Steven D. Kohl

The IMPROVE_A Temperature Protocol for Thermal/Optical Carbon Analysis: Maintaining Consistency with a Long-Term Database

Abstract Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 °C for OC1, 280 °C for OC2, 480 °C for OC3, and 580 °C for OC4 in a helium (He) carrier gas and 580 °C for EC1, 740 °C for EC2, and 840 °C for EC3 in a 98% He/2% oxygen (O2) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O2 in the pure He carrier gas shows that O2 levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.

Molecular composition of organic fine particulate matter in Houston, TX

Organic fine particulate matter collected in Houston, TX between March 1997 and March 1998 was analyzed to determine the concentration of individual organic compounds. Samples from four sites were analyzed including two industrial locations (Houston Regional Monitoring Corporation (HRM-3) site in Channelview and Clinton Drive site near the Ship Channel Turning Basin), one suburban location (Bingle Drive site in Northwest Houston) and one background site (Galveston Island). At the three urban locations, samples were divided into three seasonal sample aggregates (spring, summer and winter), while at the background site a single annual average sample pool was used. Between 10 and 16 individual samples were pooled to get aggregate samples with enough organic carbon mass for analysis. Overall, 82 individual organic compounds were quantified. These include molecular markers which are compounds unique to specific fine particle sources and can be used to track the relative contribution of source emissions to ambient fine particle levels. The differences both spatially and temporally in these tracers can be used to evaluate the variability in emission source strengths.

Middle- and neighborhood-scale variations of PM10 source contributions in Las Vegas, Nevada

The Las Vegas Valley PM10 Study was conducted during 1995 to determine the contributions to PM10 aerosol from fugitive dust, motor vehicle exhaust, residential wood combustion, and secondary aerosol sources. Twenty-four-hr PM10 samples were collected at two neighborhood-scale sites every sixth day for 13 months. Five week-long intensive studies were conducted over a middle-scale sub-region at 29 locations that contained many construction projects emitting fugitive dust. The study found that the zone of influence around individual emitters was less than 1 km. Most of the sampling sites in residential and commercial areas yielded equivalent PM10 concentrations in the neighborhood region, even though they were more distant from each other than they were from the nearby construction sources. Based on chemical mass balance (CMB) receptor modeling, fugitive dust accounted for 80-90% of the PM10, and motor vehicle exhaust accounted for 3-9% of the PM10 in the Las Vegas Valley.

The Treasure Valley secondary aerosol study I: measurements and equilibrium modeling of inorganic secondary aerosols and precursors for southwestern Idaho

Abstract The SCAPE2 aerosol equilibrium model was applied to measured concentrations of PM2.5 aerosol and precursor gases. Ambient measurements in the Treasure Valley, Idaho were collected during stagnation episodes between December 1999 and March 2000 when conditions were favorable for the formation of secondary inorganic aerosol. SCAPE2 results agreed well with measurements for the episodes tested; Monte Carlo simulation using the uncertainties of the model input variables indicated that discrepancies between measured and modeled results were within the range of analytical precision. Air pollution control strategies were evaluated by perturbing the model input concentrations of total sulfate, nitrate, and ammonium. The largest reductions in secondary aerosol concentrations occurred when total nitrate was reduced, indicating that the formation of ammonium nitrate was limited by the availability of nitrate.

Overview of Real-World Emission Characterization Methods

Abstract Real-world emissions do not necessarily correspond with those derived from certification tests, owing to changes in equipment, fuels, and operating cycles. Therefore, emission rates from sources that affect ambient air quality are needed to drive air quality models and to provide accountability for air quality management strategies. Since the early 1960s, source characterization methods have been established that quantify emission rates to certify sources and determine their compliance over time. However, these certification and compliance methods have not been adapted to changes in emission processes and controls nor have they incorporated advances in measurement technology. This results in source tests that are incompatible with each other and with ambient measurement methods. Source characterization methods need to be improved to better represent real-world hardware, operating conditions, and feedstocks and to obtain more information at lower costs. Hot-ducted exhaust can be cooled to ambient temperatures prior to measurement to better approximate emissions as they appear in the atmosphere. Engine exhaust can be characterized in situ with portable monitoring systems. A portable wind tunnel can characterize fugitive dust threshold suspension velocities, reservoir sizes, particle size distributions, and chemical profiles.

