Previously unaccounted atmospheric mercury deposition in a midlatitude deciduous forest.

Mercury is toxic to wildlife and humans, and forests are thought to be a globally important sink for gaseous elemental mercury (GEM) deposition from the atmosphere. Yet there are currently no annual GEM deposition measurements over rural forests. Here we present measurements of ecosystem-atmosphere GEM exchange using tower-based micrometeorological methods in a midlatitude hardwood forest. We measured an annual GEM deposition of 25.1 µg ⋅ m-2 (95% CI: 23.2 to 26.7 1 µg ⋅ m-2), which is five times larger than wet deposition of mercury from the atmosphere. Our observed annual GEM deposition accounts for 76% of total atmospheric mercury deposition and also is three times greater than litterfall mercury deposition, which has previously been used as a proxy measure for GEM deposition in forests. Plant GEM uptake is the dominant driver for ecosystem GEM deposition based on seasonal and diel dynamics that show the forest GEM sink to be largest during active vegetation growing periods and middays, analogous to photosynthetic carbon dioxide assimilation. Soils and litter on the forest floor are additional GEM sinks throughout the year. Our study suggests that mercury loading to this forest was underestimated by a factor of about two and that global forests may constitute a much larger global GEM sink than currently proposed. The larger than anticipated forest GEM sink may explain the high mercury loads observed in soils across rural forests, which impair water quality and aquatic biota via watershed Hg export.

Measurement of Light Absorbing Aerosols with Folded-Jamin Photothermal Interferometry.

In this study, a photothermal interferometer was developed, based on a folded-Jamin polarization instrument with refractive-index sensitive configuration, in order to characterize light-absorbing aerosols. The feasibility of our interferometric technique was demonstrated by performing photothermal spectroscopy characterizing spark-generated black carbon particles with atmospherically relevant concentrations and atmospheric aerosols in a metropolitan area. The sensitivity of this interferometric system for both laboratory-generated aerosols and atmospheric aerosols was ~ 1 (µg/m3)/µV, which is sufficient for the monitoring of black carbon aerosol in urban areas.

Beam characteristics of fiber-based supercontinuum light sources with mirror- and lens-based beam collimators.

Commercially available supercontinuum light sources that cover most of the solar spectrum are well suited for instrumentation, where a well-collimated beam with wide spectral coverage is needed. Typically, the optical power is emitted from a single-mode photonic-crystal fiber and the output can either be collimated using a proprietary, permanently integrated, lens-based collimator or with a customer-provided, off-axis parabolic mirror. Here, we evaluate both approaches and conclude that, superior beam quality and collimation over the whole spectral range can be obtained with an off-axis parabolic mirror, however at the price of a more complex and bulky system requiring additional user alignment.

Characterizing elemental, equivalent black, and refractory black carbon aerosol particles: a review of techniques, their limitations and uncertainties.

Elemental-, equivalent black- and refractory black-carbon are terms that have been defined in order to dissect the more general term, black carbon, into its component parts related to its specific chemical and optical properties and its impact on climate and health. Recent publications have attempted to clarify the meaning of these terms with respect to their environmental impact, particularly on climate. Here, we focus on the measurement aspects, reviewing the most commonly implemented techniques for the direct and indirect derivation of black carbon properties, their strengths, limitations, and uncertainties, and provide a non-exhaustive bibliography where the reader can find more detailed information. This review paper is designed as a guide for those wishing to learn about the current state of black carbon measurement instrumentation, how calibration is carried out, when one instrument may have the advantage over another, and where new techniques are needed to fill important knowledge gaps.

Blue moons and Martian sunsets.

