Abstract:
When high mineral loads in atmospheric particulate matter (PM) are present, particular
attention should be paid to the selection of appropriate acidic digestion protocols for wet
chemical analysis. We report on a comparative study of elemental recovery yields from five
different pre-analytical acid digestion procedures for mineral-rich urban background PM10
samples collected in the city of Constantine (Northeastern Algeria). Five reference materials
(NIST 1633b, UPM 1648, NAT-7, SO-2 and SO-4) were also digested according to the same
protocols. The selected acidic digestion procedures are widely used for PM chemical analysis,
and comprise: P1 (HNO3/HF/HCl), P2 (HCl/HNO3), P3 (HCl/H2O2/HNO3), P4
(HNO3/HF/HClO4) and P5 (HNO3/H2O2); the latter is assisted with micro-wave digestion.
Elemental recovery yields were compared for major and trace elements typically determined
in PM for source apportionment analysis and the results evidenced large differences. For most
elements, the bulk extraction procedures (requiring the use of HF) allowed a full elemental
recovery, particularly for elements that are associated with aluminum-silicate species and
oxides that are resistant to mild acid attack. In contrast, in the extraction protocols without
HF, low recovery yields were obtained for elements such as Al, Ti, Zr, Sc, and other
aluminumsilicate-related elements in PM10 samples with high mineral dust load. We highlight
that the European standard digestion method EN-14902: 2005 should be applied specifically
for the metals for which this method was developed, but caution should be taken when the
analysis of other elements in PM is required, especially in urban areas where road and vehicle
wear dust is likely to be a major component of ambient PM. When using wet chemistry
analysis for PM source apportionment studies, we strongly recommend HF bulk dissolution of
samples to ensure the reliability of the geochemical information when coupled with an
appropriate analytical tool.