Loading Effect Correction for Real-Time Aethalometer Measurements of Fresh Diesel Soot

Abstract

In this study, a correction was developed for the aethalometer to measure real-time black carbon (BC) concentrations in an environment dominated by fresh diesel soot. The relationship between the actual mass-specific absorption coefficient for BC and the BC-dependent attenuation coefficients was determined from experiments conducted in a diesel exposure chamber that provided constant concentrations of fine particulate matter (PM; PM_2.5; PM <2.5 µm in aerodynamic diameter) from diesel exhaust. The aethalometer reported BC concentrations decreasing with time from 48.1 to 31.5 µg m^?3when exposed to constant PM_2.5concentrations of 55 ± 1 µg m^?3and b_scat= 95 ± 3 Mm^?1from diesel exhaust. This apparent decrease in reported light-absorbing PM concentration was used to derive a correction K(ATN) for loading of strong light-absorbing particles onto or into the aethalometer filter tape, which was a function of attenuation of light at 880 nm by the embedded particles.     

Aerosol properties,in-canopy gradients,turbulent fluxes and VOC concentrations at a pristine forest site in Amazonia

Aerosol physical and chemical properties were measured in a forest site in central Amazonia (Cuieiras reservation, 2.61S; 60.21W) during the dry season of 2004 (Aug–Oct). Aerosol light scattering and absorption, mass concentration, elemental composition and size distributions were measured at three tower levels (Ground: 2 m; Canopy: 28 m, and Top: 40 m). For the first time, simultaneous eddy covariance fluxes of fine mode particles and volatile organic compounds (VOC) were measured above the Amazonian forest canopy. Aerosol fluxes were measured by eddy covariance using a Condensation Particle Counter (CPC) and a sonic anemometer. VOC fluxes were measured by disjunct eddy covariance using a Proton Transfer Reaction Mass Spectrometer (PTR-MS). At nighttime, a strong vertical gradient of phosphorus and potassium in the aerosol coarse mode was observed, with higher concentrations at Ground level. This suggests a source of primary biogenic particles below the canopy. Equivalent black carbon measurements indicate the presence of light-absorbing aerosols from biogenic origin. Aerosol number size distributions typically consisted of superimposed Aitken (76 nm) and accumulation modes (144 nm), without clear events of new particle formation. Isoprene and monoterpene fluxes reached respectively 7.4 and 0.82 mg m^?2 s^?1 around noon. An average fine particle flux of 0.05 ± 0.10 10⁶ m^?2 s^?1 was calculated, denoting an equilibrium between emission and deposition fluxes of fine mode particles at daytime. No significant correlations were found between VOC and fine mode aerosol concentrations or fluxes.     

Measurement of black carbon aerosols near two Chinese megacities and the implications for improving emission inventories

Knowledge of the distribution and sources of black carbon (BC) is essential to understanding its impact on radiative forcing and the establishment of a control strategy. In this study, we analyze atmospheric BC and its relationships with fine particles (PM_2.5) and trace gases (CO, NO_y and SO₂) measured in the summer of 2005 in two areas frequently influenced by plumes from Beijing and Shanghai, the two largest cities in China. The results revealed different BC source characteristics for the two megacities. The average concentration of BC was 2.37 (±1.79) and 5.47 (±4.00) μg m^?3, accounting for 3.1% and 7.8% of the PM_2.5 mass, in Beijing and Shanghai, respectively. The good correlation between BC, CO and NO_y (R² = 0.54–0.77) and the poor correlation between BC and SO₂ suggest that diesel vehicles and marine vessels are the dominant sources of BC in the two urban areas during summer. The BC/CO mass ratio in the air mass from Shanghai was found to be much higher than that in the air mass from Beijing (0.0101 versus 0.0037 ΔgBC/ΔgCO), which is attributable to a larger contribution from diesel burning (diesel-powered vehicles and marine vessels) in Shanghai. Based on the measured ratios of BC/CO and annual emissions of CO, we estimate that the annual emissions of BC in Beijing and Shanghai are 9.51 Gg and 18.72 Gg, respectively. The improved emission rates of BC will help reduce the uncertainty in the assessment of the impact of megacities on regional climate.     