The familiar yellow or orange disks of the moon and sun, especially when they are low in the sky, and brilliant red sunsets are a result of the selective extinction (scattering plus absorption) of blue light by atmospheric gas molecules and small aerosols, a phenomenon explainable using the Rayleigh scattering approximation. On rare occasions, dust or smoke aerosols can cause the extinction of red light to exceed that for blue, resulting in the disks of the sun and moon to appear as blue. Unlike Earth, the atmosphere of Mars is dominated by micron-size dust aerosols, and the sky during sunset takes on a bluish glow. Here we investigate the role of dust aerosols in the blue Martian sunsets and the occasional blue moons and suns on Earth. We use the Mie theory and the Debye series to calculate the wavelength-dependent optical properties of dust aerosols most commonly found on Mars. Our findings show that while wavelength selective extinction can cause the sun's disk to appear blue, the color of the glow surrounding the sun as observed from Mars is due to the dominance of near-forward scattering of blue light by dust particles and cannot be explained by a simple, Rayleigh-like selective extinction explanation.

Influence of photolysis on multispectral photoacoustic measurement of nitrogen dioxide concentration.

Multispectral photoacoustic instruments are commonly used to measure aerosol and nitrogen dioxide (NO2) light absorption coefficients to determine the radiation budget of the atmosphere. Here a new photoacoustic system is developed to explore the effect of photolysis on the measured signal in a multispectral photoacoustic spectrometer In this system, a 405-nm laser is used primarily as light source for photolysis. Additionally, a well-overlapped 532-nm laser, modulated at the resonant frequency of the photoacoustic instrument, is used to probe the NO2 concentration. As a result, the photolysis effect at 405 nm can be observed by the photoacoustic instrument through the 532-nm laser. This work determines an 11% reduction of the photoacoustic signal caused by the photolysis effect for typical conditions, which needs to be taken into account when calibrating multispectral photoacoustic spectrometers with NO2.

Emission factors for polycyclic aromatic hydrocarbons from laboratory biomass-burning and their chemical transformations during aging in an oxidation flow reactor.

Atmospheric polycyclic aromatic hydrocarbons (PAHs) can be emitted from different combustion sources including domestic biomass burning, internal combustion engines, and biomass burning (BB) in wild, prescribed, and agricultural fires. With climate warming and consequent global increases in frequency and severity of wildfires, BB is a dominant source of PAHs emitted into the atmosphere. In this study, six globally and regionally important and representative fuels (Alaskan peat, Moscow peat, Pskov peat, eucalyptus, Malaysian peat, and Malaysian agricultural peat) were burned under controlled conditions in the combustion chamber facility at the Desert Research Institute (DRI, Reno, NV, USA). Gas- and particle-phase BB emissions were aged in an oxidation flow reactor (OFR) to mimic five to sevendays of atmospheric aging. To sample gas- and particle-phase BB emissions, fresh and OFR-aged biomass-burning aerosols were collected on Teflon-impregnated glass fiber filters (TIGF) in tandem with XAD resin media for organic carbon speciation. The objectives of this study were to i) quantify the emission factors for 113 PAHs emitted from the combustion of the six selected fuels, ii) characterize the distribution of PAH compounds between gas and particle phases for these fuels, iii) identify the changes in PAHs during OFR-aging, and iv) evaluate toxicity potential with characterized compounds. We found that combustion emissions of gas-phase PAHs were more abundant (>80 % by mass) than particle-phase PAHs, for emissions from all combusted fuels. The mass fraction of substituted napthalenes in Moscow peat and Malaysian peat emissions were ∼70 % & 84 %, respectively, whereas in Eucalyptus the same fraction was <50 %, which indicates that these substituted compounds can be used as tracers for peat emissions. Mass concentrations of gas- and particle-phase PAHs were reduced by ∼70 % after OFR oxidation. However, the understanding of the fate of PAHs during OFR oxidation requires further investigations. Our results also indicate that the PAH toxicity of BB samples would be underestimated by 10-100 times if only the BaPeq for the 16 US EPA priority PAHs in the particle phase are included.

Snow cover duration in northern Finland and the influence of key variables through a conceptual framework based on observed variations in snow depth.