Characterization of PM2.5 and PM10 fugitive dust source profiles in the Athabasca Oil Sands Region

Geological samples were collected from 27 representative locations in the Athabasca Oil Sands Region (AOSR) in Alberta, Canada. These samples were resuspended onto filter substrates for PM2.5 and PM10 size fractions. Samples were analyzed for 229 chemical species, consisting of elements, ions, carbon, and organic compounds. These chemical species are normalized to gravimetric mass to derive individual source profiles. Individual profiles were grouped into six categories typical of those used in emission inventories: paved road dust, unpaved road dust close to and distant from oil sand operations, overburden soil, tailings sands, and forest soils. Consistent with their geological origin, the major components are minerals, organic and elemental carbon, and ions. The sum of five major elements (i.e., Al, Si, K, Ca, and Fe) and their oxidized forms account for 25–40% and 45–82% of particulate matter (PM) mass, respectively. Si is the most abundant element, averaging 17–18% in the Facility (oil sand operations) and 23–27% in the Forest profiles. Organic carbon is the second most abundant species, averaging 9–11% in the Facility and 5–6% in the Forest profiles. Elemental carbon abundance is 2–3 times higher in Facility than Forest profiles. Sulfate abundance is ~7 times higher in the Facility than in the Forest profiles. The ratios of cation/anion and base cation (sum of Na+, Mg2+, K+, and Ca2+)/nitrogen- and sulfur-containing ions (sum of NH4+, NO2-, NO3-, and SO42-) exceed unity, indicating that the soils are basic. Lead (Pb) isotope ratios of facility soils are similar to the AOSR stack and diesel emissions, while those of forest soils have much lower 206Pb/207Pb and 208Pb/207Pb ratios. High-molecular-weight n-alkanes (C25-C40), hopanes, and steranes are more than an order of magnitude more abundant in Facility than Forest profiles. These differences may be useful for separating anthropogenic from natural sources of fugitive dust at receptors. Implications: Several organic compounds typical of combustion emissions and bitumen are enriched relative to forest soils for fugitive dust sources near oil sands operations, consistent with deposition uptake by biomonitors. AOSR dust samples are alkaline, not acidic, indicating that potential acid deposition is neutralized. Chemical abundances are highly variable within emission inventory categories, implying that more specific subcategories can be defined for inventory speciation.

Composition of water-soluble organic carbon in non-urban atmospheric aerosol collected at the Storm Peak Laboratory

Environmental context The organic fraction of atmospheric aerosols is a complex mixture of thousands of species, which play an important role in many atmospheric processes, such as absorbing and scattering solar radiation. We analysed the water-soluble organic fraction of ambient aerosol samples, and quantified over 45 carboxylic acids, sugars, sugar anhydrides and sugar alcohols. The presence of fairly high concentrations of sugars and sugar-alcohols suggests a significant biological input (e.g. pollen, fungi and bacteria) to the water-soluble organic fraction of non-urban aerosols. Abstract Water-soluble organic constituents of PM2.5 aerosol (particulate matter with an aerodynamic diameter ≤2.5µm) have not been well characterised so far. The goal of this work was to perform quantitative analysis of individual water-soluble organic species in aerosol samples collected in July of 2010 at the Storm Peak Laboratory (3210m above sea level) located in the Colorado Park Range (Steamboat Springs, CO, USA). Aqueous extracts were combined into six composites and analysed for organic carbon (OC), water-soluble organic carbon (WSOC), water-insoluble OC, inorganic ions, organic acids, lignin derivatives, sugar-alcohols, sugars and sugar-anhydrates. Analysis of higher molecular weight water-soluble organics was done using ultrahigh resolution mass spectrometry. Approximately 2400 positive and 4000 negative ions were detected and assigned to monoisotopic molecular formulae in the mass range of 100–800Da. The higher number of negative ions reflects a predominant presence of highly oxidised organic compounds. Individual identified organic species represented up to 30% of the water-soluble organic mass (WSOM). The WSOM fractions of the low molecular weight organic acids, sugars and sugar alcohols were 3–12%, 1.0–16% and 0.4–1.9%. Significant amounts of arabitol, mannitol and oxalic acid are most likely associated with airborne fungal spores and conidia that were observed on the filters using high resolution electron microscopy. Overall, higher concentrations of sugars (glucose, sucrose, fructose etc.) in comparison with biomass burning tracer levoglucosan indicate that a significant mass fraction of WSOC is related to airborne biological species.

