument.

2. The XACT was evaluated in three contrasting field deployments; a heavily trafficked roadside site (PM₁₀ and PM_2.5), an industrial location downwind of a nickel refinery (PM₁₀) and an urban background location influenced by nearby industries and motorways (PM₁₀). The XRF technique agreed well with the ICP-MS measurements of daily filter samples in all cases with a median R² of 0.93 and a median slope of 1.07 for the elements As, Ba, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, Se, Sr, Ti, V and Zn. Differences in the results were attributed to a combination of inlet location and sampling temperature, variable blank levels in filter paper and recovery rates from acid digestion. The XRF technique also agreed well with the other high time resolution measurements but showed a clear positive difference (slopes between 1.41 and 4.6), probably due to differences in the size selection methodology, volatility and water solubility of the PM in aerosol mass spectrometry (SO₄) and ion chromatography (Ca, Cl, K and SO₄), respectively.

3. A novel filter analysis technique using the XACT showed promising initial results: filters analysed off-line with the XACT compared well to in situ XACT measurements with a median R² of 0.96 and median slope of 1.07. The resulting range of slopes was comparable to slopes produced in the ICP-MS comparison. This technique provides an opportunity to use the XACT when it is not deployed in the field; thus expanding the potential use of this instrument in future studies.