Seasonal snow cover duration is the net result from many processes acting on snow fallen on the Earth's surface. Several of these processes feed back into the atmosphere-cryosphere system causing non-linear interactions. The timing of snow retreat is of essential importance, but the duration of snow cover has large spatiotemporal variabilities. However, from a large data set of observed snow depth changes in northern Finland, systematic similar evolutions are identified that allow for a considerable simplification and reduction of the complexity in snow depth changes. Here, a novel conceptual framework is designed based on dividing the season into two main periods (dark and bright period, based on solar irradiance), for which snow depth decrease is parameterized based on three variables, average temperature, incoming shortwave radiation, and light-absorbing particles (LAP) in the snow. The processes are simplified into two linear relations, and a new formulation for concentration enhancement of LAP, which is dependent on snow depth decrease, is given. The results show that the seasonal snow cover duration is shifted by about one day for every 10 mm snow water equivalent of precipitation. This effect is comparable in scale to that of doubling of the amount of LAP concentration in snow. We also found that the combined shift in snow cover duration from interannual variability in ambient temperature and shortwave radiation (warm and bright vs. cold and dark season) is large enough to explain the variability of a couple of weeks for a given precipitation amount in Northern Finland.

Laboratory and field evaluation of real-time and near real-time PM2.5 smoke monitors.

Increases in large wildfire frequency and intensity and a longer fire season in the western United States are resulting in a significant increase in air pollution, including concentrations of PM2.5 (particulate matter <2.5 µm in aerodynamic diameter) that pose significant health risks to nearby communities. During wildfires, government agencies monitor PM2.5 mass concentrations providing information and actions needed to protect affected communities; this requires continuously measuring instruments. This study assessed the performance of seven candidate instruments: (1) Met One Environmental beta attenuation monitor (EBAM), (2) Met One ES model 642 (ES642), (3) Grimm Environmental Dust Monitor 164 (EDM), (4) Thermo ADR 1500 (ADR), (5) TSI DRX model 8543 (DRX), (6) Dylos 1700 (Dylos), and (7) Purple Air II (PA-II) in comparison with a BAM 1020 (BAM) reference instrument. With the exception of the EBAM, all candidates use light scattering to determine PM2.5 mass concentrations. Our comparison study included environmental chamber and field components, with two of each candidate instrument operating next to the reference instrument. The chamber component involved 6 days of comparisons for biomass combustion emissions. The field component involved operating all instruments in an air monitoring station for 39.5 days with hourly average relative humidity (RH) ranging from 19% to 98%. Goals were to assess instrument precision and accuracy and effects of RH, elemental carbon (EC), and organic carbon (OC) concentrations. All replicate candidate instruments showed high hourly correlations (R2 ≥ 0.80) and higher daily average correlations (R2 ≥ 0.90), where all instruments correlated well (R2 ≥ 0.80) with the reference. The DRX and Purple Air overestimated PM2.5 mass concentrations by a factor of ~two. Differences between candidates and reference were more pronounced at higher PM2.5 concentrations. All optical instruments were affected by high RH and by the EC/OC ratio. Equations to convert candidate instruments data to FEM BAM type data are provided to enhance the usability of data from candidate instruments.Implications: This study tested the performance of seven candidate PM2.5 mass concentration measuring instruments in two settings - environmental chamber and field. The instruments were tested to determine their suitability for use during biomass combustion events and the effects of RH, PM mass concentrations, and concentrations of EC and OC on their performance. The accuracy and precision of each monitor and effect of RH, PM concentration, EC and OC concentrations are varied. The data show that most of these candidate instruments are suitable for measuring PM2.5 concentration during biomass combustions with a proper correction factor for each instrument type.

Particle optics in the Rayleigh regime.

