Michael R. Olson

Size-Segregated Inorganic and Organic Components of PM in the Communities of the Los Angeles Harbor

The Los Angeles Ports complex consists of the port of Long Beach and the port of Los Angeles. Due to the high levels of particulate matter (PM) emitted from many sources in the vicinity of these ports and to their projected massive expansion, the Harbor area will be the focus of future governmental regulations. This study aims to characterize the physicochemical properties of PM at locations influenced by port-affiliated sources. PM samples were collected concurrently at six sites in the southern Los Angeles basin for a 7 week period between March and May 2007. Four sites were set-up within the communities of Wilmington and Long Beach; one site was located at a background location near the harbors of the Los Angeles port; the sixth site, near downtown Los Angeles, was chosen to represent a typical urban area. Coarse (PM 2.5 − 10 ), accumulation (PM 0.25 − 2.5 ), and quasi-ultrafine (PM 0.25 ) mode particles were collected at each site. Samples were analyzed for organic and elemental carbon content (OC and EC, respectively), organic species, inorganic ions, water soluble and total elements. The carbon preference index (CPI) for quasi-UF and accumulation mode particles varied from 0.65 to 1.84 among sites, which is in the range of previous findings in areas with high influence of anthropogenic sources. The ratio of hopanes to EC and hopanes to OC over all the sites were in the range of previous roadside measurements near freeways with variable volumes of diesel truck traffic. High overall correlation of vanadium with nickel (R = 0.9) and a considerable gradient of vanadium centrations with distance to the port, suggest marine vessels as the major sources of these elements.

Investigation of black and brown carbon multiple‐wavelength‐dependent light absorption from biomass and fossil fuel combustion source emissions

Quantification of the black carbon (BC) and brown carbon (BrC) components of source emissions is critical to understanding the impact combustion aerosols have on atmospheric light absorption. Multiple-wavelength absorption was measured from fuels including wood, agricultural biomass, coals, plant matter, and petroleum distillates in controlled combustion settings. Filter-based absorption measurements were corrected and compared to photoacoustic absorption results. BC absorption was segregated from the total light extinction to estimate the BrC absorption from individual sources. Results were compared to elemental carbon (EC)/organic carbon (OC) concentrations to determine compositions impact on light absorption. Multiple-wavelength absorption coefficients, Angstrom exponent (6.9 to 0.9 OC/TC), source emissions have variable absorption spectra, and nonbiomass combustion sources can be significant contributors to BrC.

Sensitivity of diesel particulate material emissions and composition to blends of petroleum diesel and biodiesel fuel

A number of investigations have examined the impact of the use of biodiesel on the emissions of carbon dioxide and regulated emissions, but limited information exists on the chemical composition of particulate matter from diesel engines burning biodiesel blends. This study examines the composition of diesel particulate matter (DPM) emissions from a commercial agriculture tractor burning a range of biodiesel blends operating under a load that is controlled by a power take off (PTO) dynamometer. Ultra-low sulfur diesel (ULSD) fuel was blended with soybean and beef tallow based biodiesel to examine fuels containing 0% (B0), 25% (B25), 50% (B50), 75% (B75), and 100% (B100) biodiesel. Samples were then collected using a dilution source sampler to simulate atmospheric dilution. Diluted and aged exhaust was analyzed for particle mass and size distribution, PM2.5 particle mass, PM2.5 organic and elemental carbon, and speciated organic compounds. PM2.5 mass emissions rates for the B25, B50, and B75 soybean oil biodiesel mixtures had 20%–30% lower emissions than the petroleum diesel, but B100 emissions were about 40% higher than the petroleum diesel. The trends in mass emission rates with the increasing biodiesel content can be explained by a significant decrease in elemental carbon (EC) emissions across all blending ranges and increasing organic carbon (OC) emissions with pure biodiesel. Beef tallow biodiesel blends showed similar trends. Nevertheless, it is important to note that the study measurements are based on low dilution rates and the OC emissions changes may be affected by ambient temperature and different dilution conditions spanning micro-environments and atmospheric conditions. The results show that the use of biodiesel fuel for economic or climate change mitigation purposes can lead to reductions in PM emissions and a co-benefit of EC emission reductions. Detailed speciation of the OC emissions were also examined and are presented to understand the sensitivity of OC emissions with respect to biodiesel fuel blends. Copyright 2012 American Association for Aerosol Research