Development of an improved optical transmission technique for black carbon (BC) analysis

A new optical transmission technique for black carbon (BC) analysis was developed to minimize interferences due to scattering effects in filter samples. A standard thermal analysis method (VDI, 1999) is used to link light attenuation by the filter samples to elemental carbon (EC) concentration. Scattering effects are minimized by immersion of the filters in oil of a similar refractive index, as is often done for microscopy purposes. Light attenuation was measured using both a white light source and a red LED of 650 nm. The usual increase in overestimation of BC concentrations with decreasing BC amount in filter samples was found considerably reduced. Some effects of BC properties (e.g. fractal dimension, microstructure and size distribution) on the specific attenuation coefficient B_ATN, however, are still present for the treated samples. B_ATN was found close to 1 m² g⁻¹ for dry-dispersed industrial BC and 7 m² g⁻¹ for nebulized BC. Good agreement was found between the oil immersion, integrating sphere and a polar photometer technique and Mie calculations. The average specific attenuation coefficient of ambient samples in oil varied between 7 and 11 m² g⁻¹ for white light and 6 and 9 m² g⁻¹ for red light (LED). B_ATN was found to have much less site variation for the treated than for the untreated samples. The oil immersion technique improved also the correlation with thermally analyzed EC. This new immersion technique therefore presents a considerable improvement over conventional optical transmission techniques and may therefore serve as a simple, fast and cost-effective alternative to thermal methods.     

Spectroscopic study of organic coatings on fine particles,exposed to ozone and simulated sunlight

This work intends to quantify the variation in optical properties of aerosol by in-situ spectroscopic monitoring the ozonolysis of a mixture of typical biomass burning compounds. The reaction occurs on silica and glass particles in the presence of simulated sunlight.Fused silica particles (Aerosil) were coated with a thin film of a 1:1 mixure of 4-phenoxyphenol with 4-carboxyphenone as a photosensitizer. UV–VIS spectra of dichloromethane extracts from the particles recorded before and after treatment, show development of a new band after prolonged ozone and light exposure.Changes in optical properties are reported, and variations of spectroscopic features are discussed. We show that the ozone-induced heterogeneous photochemical reaction does produce species absorbing light in the solar spectral range. Further, we demonstrate that the heterogeneous photosensitized reactions at 200 ppb ozone (strongly ozone polluted regions) for a time period of 7 h aging process, can increase light absorption of atmospheric aerosols in the tropospheric actinic window (>290 nm) by 0.4 absorption units ng-C^?1 O₃ ppm^?1 in the region 290–358 nm and by 1.0 absorption units ng-C^?1 O₃ ppm^?1 in the region 360–448 nm.Chemical changes of such surface films were identified by diffuse reflectance infrared Fourier transform spectroscopy of coated glass spheres, and we suggest formation of humic-like substances comparable to those reported in continental aerosol.     

A contribution of brown carbon aerosol to the aerosol light absorption and its radiative forcing in East Asia

Brown carbon aerosols were recently found to be ubiquitous and effectively absorb solar radiation. We use a 3-D global chemical transport model (GEOS-Chem) together with aircraft and ground based observations from the TRACE-P and the ACE-Asia campaigns to examine the contribution of brown carbon aerosol to the aerosol light absorption and its climatic implication over East Asia in spring 2001. We estimated brown carbon aerosol concentrations in the model using the mass ratio of brown carbon to black carbon (BC) aerosols based on measurements in China and Europe. The comparison of simulated versus observed aerosol light absorption showed that the model accounting for brown carbon aerosol resulted in a better agreement with the observations in East Asian-Pacific outflow. We then used the model results to compute the radiative forcing of brown carbon, which amounts up to ?2.4 W m^?2 and 0.24 W m^?2 at the surface and at the top of the atmosphere (TOA), respectively, over East Asia. Mean radiative forcing of brown carbon aerosol is ?0.43 W m^?2 and 0.05 W m^?2 at the surface and at the TOA, accounting for about 15% of total radiative forcing (?2.2 W m^?2 and 0.33 W m^?2) by absorbing aerosols (BC + brown carbon aerosol), having a significant climatic implication in East Asia.     

Fine Particulate Chemical Composition and Light Extinction at Meadview,AZ

Abstract

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was ±0.6 μg/m³ organic material, ±0.3 μg/m³ ammonium sulfate, and ±0.07 μg/m³ ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.     