Light scattering and absorption by particles suspended in the atmosphere modifies the transfer of solar energy in the atmosphere, thereby influencing global and regional climate change and atmospheric visibility. Of particular interest are the optical properties of particles in the Rayleigh regime, where particles are small compared with the wavelength of the scattered or absorbed light, because these particles experience little gravitational settlement and may have long atmospheric lifetimes. Optical properties of particles in the Rayleigh regime are commonly derived from electromagnetic theory using Maxwell's equations and appropriate boundary conditions. The size dependence of particle scattering and absorption are derived here from the most basic principles for coherent processes such as Rayleigh scattering (i.e., add amplitudes if in phase) and incoherent processes such as absorption (i.e., add cross sections), at the same time yielding understanding of the upper particle size limit for the Rayleigh regime. The wavelength dependence of Rayleigh scattering and absorption are also obtained by adding a basic scale invariance for particle optics. Simple consequences for particle single-scattering albedo ("whiteness") and the optical measurement of particle mass densities are explained. These alternative derivations complement the conventional understanding obtained from electromagnetic theory.

The In-Plume Emission Test Stand: an instrument platform for the real-time characterization of fuel-based combustion emissions.

The In-Plume Emission Test Stand (IPETS) characterizes gaseous and particulate matter (PM) emissions from combustion sources in real time. Carbon dioxide (CO2), carbon monoxide (CO), nitric oxide (NO), nitrogen dioxide (NO2), and other gases are quantified with a closed-path Fourier transform infrared spectrometer (FTIR). Particle concentrations, chemical composition, and other particle properties are characterized with an electrical low-pressure impactor (ELPI), a light-scattering particle detector, an optical particle counter, and filter samples amenable to different laboratory analysis. IPETS measurements of fuel-based emission factors for a diesel generator are compared with those from a Mobile Emissions Laboratory (MEL). IPETS emission factors ranged from 0.3 to 11.8, 0.2 to 3.7, and 22.2 to 32.8 g/kg fuel for CO, NO2, and NO, respectively. IPETS PM emission factors ranged from 0.4 to 1.4, 0.3 to 1.8, 0.3 to 2.2, and 1 to 3.4 g/kg fuel for filter, photoacoustic, nephelometer, and impactor measurements, respectively. Observed linear regression statistics for IPETS versus MEL concentrations were as follows: CO slope = 1.1, r2 = 0.99; NO slope = 1.1, r2 = 0.92; and NO2 slope = 0.8, r2 = 0.96. IPETS versus MEL PM regression statistics were: filter slope = 1.3, r2 = 0.80; ELPI slope = 1.7, r2 = 0.87; light-scattering slope = 2.7, r2 = 0.92; and photoacoustic slope = 2.1, r2 = 0.91. Lower temperatures in the dilution air (approximately 25 degrees C for IPETS vs. approximately 50 degrees C for MEL) may result in greater condensation of semi-volatile compounds on existing particles, thereby explaining the 30% difference for filters. The other PM measurement devices are highly correlated with the filter, but their factory-default PM calibration factors do not represent the size and optical properties of diesel exhaust. They must be normalized to a simultaneous filter measurement.

In-Plume Emission Test Stand 2: emission factors for 10- to 100-kW U.S. military generators.

Although emissions of air pollutants from some military tactical equipment are not subject to the emissions standards, local communities near military bases must conform to the National Ambient Air Quality Standards. Military diesel generators are widely used in training. A portable in-plume system was used to measure fuel-based emission factors (EFs) for particulate matter (PM), carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbons (HCs) for 30-, 60-, and 100-kW generators at five load levels and for cold starts. It was found that EFs depend on multiple parameters including engine size, engine load, unit age, and total running hours. The average CO EF of generators tested was 5% lower, and the average NOx EF was 63% lower than AP-42 estimates; average PM EF was 80% less than the AP-42 estimates. A 2002 model-year 60-kW engine produced 25% less PM than a 1995 engine of the same family with similar running hours. CO EFs decrease with increasing engine load, NOx EFs increase up to mid-loads and decrease slightly at high loads, PM EFs increase with loads for 30- and 60-kW engines. CO and PM have higher EFs and NOx has a lower EF during cold starts than during hot-stabilized operation. PM chemical source profiles were also examined.

Optical determination of black carbon mass concentrations in snow samples: A new analytical method.