Light absorption by black sand dust.

Light absorption by fine and coarse aerosols derived from Hawaiian black sand was determined by light transmission. The real part of the refractive index of this material was measured directly, and the imaginary part was estimated. The measured light absorption coefficients (B(ap)) were adjusted for multiple scattering artifacts by use of absorption-to-extinction ratios estimated with Mie theory. The best agreement between calculated and measured fine and coarse B(ap) was achieved with a value of 0.014 for the imaginary part of the refractive index. The corresponding absorption efficiencies for the fine and coarse black sand aerosols were 0.22 and 0.09 m(2)/g, respectively.

Hong Kong Vehicle Emission Changes from 2003 to 2015 in the Shing Mun Tunnel

ABSTRACT This study characterized motor vehicle emission rates and compositions in Hong Kongs Shing Mun tunnel (SMT) during 2015 and compared them to similar measurements from the same tunnel in 2003. Average PM2.5 concentrations in the SMT decreased by ∼70% from 229.1 ± 22.1 µg/m3 in 2003 to 74.2 ± 2.1 µg/m3 in 2015. Both PM2.5 and sulfur dioxide (SO2) emission factors (EFD) were reduced by ∼80% and total non-methane (NMHC) hydrocarbons EFD were reduced by 44%. These reductions are consistent with long-term trends of roadside ambient concentrations and emission inventory estimates, indicating the effectiveness of emission control measures. EFD changes between 2003 and 2015 were not statistically significant for carbon monoxide (CO), ammonia (NH3), and nitrogen oxides (NOx). Tunnel nitrogen dioxide (NO2) concentrations and NO2/NOx volume ratios increased, indicating an increased NO2 fraction in the primary vehicle exhaust emissions. Elemental carbon (EC) and organic matter (OM) were the most abundant PM2.5 constituents, with EC and OM, respectively, contributing to 51 and 31% of PM2.5 in 2003, and 35 and 28% of PM2.5 in 2015. Average EC and OM EFD decreased by ∼80% from 2003 to 2015. The sulfate EFD decreased to a lesser degree (55%) and its contribution to PM2.5 increased from 10% in 2003 to 18% in 2015, due to influences from ambient background sulfate concentrations. The contribution of geological materials to PM2.5 increased from 2% in 2003 to 5% in 2015, signifying the importance of non-tailpipe emissions.

Air Quality Scoping Study for Ash Meadows National Wildlife Refuge, Nevada (EMSI April 2007)

The Desert Research Institute (DRI) is performing a scoping study as part of the U.S.Department of Energy’s Yucca Mountain Environmental Monitoring Systems Initiative (EMSI). The main objective is to obtain baseline air quality information for Yucca Mountain and an area surrounding the Nevada Test Site (NTS). Air quality and meteorological monitoring and sampling equipment housed in a mobile trailer (shelter) is collecting data at seven sites outside the NTS, including Ash Meadows National Wildlife Refuge, Sarcobatus Flat, Beatty, Rachel, Caliente, Pahranagat National Wildlife Refuge, and Crater Flat, and at four sites on the NTS. The trailer is stationed at any one site for approximately eight weeks at a time. Letter reports provide summaries of air quality and meteorological data, on completion of each site’s sampling program.