Climate Sensitivity of Gaseous Elemental Mercury Dry Deposition to Plants: Impacts of Temperature, Light Intensity, and Plant Species

Foliar accumulations of gaseous elemental mercury (GEM) were measured in three plant species between nominal temperatures of 10 and 30 °C and nominal irradiances of 0, 80, and 170 W m(-2) (300 nm-700 nm) in a 19 m(3) controlled environment chamber. The plants exposed were as follows: White Ash (Fraxinus americana; WA); White Spruce (Picea glauca; WS); and Kentucky Bluegrass (Poa partensis; KYBG). Foliar enrichments in the mercury stable isotope ((198)Hg) were used to measure mercury accumulation. Exposures lasted for 1 day after which the leaves were digested in hot acid and the extracted mercury was analyzed with ICPMS. Resistances to accumulative uptake by leaves were observed to be dependent on both light and temperature, reaching minima at optimal growing conditions (20 °C; 170 W m(-2) irradiance between 300-700 nm). Resistances typically increased at lower (10 °C) and higher (30 °C) temperatures and decreased with higher intensities of irradiance. Published models were modified and used to interpret the trends in stomatal and leaf interior resistances to GEM observed in WA. The model captured the experimental trends well and revealed that stomatal and internal resistances were both important across much of the temperature range. At high temperatures, however, stomatal resistance dominated due to increased water vapor pressure deficits. The resistances measured in this study were used to model foliar accumulations of GEM at a northern US deciduous forest using atmospheric mercury and climate measurements made over the 2003 growing season. The results were compared to modeled accumulations for GEM, RGM, and PHg using published deposition velocities. Predictions of foliar GEM accumulation were observed to be a factor of 5-10 lower when the temperature and irradiance dependent resistances determined in this study were used in place of previously published data. GEM uptake by leaves over the growing season was shown to be an important deposition pathway (2.3-3.7 μg m(-2) of one-sided leaf area; OSLA) when compared to total mercury wet deposition (1.2 μg m(-2) OSLA) and estimates of reactive mercury dry deposition (0.1-6 μg m(-2) OSLA). Resistance-Temperature-Irradiance relationships are provided for use in models.

The effects of emission control strategies on light-absorbing carbon emissions from a modern heavy-duty diesel engine

Control of atmospheric black carbon (BC) and brown carbon (BrC) has been proposed as an important pathway to climate change mitigation, but sources of BC and BrC are still not well understood. In order to better identify the role of modern heavy-duty diesel engines on the production of BC and BrC, emissions from a heavy-duty diesel engine operating with different emission control strategies were examined using a source dilution sampling system. The effect of a diesel oxidation catalyst (DOC) and diesel particulate filter (DPF) on light-absorbing carbon (LAC) was evaluated at three steady-state engine operation modes: idle, 50% speed and load, and 100% speed and load. LAC was measured with four different engine configurations: engine out, DOC out, DPF out, and engine out with an altered combustion calibration. BC and BrC emission rates were measured with the Aethalometer (AE-31). EC and BC emission rates normalized to the mass of CO2 emitted increased with increasing engine speed and load. Emission rates normalized to brake-specific work did not exhibit similar trends with speed and load, but rather the highest emission rate was measured at idle. EC and OC emissions were reduced by 99% when the DOC and DPF architecture was applied. The application of a DPF was equally effective at removing 99% of the BC fraction of PM, proving to be an important control strategy for both LAC and PM. BC emissions were unexpectedly increased across the DOC, seemingly due to a change aerosol optical properties. Removal of exhaust gas recirculation (EGR) flow due to simulated EGR cooler failure caused a large increase in OC and BrC emission rates at idle, but had limited influence during high load operation. LAC emissions proved to be sensitive to the same control strategies effective at controlling the total mass of diesel PM. Implications: In the context of black carbon emissions, very small emission rates of brown carbon were measured over a range of control technologies and engine operating conditions. During specific idle engine operation without EGR and adjusted fueling conditions, brown carbon can be formed in significant amounts, requiring careful management tactics. Control technologies for particulate matter are very effective for light-absorbing carbon, reducing black carbon emissions to near zero for modern engines equipped with a DPF. Efforts to control atmospheric brown carbon need to focus on other sources other than modern diesel engines, such as biomass burning.

