Nicholas Spada

Multi-elemental characterization of tunnel and road dusts in Houston, Texas using dynamic reaction cell-quadrupole-inductively coupled plasma–mass spectrometry: Evidence for the release of platinum group and anthropogenic metals from motor vehicles

Platinum group elements (PGEs) including Rh, Pd, and Pt are important tracers for vehicular emissions, though their measurement is often challenging and difficult to replicate in environmental campaigns. These challenges arise from sample preparation steps required for PGE quantitation, which often cause severe isobaric interferences and spectral overlaps from polyatomic species of other anthropogenically emitted metals. Consequently, most previous road dust studies have either only quantified PGEs or included a small number of anthropogenic elements. Therefore a novel analytical method was developed to simultaneously measure PGEs, lanthanoids, transition and main group elements to comprehensively characterize the elemental composition of urban road and tunnel dusts. Dust samples collected from the vicinity of high-traffic roadways and a busy underwater tunnel restricted to single-axle (predominantly gasoline-driven) vehicles in Houston, TX were analyzed for 45 metals with the newly developed method using dynamic reaction cell-quadrupole-inductively coupled plasma-mass spectrometry (DRC-q-ICP-MS). Average Rh, Pd and Pt concentrations were 152±52, 770±208 and 529±130 ng g(-1) respectively in tunnel dusts while they varied between 6 and 8 ng g(-1), 10 and 88 ng g(-1) and 35 and 131 ng g(-1) in surface road dusts. Elemental ratios and enrichment factors demonstrated that PGEs in dusts originated from autocatalyst attrition/abrasion. Strong evidence is also presented for mobile source emissions of Cu, Zn, Ga, As, Mo, Cd, Sn, Sb, Ba, W and Pb. However, all other elements including rare earths most likely arose from weathering, erosion and resuspension of crustal material. These are the first such detailed measurements in Houston, the largest city in TX and fourth largest in the United States. We posit that such investigations will assist in better understanding PGE concentrations in urban environments while providing elemental data necessary to better understand anthropogenic influences on their biogeochemical cycling.

Very Fine and Ultrafine Metals and Ischemic Heart Disease in the California Central Valley 1: 2003–2007

The enhancement of mortality associated with cardiovascular and specifically ischemic heart disease (IHD) has been observed in the southern California Central Valley since at least 1990, and it continues to be a major source of mortality. While there is a strong statistical association of IHD with wintertime PM2.5 mass, the causal agents are uncertain. Medical studies identify some potential causal agents, such as very fine and ultrafine metals, but they have not been fully characterized in most Central Valley regions. To provide improved information on specific and potentially causal agents, a five site aerosol sampling transect was conducted from Redding to Bakersfield during a 17-day period of strong stagnation, January 5–22, 2009. Mass and elemental components were measured every 3 h in eight particle size modes, ranging from 10 to 0.09 μm, while the ultrafine particles (<0.09 μm) were collected on Teflon filters. Ancillary studies were performed including direct upwind–downwind profiles across a heavily traveled secondary street near a stoplight. Very fine and ultrafine iron, nickel, copper, and zinc were identified as vehicular, with the most probable sources being brake drums and pads and the lubrication oil additive zinc thiophosphate. High correlations, many with r 2 > 0.9, were found between these vehicular metals and IHD mortality, enhanced by the meteorology, terrain, and traffic patterns of the southern Central Valley. The braking systems of cars and trucks must now be considered along with direct exhaust emissions in estimating the health impacts from traffic.

Inorganic and organic aerosols downwind of California's Roseville Railyard

Inorganic and organic constituents of aerosols from a major railyard and repair facility were characterized to develop a profile of emissions from railyard activities. The railyard has very consistent downslope winds blowing laterally across the railyard for about 8 hours each night, so two sampling stations were used, one just upwind of the railyard and one downwind adjacent to the railyard fence line. Aerosol samples were collected by rotating drum impactors (DRUM and Lundgren) in up to 9 size modes for 5 weeks in summer and fall of 2005 in tandem with the Roseville Railyard Aerosol Monitoring Project (RRAMP), which measured, black carbon (BC) PM2, as well as NO and NO2. The DRUM aerosol samples were analyzed for mass, optical absorption, and elemental content in 3 h time resolution to allow separation of day and night. Organic analysis was conducted on another set of time integrated size-segregated samples taken by a Lundgren impactor during nighttime hours. The ratio between the downwind versus upwind sites at night was as high as 21.9 (NO, RRAMP) and 6.4 (optical absorption, DRUM) but many species had ratios greater than 2, demonstrating which aerosols arose from railyard activities. The main emissions from the railyard consisted of very fine (0.26 > D p > 0.09 μm) and ultrafine (<0.1 μm) aerosols associated with diesel exhaust such as mass, organic matter, transition metals, and sulfur, the latter 3.3% of the mass since locomotive diesel fuel still contained sulfur. There were also coarse soil aerosols contaminated with anthropogenic metals and petroleum-derived n-alkanes. The aerosol PAH (polycyclic aromatic hydrocarbons) profile showed higher proportions of the heavier PAHs, such as benzo[a]pyrene, compared to diesel truck exhaust on a per unit mass. These aerosols were mostly in the ultrafine (<0.1 μm) size mode, enhancing lung capture. These results and those of Roseville Railyard Aerosol Monitoring Project (RRAMP) largely confirm earlier California Air Resources Boards (ARB) model estimates of health impacts downwind of the railyard based on diesel exhaust, while adding data on very fine transition metals and contaminated soils, potentially important to human health.

A decreasing vanadium footprint of bunker fuel emissions

The Interagency Monitoring of Protected Visual Environments (IMPROVE) network measures the chemical composition of atmospheric particulate matter at over 160 locations throughout the United States. As part of the routine quality control process, we noted decreases in the network-wide vanadium (V) and nickel (Ni) concentrations in 2015 relative to the previous years. Enriched V and Ni with respect to soil are indicative of heavy fuel oil burning and are often used as tracers for emissions from marine vessels. Multiple regulations on the fuel used by marine vessels were implemented in North America since 2010, and the most sweeping regulation was implemented at the start of 2015. The 2015 regulations reduced the allowable fuel oil sulfur concentrations within the North America Emissions Control Area from 1.0% to 0.1% to reduce the environmental and human health impacts of sulfates. As a side effect, these requirements economically favored fuels with lower V and Ni concentrations. The atmospheric concentrations of V and Ni decreased markedly at many IMPROVE monitoring sites, particularly sites near major ports. Between 2011 and 2015, annual mean V concentrations measured on IMPROVE samples collected near the ports of Seattle, Washington and New Orleans, Louisiana decreased by 35% and 85%, respectively. These decreases have brought the coastal V and Ni concentrations much closer to those measured far inland.