Black carbon (BC) aerosols in the atmosphere strongly affect direct radiative forcing and climate, not only while suspended in the atmosphere but also after deposition onto high albedo surfaces. Snow surfaces are especially sensitive to BC deposition, because of their high surface albedo and additional positive feedbacks further enhance faster snowpack melting caused by BC deposition, resulting in modifications in water resources and recession of glaciers. For the analysis of BC deposition on snow, a precise quantification of BC mass is needed. Instead, optical methods have the potential of quantifying only BC, based on its characteristic spectral absorption. Commercial optical transmissometers commonly use quartz filters to filter BC and measure its optical attenuation. They are calibrated for the determination of BC mass concentrations in air, but not adapted or calibrated for their determination in water or snowmelt samples. Additionally, they are generally calibrated using BC-simulating materials that are not representative of ambient BC particles. Here, a new analytical method is demonstrated for the quantitative determination of BC mass concentration in snow samples that considers filtering of melted snow with polycarbonate filters in a new device, and optical filter attenuation BC mass concentration measurement (880 nm). The attenuation can be obtained with any optical equipment that can measure the 880-nm attenuation of filters impacted with BC/snow impurities. This method has been calibrated using real diesel vehicle exhaust soot with well-known optical properties as reference material, yielding a multipoint calibration curve for common BC concentration levels in snow. The limits of detection (0.011 mg of BC), quantification (0.036 mg of BC) and reproducibility (96.39%) of this new analytical method have been determined. Real surface snow samples collected at different locations in "Los Andes" mountains of Chile were measured with this method given a BC concentrations ranged from 151 to 5987 µg kg-1.

Extensive Soot Compaction by Cloud Processing from Laboratory and Field Observations.

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.

A case study of real-world tailpipe emissions for school buses using a 20% biodiesel blend.

Numerous laboratory studies report carbon monoxide, hydrocarbon, and particulate matter emission reductions with a slight nitrogen oxides emission increase from engines operating with biodiesel and biodiesel blends as compared to using petroleum diesel. We conducted a field study on a fleet of school buses to evaluate the effects of biodiesel use on gaseous and particulate matter fuel-based emission factors under real-world conditions. The field experiment was carried out in two phases during winter 2004. In January (phase I), emissions from approximately 200 school buses operating on petroleum diesel were measured. Immediately after the end of the first phase measurement period, the buses were switched to a 20% biodiesel blend. Emission factors were measured again in March 2004 (phase II) and compared with the January emission factors. To measure gaseous emission factors we used a commercial gaseous remote sensor. Particulate matter emission factors were determined with a combination of the gaseous remote sensor, a Lidar (light detection and ranging), and transmissometer system developed at the Desert Research Institute of Reno, NV, U.S.A. Particulate matter emissions from school buses significantly increased (up to a factor of 1.8) after the switch from petroleum diesel to a 20% biodiesel blend. The fuel used during this campaign was provided by a local distributor and was independently analyzed at the end of the on-road experiment. The analysis found high concentrations of free glycerin and reduced flash points in the B 100 parent fuel. Both measures indicate improper separation and processing of the biodiesel product during production. The biodiesel fuels used in the school buses were not in compliance with the U.S.A. ASTM D6751 biodiesel standard that was finalized in December of 2001. The U.S.A. National Biodiesel Board has formed a voluntary National Biodiesel Accreditation Program for producers and marketers of biodiesel to ensure product quality and compliance with the ASTM standard. The results of our study underline the importance of the program since potential emission benefits from biodiesel may be reduced or even reversed without appropriate fuel quality control on real-world fuels.

Polycyclic aromatic hydrocarbons in biomass-burning emissions and their contribution to light absorption and aerosol toxicity.