Temporal variations of black carbon during haze and non-haze days in Beijing

Black carbon (BC) aerosol has been identified as one of key factors responsible for air quality in Beijing. BC emissions abatement could help slow regional climate change while providing benefits for public health. In order to quantify its variations and contribution to air pollution, we systematically studied real-time measurements of equivalent black carbon (eBC) in PM2.5 aerosols at an urban site in Beijing from 2010 to 2014. Equivalent black carbon (eBC) is used instead of black carbon (BC) for data derived from Aethalometer-31 measurement. Equivalent BC concentrations showed significant temporal variations with seasonal mean concentration varying between 2.13 and 5.97 μg m−3. The highest concentrations of eBC were found during autumn and winter, and the lowest concentrations occurred in spring. We assessed the temporal variations of eBC concentration during haze days versus non-haze days and found significantly lower eBC fractions in PM2.5 on haze days compared to those on non-haze days. Finally, we observed a clear inverse relationship between eBC and wind speed. Our results show that wind disperses PM2.5 more efficiently than eBC; so, secondary aerosols are not formed to the same degree as primary aerosols over the same transport distance during windy conditions.

Understanding the sources and composition of the incremental excess of fine particles across multiple sampling locations in one air shed

Well-designed health studies and the development of effective regulatory policies need to rely on an understanding of the incremental differences in particulate matter concentrations and their sources. Although only a limited number of studies have been conducted to examine spatial differences in sources to particulate matter within an air shed, routine monitoring data can be used to better understand these differences. Measurements from the US EPA Chemical Speciation Network (CSN) collected between 2002-2008 were analyzed to demonstrate the utility of regulatory data across three sites located within 100 km of each other. Trends in concentrations, source contribution, and incremental excesses across three sites were investigated using the Positive Matrix Factorization model. Similar yearly trends in chemical composition were observed across all sites, however, excesses of organic matter and elemental carbon were observed in the urban center that originated from local emissions of mobile sources and biomass burning. Secondary sulfate and secondary nitrate constituted over half of the PM2.5 with no spatial differences observed across sites. For these components, the excess of emissions from industrial sources could be directly quantified. This study demonstrates that CSN data from multiple sites can be successfully used to derive consistent source profiles and source contributions for regional pollution, and that CSN data can be used to quantify incremental differences in source contributions of across these sites. The analysis strategy can be used in other regions of the world to take advantage of existing ambient particulate matter monitoring data to better the understanding of spatial differences in source contributions within a given air shed.

Atmospheric impacts of black carbon emission reductions through the strategic use of biodiesel in California.

The use of biodiesel as a replacement for petroleum-based diesel fuel has gained interest as a strategy for greenhouse gas emission reductions, energy security, and economic advantage. Biodiesel adoption may also reduce particulate elemental carbon (EC) emissions from conventional diesel engines that are not equipped with after-treatment devices. This study examines the impact of biodiesel blends on EC emissions from a commercial off-road diesel engine and simulates the potential public health benefits and climate benefits. EC emissions from the commercial off-road engine decreased by 76% when ultra-low sulfur commercial diesel (ULSD) fuel was replaced by biodiesel. Model calculations predict that reduced EC emissions translate directly into reduced EC concentrations in the atmosphere, but the concentration of secondary particulate matter was not directly affected by this fuel change. Redistribution of secondary particulate matter components to particles emitted from other sources did change the size distribution and therefore deposition rates of those components. Modification of meteorological variables such as water content and temperature influenced secondary particulate matter formation. Simulations with a source-oriented WRF/Chem model (SOWC) for a severe air pollution episode in California that adopted 75% biodiesel blended with ULSD in all non-road diesel engines reduced surface EC concentrations by up to 50% but changed nitrate and total PM2.5 mass concentrations by less than ±5%. These changes in concentrations will have public health benefits but did not significantly affect radiative forcing at the top of the atmosphere. The removal of EC due to the adoption of biodiesel produced larger coatings of secondary particulate matter on other atmospheric particles containing residual EC leading to enhanced absorption associated with those particles. The net effect was a minor change in atmospheric optical properties despite a large change in atmospheric EC concentrations. These results emphasize the importance of considering EC mixing state in climate research.

