Evaluating IMPROVE PM

The Interagency Monitoring of PROtected Visual Environments (IMPROVE) network has collected airborne particulate matter (PM) samples at locations throughout the United States since 1988 and provided chemical speciation measurements on the samples using several techniques including X-ray fluorescence (XRF). New XRF instruments for measuring PM elemental content of IMPROVE samples were introduced in 2011. To evaluate the performance of these new instruments relative to the old instruments, archived sample from three IMPROVE monitoring sites were retrieved and analyzed on the new instruments. The agreement between the two instruments varied by element. Comparisons of the results were very good (slopes within 10% of unity) for most elements regularly measured well above the detection limits (sulfur, chlorine, potassium, titanium, vanadium, manganese, iron, copper, zinc, selenium, lead). Different particle compositions at the three sites highlighted different measurement interferences. High sea salt concentrations at the coastal site emphasized corrections applied in the old systems to light elements - sodium and magnesium - and resulted in poor agreement for these elements. Comparisons of the XRF measurements with collocated sulfate measurements by ion chromatography suggest that sulfur measurements from the new instruments are more precise but slight underestimates. Comparing elemental ratios to expected ratios for soil-derived PM demonstrate the new instruments are better at resolving the aluminum and silicon peaks.