Mixing properties of submicrometer aerosol particles in the urban atmosphere—with regard to soot particles

Individual aerosol particles were collected on three days with different meteorological conditions in June 2000 in the urban atmosphere of Tsukuba, Japan. The samples collected with an electrostatic aerosol sampler (EAS) were examined by electron microscopy. The mixing properties of submicrometer aerosol particles of 0.02–0.2 μm radius were studied using the dialysis (extraction) of water-soluble material. Atmospheric aerosol particles were classified into four types with respect to the mixtures of water-soluble and water-insoluble material. The proportions of particles with water-soluble material (hygroscopic particles) ranged from 20% to 80% in the whole radius range and tended to increase with increasing radius. Moreover, by the morphological appearance, soot-containing particles were classified into two types, i.e., externally mixed soot-particles and internally mixed soot-particles. The number fractions of internally mixed soot-particles increased with increasing radius. It is found that the volume fraction of water-soluble material (ε) for the internally mixed soot-particles increased with increasing radius. In a “polluted” case, the sample showed a dominant number fraction (75%) of internally mixed soot-particles in the larger radius range of 0.1–0.2 μm.     

Carbonaceous aerosol in jet engine exhaust: emission characteristics and implications for heterogeneous chemical reactions

Characteristic parameters of black carbon aerosol (BC) emitted from jet engine were measured during ground tests and in-flight behind the same aircraft. Size distribution features were a primary BC mode at a modal diameter D≈0.045 μm, and a BC agglomeration mode at D<0.2 μm. The total BC number concentration at the engine exit was 2.9×10⁷ cm^-3 with good agreement between model results and in-flight measured number concentrations of non-volatile particles with D⩾0.014 μm. A comparison between total number concentration of BC particles and the non-volatile fraction of the total aerosol at the exit plane suggests that the non-volatile fraction of jet engine exhaust aerosol consists almost completely of BC. In-flight BC mass emission indices ranged from 0.11 to 0.15 g BC (kg fuel)^-1. The measured in-flight particle emission value was 1.75±0.15×10¹⁵ kg^-1 with corresponding ground test values of 1.0–8.7×10¹⁴ kg^-1. Both size distribution properties and mass emission indices can be scaled from ground test to in-flight conditions. Implications for atmospheric BC loading, BC and cirrus interaction and the potential of BC for perturbation of atmospheric chemistry are briefly outlined.     

Light-induced heterogeneous ozone processing on organic coated particles: Kinetics and condensed-phase products

For the first time we investigated the effect of solar irradiation upon the heterogeneous ozonation of adsorbed 3,4,5-trimethoxybenzaldehyde on solid surface. Light-induced heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde adsorbed on silica particles were performed and the consecutive reaction products were identified. At an ozone mixing ratio of 250 ppb, the loss of 3,4,5-trimethoxybenzaldehyde ranged from 1.0 · 10^?6 s^?1 in the dark to 2.9 · 10^?5 s^?1 under light irradiation. Such large enhancement of 29 times clearly shows the importance of light (λ > 300 nm) during the heterogeneous ozonolysis on organic coated particles.The reaction products identified in this study (3,4,5-trimethoxybenzoic acid, syringic acid, methyl 3,4,5-trimethoxybenzoate) absorb light in the spectral window (λ > 300 nm) which implies that light-induced heterogeneous ozone processing can have an influence on the aerosol surfaces by changing their physico-chemical properties.The main identified product of the heterogeneous reactions between gas-phase ozone and 3,4,5-trimethoxybenzaldehyde under dark conditions and in presence of light was 3,4,5-trimethoxybenzoic acid. For this reason we estimated the carbon yield of 3,4,5-trimethoxybenzoic acid. Carbon yields of 3,4,5-trimethoxybenzoic acid decreased with increasing ozone mixing ratio; from 40% at 250 ppb to 15% at ≥2.5 ppm under dark conditions. At ozone mixing ratio (250 ppb–1 ppm), carbon yields of 3,4,5-trimethoxybenzaldehyde are relatively higher in the experiment under dark condition than under simulated solar light.     