Quantification of elemental and organic carbon in atmospheric particulate matter using color space sensing—hue, saturation, and value (HSV) coordinates

A fast and cost effective application of color sensing was used to quantify color coordinates of atmospheric particulate matter collected on filters to quantify elemental and organic carbon (EC/OC) loading. This is a unique and novel approach for estimating OC composition. The method used a colorimeter and digital photography to obtain XYZ color space values and mathematically transformed them to HSV cylindrical-coordinates; a quantification method was applied to estimate the NIOSH and IMPROVE (TOR) EC/OC loadings from a set of globally diverse PM samples. When applied to 315 samples collected at three US EPA Chemical Speciation Network (CSN) sampling sites, the HSV model proved to be a robust method for EC measurement with an R(2)=0.917 for predicted versus measured loading results and a CV(RMSE)=16.1%. The OC quantified from the same sample filters had an R(2)=0.671 and a CV(RMSE)=24.8% between the predicted and measured results. The method was applied to NIOSH EC/OC results from a set of samples from rural China, Bagdad, and the San Joaquin Valley, CA, and the EC and OC CV(RMSE) were 30.8% and 49.3%, respectively. Additionally, the method was applied to samples with color quantified by a digital photographic image (DPI) with EC results showing good agreement with a CV(RMSE) of 22.6%. OC concentrations were not captured as accurately with the DPI method, with a CV(RMSE) of 77.5%. The methods low analytical cost makes it a valuable tool for estimating EC/OC exposure in developing regions and for large scale monitoring campaigns.

Source apportionment of PM 2.5 organic carbon in the San Joaquin Valley using monthly and daily observations and meteorological clustering

Two hundred sixty-three fine particulate matter (PM2.5) samples collected on 3-day intervals over a 14-month period at two sites in the San Joaquin Valley (SJV) were analyzed for organic carbon (OC), elemental carbon (EC), water soluble organic carbon (WSOC), and organic molecular markers. A unique source profile library was applied to a chemical mass balance (CMB) source apportionment model to develop monthly and seasonally averaged source apportionment results. Five major OC sources were identified: mobile sources, biomass burning, meat smoke, vegetative detritus, and secondary organic carbon (SOC), as inferred from OC not apportioned by CMB. The SOC factor was the largest source contributor at Fresno and Bakersfield, contributing 44% and 51% of PM mass, respectively. Biomass burning was the only source with a statistically different average mass contribution (95% CI) between the two sites. Wintertime peaks of biomass burning, meat smoke, and total OC were observed at both sites, with SOC peaking during the summer months. Exceptionally strong seasonal variation in apportioned meat smoke mass could potentially be explained by oxidation of cholesterol between source and receptor and trends in wind transport outlined in a Residence Time Analysis (RTA). Fast moving nighttime winds prevalent during warmer months caused local emissions to be replaced by air mass transported from the San Francisco Bay Area, consisting of mostly diluted, oxidized concentrations of molecular markers. Good agreement was observed between SOC derived from the CMB model and from non-biomass burning WSOC mass, suggesting the CMB model is sufficiently accurate to assist in policy development. In general, uncertainty in monthly mass values derived from daily CMB apportionments were lower than that of CMB results produced with monthly marker composites, further validating daily sampling methodologies. Strong seasonal trends were observed for biomass and meat smoke OC apportionment, and monthly mass averages had lowest uncertainty when derived from daily CMB apportionments.