R. Bahreini

Evaluation of Composition-Dependent Collection Efficiencies for the Aerodyne Aerosol Mass Spectrometer using Field Data

In recent years, Aerodyne aerosol mass spectrometers (AMS) have been used in many locations around the world to study the size-resolved, nonrefractory chemical composition of ambient particles. In order to obtain quantitative data, the mass or (number) of particles detected by the AMS relative to the mass (or number) of particles sampled by the AMS, i.e., the AMS collection efficiency (CE) must be known. Previous studies have proposed and used parameterizations of the AMS CE based on the aerosol composition and sampling line relative humidity. Here, we evaluate these parameterizations by comparing AMS mass concentrations with independent measurements of fine particle volume or particle-into-liquid sampler (PILS) ion chromatography measurements for 3 field campaigns with different dominant aerosol mixtures: (1) acidic sulfate particles, (2) aerosol containing a high mass fraction of ammonium nitrate, and (3) aerosol composed of primarily biomass burning emissions. The use of the default CE of 0.5 for all campaigns resulted in 81–90% of the AMS speciated and total mass concentrations comparing well with fine particle volume or PILS measurements within experimental uncertainties, with positive biases compared with a random error curve. By using composition-dependent CE values (sometimes as a function of size) which increased the CE for the above aerosol types, the fraction of data points within the measurement uncertainties increased to more than 92% and the mass concentrations decreased by ∼5–15% on an average. The CE did not appear to be significantly dependent on changes in organic mass fraction although it was substantial in the 3 campaigns (47, 30, and 55%). Copyright 2012 American Association for Aerosol Research

Biomass burning in Siberia and Kazakhstan as an important source for haze over the Alaskan Arctic in April 2008

[1]xa0During the ARCPAC (Aerosol, Radiation, and Cloud Processes affecting Arctic Climate) airborne field experiment in April 2008 in northern Alaska, about 50 plumes were encountered with the NOAA WP-3 aircraft between the surface and 6.5 km. Onboard measurements and the transport model FLEXPART showed that most of the plumes were emitted by forest fires in southern Siberia-Lake Baikal area and by agricultural burning in Kazakhstan-southern Russia. Unexpectedly, these biomass burning plumes were the dominant aerosol and gas-phase features encountered in this area during April. The influence on the plumes from sources other than burning was small. The chemical characteristics of plumes from the two source regions were different, with higher enhancements relative to CO for most gas and aerosol species from the agricultural fires. In 2008, the fire season started earlier than usual in Siberia, which may have resulted in unusually efficient transport of biomass burning emissions into the Arctic.

Organic aerosol formation in urban and industrial plumes near Houston and Dallas, Texas

[1]xa0We present measurements of organic aerosol (OA) in urban plumes from Houston and Dallas/Fort Worth as well as in industrial plumes in the Houston area during TexAQS-2006. Consistent with the TexAQS-2000 study, measurements show greater amount of aerosol mass downwind of the industrial centers compared to urban areas. This is likely due to higher emission and processing of volatile organic compounds (VOCs) from the industrial sources along the Houston ship channel. Comparisons of the current measurements with observations from the northeastern (NE) United States indicate that the observed ratios of the enhancement above background in OA, ΔOA, to the enhancement above background in CO, ΔCO, downwind of urban centers of Houston and Dallas/Fort Worth are within a factor of 2 of the same values in plumes from urban areas in the NE United States. In the ship channel plumes, ΔOA/ΔCO exceeds that in the urban areas by factors ranging from 1.5 to 7. We use a chemical box model to simulate secondary organic aerosol (SOA) formation from anthropogenic and biogenic VOCs in different plumes using recently reported dependencies of SOA yields on VOC/NOx ratios. Modeled SOA to CO enhancement ratios are within a factor of 2 of measurements. The increase in SOA from biogenic VOCs (BVOCs) predicted by the chemical box model as well as by a separate analysis using a Lagrangian particle dispersion model (FLEXPART) is <0.7 μg per standard m3 (sm−3). We find no evidence for a substantial influence of BVOCs on OA formation in our measurements in Houston area.