Optical and thermal characteristics of carbonaceous aerosols measured at an urban site in Gwangju,Korea, in the winter of 2011

Carbonaceous components (organic carbon [OC] and elemental carbon [EC]) and optical properties (light absorption and scattering) of fine particulate matter (aerodynamic diameter <2.5 μm; PM_2.5) were simultaneously measured at an urban site in Gwangju, Korea, during the winter of 2011. OC was further classified into OC1, OC2, OC3, and OC4, based on a temperature protocol using a Sunset OC/EC analyzer. The average OC and EC concentrations were 5.0 ± 2.5 and 1.7 ± 0.9 μg C m^?3, respectively. The average single-scattering albedo (SSA) at a wavelength of 550 nm was 0.58 ± 0.11, suggesting that the aerosols observed in the winter of 2011 had a local warming effect in this area. During the whole sampling period, “stagnant PM” and “long-range transport PM” events were identified. The light absorption coefficient (b_abs) was higher during the stagnant PM event than during the long-range transport PM event due to the existence of abundant light-absorbing OC during the stagnant PM event. In particular, the OC2 and OC3 concentrations were higher during the stagnant PM event than those during the long-range transport event, suggesting that OC2 and OC3 might be more related to the light-absorbing OC. The light scattering coefficient (b_scat) was similar between the events. On average, the mass absorption efficiency attributed to EC (σ_EC) was 9.6 m² g^?1, whereas the efficiency attributed to OC (σ_OC) was 1.8 m² g^?1 at λ = 550 nm. Furthermore, the σ_EC is comparable among the PM event days, but the σ_OC for the stagnant PM event was significantly higher than that for the long-range transport PM event (1.7 vs. 0.5).

Implications: Optical and thermal properties of carbonaceous aerosol were measured at Gwangju, and carbonaceous aerosol concentration and optical property varied between “stagnant PM” and “long-range transport PM” events. More abundant light absorbing OC was observed during the stagnant PM event.     

Mixing properties of individual submicrometer aerosol particles in Vienna

Individual aerosol particles were collected on 5 days with different meteorological conditions in March, April and June 1991 in the urban atmosphere of Vienna in Austria. The samples collected with an impactor were examined by electron microscopy. The mixing properties of submicrometer aerosol particles with radii between 0.1 and 1 μm were studied by using the dialysis (extraction) of water-soluble material. The averaged results showed that more than 85% of particles with radii between 0.1 and 0.7 μm were hygroscopic. However, more than 50% of particles with radii larger than 0.2 μm were mixed particles (hygroscopic particles with water-insoluble inclusions), and they were dominant (80%) in the size range 0.5–0.7 μm radius. The results also showed that the number proportion of mixed particles increased with increasing radius and the abundance increased with increasing particle loading in the atmosphere. The volume fraction of water-soluble material (ε) in mixed particles tended to decrease with increasing radius, implying the formation of mixed particles by heterogeneous processes such as condensation and/or surface reaction. Some results of elemental composition in individual particles analyzed with an energy-dispersive X-ray (EDX) analyzer equipped with an electron microscope are also presented in this paper.     

On radiative effects of black carbon and sulphate aerosols

Most aerosol particles, such as sulphate and sea-salt particles, mainly scatter solar radiation, whilst soot (in the form of elemental carbon or “black” carbon, BC) in addition leads to considerable absorption. This scattering and absorption by the aerosol particles constitute the so-called direct aerosol effect. In this paper, we present results from a study of possible direct effects of tropospheric BC and sulphate aerosols, with an emphasis on BC aerosols, along a line from North Africa through Europe into the Arctic. Radiative budgets in a cloud-free atmosphere are estimated. Based on model-calculated distributions of BC and sulphate (provided by Seland and Iversen, 1998) and assumed size distributions of the background aerosol, new size distributions are obtained by adding natural, biomass burning and fossil fuel contributions to the background aerosol. Added nucleation mode particles are assumed externally mixed, whereas added accumulation mode BC and sulphate is internally mixed with the background according to condensational growth and Brownian coagulation theory. Humidity effects are taken into account by use of the Köhler equation. Mie calculations provide the resulting optical parameters, and the forcing is finally estimated by use of a radiative transfer model. A reference run and a series of eleven test-runs are performed to investigate the sensitivity of various assumptions on the contribution to upward TOA irradiance from BC and non-sea-salt sulphate. The tests suggest a high sensitivity to presence of BC and to particle swelling due to humidity. The sensitivity to assumed distribution of BC on particle size is more moderate. The same is true for the vertical resolution and the number concentration of the background aerosol. The effect of mixing organic carbon (OC) internally with biomass burning BC nucleation mode particles is characterized as moderate. The role of OC is, however, still uncertain. The same holds true for the optical thickness of the background atmosphere, for which we found a high sensitivity in this study. Other assumptions that were investigated had only small effects on the forcing. For the reference run we find a minimum in the aerosol forcing of approximately −5 W m^-2 near the most polluted areas in Europe, and a maximum of approximately 2 W m^-2 over North Africa. A warming effect is also found for the Arctic region, with forcing values up to 0.4 W m^-2.     