In recent years, brown carbon (BrC) has been shown to be an important contributor to light absorption by biomass-burning atmospheric aerosols in the blue and near-ultraviolet (UV) part of the solar spectrum. Emission factors and optical properties of 113 polycyclic aromatic hydrocarbons (PAHs) were determined for combustion of five globally important fuels: Alaskan, Siberian, and Florida swamp peat, cheatgrass (Bromus tectorum), and ponderosa pine (Pinus ponderosa) needles. The emission factors of total analyzed PAHs were between 1.9±0.43.0±0.6 and 9.6±1.2-42.2±5.4mgPAHkg(-1)fuel for particle- and gas phase, respectively. Spectrophotometric analysis of the identified PAHs showed that perinaphthenone, methylpyrenes, and pyrene contributed the most to the total PAH light absorption with 17.2%, 3.3 to 10.5%, and 7.6% of the total particle-phase PAH absorptivity averaged over analyzed emissions from the fuels. In the gas phase, the top three PAH contributors to BrC were acenaphthylene (32.6%), anthracene (8.2%), and 2,4,5-trimethylnaphthalene (8.0%). Overall, the identified PAHs were responsible for 0.087-0.16% (0.13% on average) and 0.033-0.15% (0.11% on average) of the total light absorption by dichloromethane-acetone extracts of particle and gas emissions, respectively. Toxic equivalency factor (TEF) analysis of 16 PAHs prioritized by the United States Environmental Protection Agency (EPA) showed that benzo(a)pyrene contributed the most to the PAH carcinogenic potency of particle phase emissions (61.8-67.4% to the total carcinogenic potency of Σ16EPA PAHs), while naphthalene played the major role in carcinogenicity of the gas phase PAHs in the biomass-burning emission analyzed here (35.4-46.0% to the total carcinogenic potency of Σ16EPA PAHs). The 16 EPA-prioritized PAHs contributed only 22.1±6.2% to total particle and 23.4±11% to total gas phase PAH mass, thus toxic properties of biomass-burning PAH emissions are most likely underestimated.

Scattering cross-section emission factors for visibility and radiative transfer applications: military vehicles traveling on unpaved roads.

Emission factors for particulate matter (PM) are generally reported as mass emission factors (PM mass emitted per time or activity) as appropriate for air quality standards based on mass concentration. However, for visibility and radiative transfer applications, scattering, absorption, and extinction coefficients are the parameters of interest, with visibility standards based on extinction coefficients. These coefficients (dimension of inverse distance) equal cross-section concentrations, and, therefore, cross-section emission factors are appropriate. Scattering cross-section emission factors were determined for dust entrainment by nine vehicles, ranging from light passenger vehicles to heavy military vehicles, traveling on an unpaved road. Each vehicle made multiple passes at multiple speeds while scattering and absorption coefficients, wind velocity and dust plume profiles, and additional parameters were measured downwind of the road. Light absorption of the entrained PM was negligible, and the light extinction was primarily caused by scattering. The resulting scattering cross-section emission factors per vehicle kilometer traveled (vkt) range from 12.5 m2/vkt for a slow (16 km/ hr), light (1176 kg) vehicle to 3724 m2/vkt for a fast (64 km/hr), heavy (17,727 kg) vehicle and generally increase with vehicle speed and mass. The increase is approximately linear with speed, yielding emission factors per vkt and speed ranging from 4.2 m2/(vkt km/hr) to 53 m2/(vkt km/hr). These emission factors depend approximately linearly on vehicle mass within the groups of light (vehicle mass < or =3100 kg) and heavy (vehicle mass >8000 kg) vehicles yielding emission factors per vkt, speed, and mass of 0.0056 m2/(vkt km/hr kg) and 0.0024 m2/(vkt km/hr kg), respectively. Comparison of the scattering cross-section and PM mass emission factors yields average mass scattering efficiencies of 1.5 m2/g for the light vehicles and of 0.8 m2/g for the heavy vehicles indicating that the heavy vehicles entrain larger particles than the light vehicles.

Remote sensing of PM, NO, CO and HC emission factors for on-road gasoline and diesel engine vehicles in Las Vegas, NV.