A volatility basis set model for summertime secondary organic aerosols over the eastern United States in 2006

[1]xa0A new secondary organic aerosol (SOA) parameterization based on the volatility basis set is implemented in a regional air quality model WRF-CHEM. Full meteorological and chemistry simulations are carried out for the United States for August–September 2006. Predicted organic aerosol (OA) concentrations are compared against surface measurements made by several networks and aircraft data from the TexAQS-2006 field campaign. Elemental carbon simulations are also evaluated in order to evaluate the models ability to capture their emissions, transport, and removal. Certain measurement limitations, such as daily averaged OA concentrations, impose some difficulties on the model evaluation, and hourly averaged OA measurements provide more informative constraints compared to daily concentrations. The updated model demonstrates a significant improvement in simulating the OA concentrations compared to the standard WRF-CHEM, which predicts very little SOA. The improvement in organic carbon (OC) predictions is noticeable in correlations and model bias. The correlations of OC exceed that of the persistence forecasts for hourly concentrations in the southeast United States during daytime. The updated traditional SOA yields still lead to an underestimation of observed OA, while addition of the multigenerational volatile organic compound (VOC) oxidation drastically improves model performance. However, several key uncertainties remain in SOA formation and loss mechanisms, which are characterized through several perturbation simulations. Dry deposition of VOC oxidation products is an important factor in the atmospheric SOA budget. The combination of the biogenic VOC emissions, updated SOA yields, and aging mechanism result in biogenic SOA being the dominant OA component for much of the nonurban United States.

Design and Operation of a Pressure-Controlled Inlet for Airborne Sampling with an Aerodynamic Aerosol Lens

Two pressure-controlled inlets (PCI) have been designed and integrated into the Aerodyne Aerosol Mass Spectrometer (AMS) inlet system containing an aerodynamic aerosol lens system for use in airborne measurements. Laboratory experiments show that size calibration and mass flow rate into the AMS are not affected by changes in upstream pressure (P 0 ) of the PCI as long as the pressure within the PCI chamber (P PCI ) is controlled to values lower than P 0 . Numerous experiments were conducted at different P PCI , P 0 , and AMS lens pressures (P Lens ) to determine particle transmission efficiency into the AMS. Based on the results, optimum operating conditions were selected which allow for constant pressure sampling with close to 100% transmission efficiency of particles in the size range of ∼ 100–700 nm vacuum aerodynamic diameter (d va ) at altitudes up to ∼ 6.5 km. Data from an airborne field study are presented for illustration.

Reactive uptake coefficients for N2O5 determined from aircraft measurements during the Second Texas Air Quality Study: Comparison to current model parameterizations

[1]xa0This paper presents determinations of reactive uptake coefficients for N2O5, γ(N2O5), on aerosols from nighttime aircraft measurements of ozone, nitrogen oxides, and aerosol surface area on the NOAA P-3 during Second Texas Air Quality Study (TexAQS II). Determinations based on both the steady state approximation for NO3 and N2O5 and a plume modeling approach yielded γ(N2O5) substantially smaller than current parameterizations used for atmospheric modeling and generally in the range 0.5–6 × 10−3. Dependence of γ(N2O5) on variables such as relative humidity and aerosol composition was not apparent in the determinations, although there was considerable scatter in the data. Determinations were also inconsistent with current parameterizations of the rate coefficient for homogenous hydrolysis of N2O5 by water vapor, which may be as much as a factor of 10 too large. Nocturnal halogen activation via conversion of N2O5 to ClNO2 on chloride aerosol was not determinable from these data, although limits based on laboratory parameterizations and maximum nonrefractory aerosol chloride content showed that this chemistry could have been comparable to direct production of HNO3 in some cases.

Ammonia sources in the California South Coast Air Basin and their impact on ammonium nitrate formation

[1]xa0Observations from the NOAA WP-3D aircraft during CalNex in May and June 2010 are used to quantify ammonia (NH3) emissions from automobiles and dairy facilities in the California South Coast Air Basin (SoCAB) and assess their impact on particulate ammonium nitrate (NH4NO3) formation. These airborne measurements in the SoCAB are used to estimate automobile NH3 emissions, 62xa0±xa024 metric tons day−1, and dairy facility NH3 emissions, 33xa0±xa016 to 176xa0±xa088 metric tons day−1. Emission inventories agree with the observed automobile NH3:CO emission ratio, but substantially underpredict dairy facility NH3 emissions. Conditions observed downwind of the dairy facilities were always thermodynamically favorable for NH4NO3 formation due to high NH3 mixing ratios from the concentrated sources. Although automobile emissions generated lower NH3 mixing ratios, they also can thermodynamically favor NH4NO3 formation. As an aerosol control strategy, addressing the dairy NH3 source would have the larger impact on reducing SoCAB NH4NO3 formation.

