Lanthanum and lanthanides in atmospheric fine particles and their apportionment to refinery and petrochemical operations in Houston, TX

A study was conducted in Houston, TX focusing on rare earth elements (REEs) in atmospheric fine particles and their sources. PM2.5 samples were collected from an ambient air quality monitoring site (HRM3) located in the proximity of a large number of oil refineries and petrochemical industries to estimate the potential contributions of emissions from fluidized-bed catalytic cracking operations to ambient fine particulate matter. The elemental composition of ambient PM2.5, several commercially available zeolite catalysts, and local soil was measured after microwave assisted acid digestion using inductively coupled plasma—mass spectrometry. Source identification and apportionment was performed by principal component factor analysis (PCFA) in combination with multiple linear regression. REE relative abundance sequence, ratios of La to light REEs (Ce, Pr, Nd, and Sm), and enrichment factor analysis indicated that refining and petrochemical cat cracking operations were predominantly responsible for REE enrichment in ambient fine particles. PCFA yielded five physically meaningful PM2.5 sources: cat cracking operations, a source predominantly comprised of crustal material, industrial high temperature operations, oil combustion, and sea spray. These five sources accounted for 82% of the total mass of atmospheric fine particles (less carbon and sulfate). Factor analysis confirmed that emissions from cat cracking operations primarily contributed to REE enrichment in PM2.5 even though they comprised only 2.0% of the apportioned mass. Results from this study demonstrate the need to characterize catalysts employed in the vicinity of the sampling stations to accurately determine local sources of atmospheric REEs.