Insights into PM10 sources in Houston, Texas: Role of petroleum refineries in enriching lanthanoid metals during episodic emission events

Petroleum refineries may emit large quantities of pollutants during non-routine operations that include start-ups and shutdowns, planned maintenance, and unplanned equipment failures. The Texas Commission on Environmental Quality (TCEQ) tracks such events by requiring industries to self-report estimates of these emissions because they often have a detrimental impact on local air quality and potentially, public health. An inventory of non-routine episodic emission events is available via TCEQʹs website. However, there is on-going concern that such episodic emissions are sometimes under-reported or even not cataloged. Herein, we present concentrations of 42 main group, transition, and lanthanoid elements in 114 time-resolved (3 or 6 h) samples collected over a 1-month period. We also develop strategies to identify aerosol sources using elemental tracers and compare source apportionment (performed by positive matrix factorization) based on ambient measurements to inventoried non-routine emission events. Through interpretation of key marker elements, five sources impacting concentrations of metals in PM10 were identified and calculated to contribute 73% of the measured PM10 mass. On average, primary emissions from fluidized-bed catalytic cracking (FCC) units negligibly contributed to apportioned PM10 mass. However, 35 samples were identified as impacted by transient PM10 emissions from FCC units because of elevated levels of lanthanoid metals and their ratios. Only 31 of these 35 samples coincided with self-reported non-routine emission events. Further, roughly half of the emission event self-reports detailed only emissions of gaseous pollutants. Based on this, we posit that not all PM10 emission events are reported and even self-reported emission events are incomplete – those that only catalog gaseous pollutants may also include unreported PM emissions.