Characterization of organic coatings on hygroscopic salt particles and their atmospheric impacts

The photooxidation of α-pinene in the presence of NO₂, with and without added NaNO₃ seed particles, has been studied in a large-diameter flow tube. Particles formed by homogeneous nucleation and by condensation on the pre-existing seeds were sampled at various stages of the reaction, dried using four diffusion dryers, size selected at different mobility diameters (d_m) using a differential mobility analyzer (DMA), and characterized with a single particle mass spectrometer (SPLAT II). It was found that homogeneously nucleated particles are spherical, have a density (ρ) of 1.25 ± 0.02 g cm^?3 (±2σ) and contain a significant amount of organic nitrates. The mass spectra of the low volatility products condensed on the NaNO₃ seed particles were found to be virtually the same as in the case of homogeneous nucleation. The data show that the presence of even a submonolayer of organics on the NaNO₃ particles causes water retention that leads to a decrease in particle density and that the amount of water retained increases with organic coating thickness. Thicker coatings appear to inhibit water evaporation from the particle seeds altogether. This suggests that in the atmosphere, where low volatility organics are plentiful, some hygroscopic salts will retain water and have different densities and refractive indices than expected in the absence of the organic coating. This water retention combined with the organic shell on the particles can potentially impact light scattering by these particles and activity as cloud condensation nuclei (CCN), as well as heterogeneous chemistry and photochemistry on the particles.     

Variations in single scattering albedo and Angstrom absorption exponent during different seasons at Delhi,India

Simultaneous measurements of aerosol absorption and scattering coefficients for the PM_2.5 aerosols particles were done at Delhi during April 2008–March 2009 to estimate the aerosol single scattering albedo (SSA) and the Angstrom absorption exponents at the surface. The annual average SSA at 0.55 μm was found to be 0.70 ± 0.07 with only slight variations during the four seasons, summer (0.63 ± 0.06), monsoon (0.69 ± 0.07), winter (0.74 ± 0.03) and spring (0.72 ± 0.04). However, large variations in average absorption and scattering coefficients were seen during these four seasons. The average absorption coefficients during summer, monsoon, winter and spring were found to be 62.47 ± 21.27, 50.95 ± 43.61, 189.65 ± 85.94 and 90.65 ± 33.06 Mm^?1 respectively. The corresponding scattering coefficients were 110.46 ± 36.15, 95.34 ± 49.46, 565.59 ± 274.59 and 236.56 ± 96.25 Mm^?1. The Angstrom absorption exponent (α_σ(abs)) remained close to unity throughout the year averaging at 1.02 ± 0.08, 1.02 ± 0.10, 1.04 ± 0.11, and 1.03 ± 0.05 during summer, monsoon, winter and spring seasons respectively, strongly indicating that the absorption at Delhi aerosol is mainly due to the abundance of black carbon of fossil fuel origin.     

Loading effect correction for real-time aethalometer measurements of fresh diesel soot

In this study, a correction was developed for the aethalometer to measure real-time black carbon (BC) concentrations in an environment dominated by fresh diesel soot. The relationship between the actual mass-specific absorption coefficient for BC and the BC-dependent attenuation coefficients was determined from experiments conducted in a diesel exposure chamber that provided constant concentrations of fine particulate matter (PM; PM(2.5); PM < 2.5 microm in aerodynamic diameter) from diesel exhaust. The aethalometer reported BC concentrations decreasing with time from 48.1 to 31.5 microg m(-3) when exposed to constant PM(2.5) concentrations of 55 +/- 1 microg m(-3) and b(scat) = 95 +/- 3 Mm(-1) from diesel exhaust. This apparent decrease in reported light-absorbing PM concentration was used to derive a correction K(ATN) for loading of strong light-absorbing particles onto or into the aethalometer filter tape, which was a function of attenuation of light at 880 nm by the embedded particles.     