An investigation of ammonia and inorganic particulate matter in California during the CalNex campaign

Airborne observations from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign in May and June 2010 are used to investigate the role of ammonia (NH3) in fine particulate matter (PM2.5) formation and surface air quality in California and test the key processes relevant to inorganic aerosol formation in the GEOS-Chem model. Concentrations of ammonia throughout California, sulfur dioxide (SO2) in the Central Valley, and ammonium nitrate in the Los Angeles (LA) area are underestimated several-fold in the model. We find that model concentrations are relatively insensitive to uncertainties in gas-particle partitioning and deposition processes in the region. Conversely, increases to anthropogenic livestock ammonia emissions (by a factor of 5) and anthropogenic sulfur dioxide emissions in the Central Valley (by a factor of 3–10) and a reduction of anthropogenic NOx emissions (by 30%) substantially reduce the bias in the simulation of gases (SO2, NH3, HNO3) throughout California and PM2.5 near LA, although the exact magnitudes of emissions in the region remain uncertain. Using these modified emissions, we investigate year-round PM2.5 air quality in California. The model reproduces the wintertime maximum in surface ammonium nitrate concentrations in the Central Valley (regional mean concentrations are three times higher in December than in June), associated with lower planetary boundary layer heights and colder temperatures, and the wintertime minimum in the LA region (regional mean concentrations are two times higher in June than December) associated with ammonia limitation. Year round, we attribute at least 50% of the inorganic PM2.5 mass simulated throughout California to anthropogenic ammonia emissions.

Evolution of aerosol properties impacting visibility and direct climate forcing in an ammonia-rich urban environment

[1]xa0Airborne measurements of sub-micron aerosol and trace gases downwind of Los Angeles are used to investigate the influence of aging on aerosol properties relevant to climate forcing and visibility. The analysis focuses on the Los Angeles plume, which in addition to strong urban emissions is influenced by local agricultural emissions. Secondary organic aerosol formation and repartitioning of semi-volatile ammonium nitrate were identified as key factors controlling the optical behavior observed. For one case study, ammonium nitrate contributed up to 50% of total dry extinction. At 85% relative humidity, extinction in the fresh plume was enhanced by a factor of ∼1.7, and 60–80% of this was from water associated with ammonium nitrate. On this day, loss of ammonium nitrate resulted in decreasing aerosol hygroscopicity with aging. Failing to account for loss of ammonium nitrate led to overestimation of the radiative cooling exerted by the most aged aerosol by ∼35% under dry conditions. These results show that changes to aerosol behavior with aging can impact visibility and climate forcing significantly. The importance of ammonium nitrate and water also highlight the need to improve the current representation of semi-volatile aerosol species in large-scale climate models.

Relationship between photochemical ozone production and NOx oxidation in Houston, Texas

[1]xa0An instrumented aircraft was used to study anthropogenic emissions and subsequent ozone and reactive nitrogen photochemistry in the continental boundary layer downwind of Houston, Texas. Measurements of ozone, carbon monoxide, NOx, and NOx oxidation products were conducted from the NOAA WP-3 aircraft during the 2006 Texas Air Quality Study under a variety of meteorological conditions. Sixty-five crosswind transects of plumes from Houston urban and industrial areas performed on 10 daytime flights from 13 September to 6 October 2006 are examined. Coincident measurements of NOx and its oxidation products show that NOx was oxidized predominately to nitric acid and peroxy acyl nitrates on time scales of a few hours. The observed relationships between O3 and NOx oxidation products are affected by both photochemistry and mixing of different air masses. On four flights, background pollutant mixing ratios were constant and CO to NOy enhancement ratios in downwind plume transects remained at the emission ratio. The enhancement ratio of O3 to NOx oxidation products was also nearly constant and could be used to derive ozone production efficiency (OPE) in plumes downwind from the Houston area. On the other flights, variable mixing of regionally polluted background air with plumes caused CO to NOy and O3 to NOy − NOx enhancement ratios to increase as plumes were transported. In such cases, enhancement ratios do not solely reflect plume processing, and OPE could not be determined. The OPE averages 5.9 ± 1.2 in coalesced plumes from urban and petrochemical industrial sources in Houston, with higher values in isolated plumes downwind from petrochemical facilities located along the Houston ship channel.