Elemental composition of ambient aerosols measured with high temporal resolution using an online XRF spectrometer

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Abstract

The Xact 625 Ambient Metals Monitor was tested during a 3-week field campaign at the rural, traffic-influenced site Härkingen in Switzerland during the summer of 2015. The field campaign encompassed the Swiss National Day fireworks event, providing increased concentrations and unique chemical signatures compared to non-fireworks (or background) periods. The objective was to evaluate the data quality by intercomparison with other independent measurements and test its applicability for aerosol source quantification. The Xact was configured to measure 24 elements in PM10 with 1g h time resolution. Data quality was evaluated for 10 24g h averages of Xact data by intercomparison with 24g h PM10 filter data analysed with ICP-OES for major elements, ICP-MS for trace elements, and gold amalgamation atomic absorption spectrometry for Hg. Ten elements (S, K, Ca, Ti, Mn, Fe, Cu, Zn, Ba, Pb) showed excellent correlation between the compared methods, with r2 values ≥ g 0.95. However, the slopes of the regressions between Xact 625 and ICP data varied from 0.97 to 1.8 (average 1.28) and thus indicated generally higher Xact elemental concentrations than ICP for these elements. Possible reasons for these differences are discussed, but further investigations are needed. For the remaining elements no conclusions could be drawn about their quantification for various reasons, mainly detection limit issues. An indirect intercomparison of hourly values was performed for the fireworks peak, which brought good agreement of total masses when the Xact data were corrected with the regressions from the 24g h value intercomparison. The results demonstrate that multi-metal characterization at high-time-resolution capability of Xact is a valuable and practical tool for ambient monitoring.

Figures

  • Table 1. Regression coefficients for the comparison of Xact 625 and offline data. The 1 h values of the Xact 625 were averaged to 24 h values. Primed quantities are uncertainties.
  • Figure 1. Main panel: relative amount of analysed elements by Xact 625 during the field campaign. Top panel: absolute concentrations, stacked. The grey shaded area denotes the fireworks period. The red squares mark the days when 24 h filters were analysed and used for comparisons in this study. Bottom panel: relative cumulative elemental concentrations, stacked. Right panel: average relative contributions (in %) of elements for the fireworks period, the non-fireworks period, and the south and north sectors during the non-fireworks period.
  • Figure 2. Scatter plots and regression lines of Xact 625 (ordinate) vs. ICP-OES/MS (abscissa) data for groups A and B. Elements with an asterisk (∗) were analysed with ICP-OES. The axes have been scaled by the maximum concentration Cmax,ICP indicated in the legends for each element (Cmax,AuAAA for Hg). The Levenberg–Marquardt linear least-squares fitting method was applied, taking the ICP measurements as the independent data. Regression equation is y = a+ bx. See Table 1 for data.
  • Figure 3. (a) Slopes and intercept ratios (intercepts divided by the average concentrations measured with XRF) with standard deviations for all elements measured with the Xact. (b) Minimum detection limits (MDL), interference free for the Xact 625 (XRF) and for the ICP analyses. Hg was analysed with AuAAA spectrometry.
  • Table 2. Comparison of Xact data with published ICP data of other campaigns.
  • Figure 4. Time series of Xact 625 total elemental concentration, ACSM PM1 data, NABEL TEOM PM10 data, and wind speed (WSpd) and direction (WDir) measurements in Härkingen. Numbers at the peaks indicate 1 h concentration maxima.
  • Figure 5. Comparison of Xact PM10 SO4 vs. ACSM PM1 SO4. Data were split into fireworks (red) and non-fireworks (blue) periods.
  • Figure 6. Mean diurnal variations of (a) Ca and (b) Ba, stratified for fireworks (red) and non-fireworks (blue) periods. Error bars denote ±1 standard deviation of the averaging period. Diurnal variations for the other elements are shown in the Supplement (Fig. S4).

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Furger, M., Minguillón, M. C., Yadav, V., Slowik, J. G., Hüglin, C., Fröhlich, R., … Prévôt, A. S. H. (2017). Elemental composition of ambient aerosols measured with high temporal resolution using an online XRF spectrometer. Atmospheric Measurement Techniques, 10(6), 2061–2076. https://doi.org/10.5194/amt-10-2061-2017

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