A novel light detection and ranging-based remote sensing system was assembled and used to measure mass particulate matter (PM) emissions per unit of fuel burned from in-use on-road vehicles. A commercially available remote sensing system was concurrently used to measure emissions of carbon monoxide (CO), nitrogen oxide (NO) and hydrocarbons (HC). The two systems were used to measure 61,207 gasoline and 1180 diesel powered vehicle emissions in Las Vegas, NV from 4/4/2000 to 5/16/2002. Emission factors were related to vehicle age, weight class and fuel type by matching license IDs to the state registration data. Measurements of vehicle speed and acceleration permitted the analysis of emission factors by vehicle specific power (VSP). Average emission factors were calculated for light-duty (<3863 kg [8500 lbs]) gasoline vehicles (LDGV), light-duty diesel vehicles (LDDV), heavy-duty (>3863 kg [8500 lbs]) gasoline vehicles (HDGV) and heavy-duty diesel vehicles (HDDV). LDDV and HDDV emitted approximately 25 times more PM per mass of fuel than LDGV and HDGV. Sufficient numbers of LDGV were measured to relate VSP with CO, HC and NO emissions. No relationship was observed between PM emissions and VSP. PM emission factors from LDGV increased with vehicle age. Fuel-based emission factors measured by remote sensing were compared with MOBILE6 and PART5 emissions model factors. Good agreement was observed for HC emission factors for vehicles less than 20 years old. MOBILE6 CO emission factors were approximately 2 times greater than measured CO emission factors for vehicles less than 13 years old. Measured NO emission factors were approximately 50% greater than MOBILE6 factors for vehicles 7-15 years old but in good agreement for vehicles less than 7 years old. Measured PM emission factors showed a clear increase with vehicle age, however, PART5 uses only a single PM emission factor for LDGV less than 18 years old. The PM emission factors for the fleet of LDGV, HDGV, LDDV and HDDV were 0.06, 0.05, 1.6 and 1.5 g/kg, respectively.

On-road vehicle particulate matter and gaseous emission distributions in Las Vegas, Nevada, compared with other areas.

During the spring and summer of 2000, 2001, and 2002, gaseous and particulate matter (PM) fuel-based emission factors for approximately 150,000 low-tailpipe, individual vehicles in the Las Vegas, NV, area were measured via on-road remote sensing. For the gaseous pollutants (carbon monoxide, hydrocarbons, and nitrogen oxide), a commercial vehicle emissions remote sensing system (VERSS) was used. The PM emissions were determined using a Lidar-based VERSS. Emission distributions and their shapes were analyzed and compared with previous studies. The large skewness of the distributions is evident for both gaseous pollutants and PM and has important implications for emission reduction policies, because the majority of emissions are attributed to a small fraction of vehicles. Results of this Las Vegas study and studies at other geographical locations were compared. The gaseous pollutants were found to be close to those measured by VERSS in other U.S. cities. The PM emission factors for spark ignition and diesel vehicles are in the range of previous tunnel and dynamometer studies.

Soot superaggregates from flaming wildfires and their direct radiative forcing.

Wildfires contribute significantly to global soot emissions, yet their aerosol formation mechanisms and resulting particle properties are poorly understood and parameterized in climate models. The conventional view holds that soot is formed via the cluster-dilute aggregation mechanism in wildfires and emitted as aggregates with fractal dimension Df ≈ 1.8 mobility diameter Dm ≤ 1 µm, and aerodynamic diameter Da ≤ 300 nm. Here we report the ubiquitous presence of soot superaggregates (SAs) in the outflow from a major wildfire in India. SAs are porous, low-density aggregates of cluster-dilute aggregates with characteristic Df ≈ 2.6, Dm > 1 µm, and Da ≤ 300 nm that form via the cluster-dense aggregation mechanism. We present additional observations of soot SAs in wildfire smoke-laden air masses over Northern California, New Mexico, and Mexico City. At 550 nm wavelength, [corrected] we estimate that SAs contribute, per unit optical depth, up to 35% less atmospheric warming than freshly-emitted (D(f) ≈ 1.8) [corrected] aggregates, and ≈90% more warming than the volume-equivalent spherical soot particles simulated in climate models.