Sr-Nd-Hf isotopic analysis of reference materials and natural and anthropogenic particulate matter sources: Implications for accurately tracing North African dust in complex urban atmospheres.

We present novel chemical separation protocols for isotopic analysis of low mass aliquots (0.3 mg and 25 mg) of several reference materials and real-world samples of relevance to urban airborne particulate matter (PM) investigations. A high-yielding gravity flow column chromatography scheme was developed for facile and quantitative separation of Sr, Nd, and Hf prior to multi collector - inductively coupled plasma - mass spectrometry (MC-ICP-MS). Because we are interested in isolating and accurately quantitating individual anthropogenic and natural aerosol sources in complex industrial/metropolitan atmospheric environments, laboratory protocols were optimized using National Institute of Standards and Technology Standard Reference Material (SRM) 1648a (urban atmospheric PM), SRM 1633b (coal fly ash), and European Commission standards BCR-723 (vehicular road dust), and BCR-2 (basalt rock standard). Sr, Nd, and Hf procedural blanks from column chromatography were low (averaging only 37 pg, 17 pg, 11 pg, respectively) and recoveries were high (averaging 95%, 82%, and 92%, respectively). A volume-adjustment protocol was established using isotope reference solutions SRM 987 (SrCO3), JNdi (Nd2O3), and in-house Hf standards to dilute the dried samples prior to MC-ICP-MS based on projected uncertainties for low sample masses. 87Sr/86Sr, 143Nd/144Nd, and 176Hf/177Hf isotopic ratios in SRM 1648a, BCR-723, and SRM 1633b are reported for the first time that can serve as provisional reference values. The novel method was used to characterize isotopic ratios and elemental abundances in two anthropogenic urban aerosol sources, namely motor vehicles and petroleum refining using airborne fine PM collected in a vehicular tunnel and fluidized-bed catalytic cracking catalysts, respectively. Two other important mineral-rich urban PM sources, namely soil (i.e., resuspended crustal material) and concrete/cement dust (i.e., construction activity) were also characterized. These are the first isotopic measurements in these environmental compartments and were compared with literature data for long-range transported North African dust, which is a prominent summertime PM source in urban regions in southeastern United States. We demonstrate the capability of coupled Sr-Nd-Hf isotopes to uniquely trace different mineral dust sources with overlapping elemental composition (Sahara-Sahel region, local soil, and concrete/cement) and accurately isolate various urban PM sources demonstrating the superiority of isotopic markers over elemental tracers.