Temporal trends of black carbon concentrations and regional climate forcing in the southeastern United States

The effect of black carbon (BC) on climate forcing is potentially important, but its estimates have large uncertainties due to a lack of sufficient observational data. The BC mass concentration in the southeastern US was measured at a regionally representative site, Mount Gibbes (35.78°N, 82.29°W, 2006 m MSL). The air mass origin was determined using 48-h back trajectories obtained from the hybrid single-particle Lagrangian integrated trajectory model. The highest average concentration is seen in polluted continental air masses and the lowest in marine air masses. During the winter, the overall average BC value was 74.1 ng m⁻³, whereas the overall summer mean BC value is higher by a factor of 3. The main reason for the seasonal difference may be enhanced thermal convection during summer, which increases transport of air pollutants from the planetary boundary layer of the surrounding urban area to this rural site. In the spring of 1998, abnormally high BC concentrations from the continental sector were measured. These concentrations were originating from a biomass burning plume in Mexico. This was confirmed by the observations of the Earth probe total ozone mapping spectrometer. The BC average concentrations of air masses transported from the polluted continental sector during summer are low on Sunday to Tuesday with a minimum value of 256 ng m⁻³ occurring on Monday, and high on Wednesday to Friday with a maximum value of 379 ng m⁻³ occurring on Friday. The net aerosol radiative forcing (scattering effects plus absorption effects) per unit vertical depth at 2006 m MSL is calculated to be −1.38×10⁻³ W m⁻³ for the southeastern US. The magnitude of direct radiative forcing by aerosol scattering is reduced by 15±7% due to the BC absorption.     

On the contribution of black carbon to the composite aerosol radiative forcing over an urban environment

This paper discusses the extent of Black Carbon (BC) radiative forcing in the total aerosol atmospheric radiative forcing over Pune, an urban site in India. Collocated measurements of aerosol optical properties, chemical composition and BC were carried out for a period of six months (during October 2004 to May 2005) over the site. Observed aerosol chemical composition in terms of water soluble, insoluble and BC components were used in Optical Properties of Aerosols and Clouds (OPAC) to derive aerosol optical properties of composite aerosols. The BC fraction alone was used in OPAC to derive optical properties of BC aerosols. The aerosol optical properties for composite and BC aerosols were separately used in SBDART model to derive direct aerosol radiative forcing due to composite and BC aerosols. The atmospheric radiative forcing for composite aerosols were found to be +35.5, +32.9 and +47.6 Wm^?2 during post-monsoon, winter and pre-monsoon seasons, respectively. The average BC mass fraction found to be 4.83, 6.33 and 4 μg m^?3 during the above seasons contributing around 2.2 to 5.8% to the total aerosol load. The atmospheric radiative forcing estimated due to BC aerosols was +18.8, +23.4 and +17.2 Wm^?2, respectively during the above seasons. The study suggests that even though BC contributes only 2.2–6% to the total aerosol load; it is contributing an average of around 55% to the total lower atmospheric aerosol forcing due to strong radiative absorption, and thus enhancing greenhouse warming.     

Contribution of transition metals in the reactive oxygen species activity of PM emissions from retrofitted heavy-duty vehicles

We assessed the contribution of water-soluble transition metals to the reactive oxygen species (ROS) activity of diesel exhaust particles (DEPs) from four heavy-duty vehicles in five retrofitted configurations (V-SCRT, Z-SCRT, DPX, hybrid, and school bus). A heavy-duty truck without any control device served as the baseline vehicle. Particles were collected from all vehicle-configurations on a chassis dynamometer under three driving conditions: cruise (80 km h^?1), transient UDDS, and idle. A sensitive macrophage-based in vitro assay was used to determine the ROS activity of collected particles. The contribution of water-soluble transition metals in the measured activity was quantified by their removal using a Chelex^® complexation method. The study demonstrates that despite an increase in the intrinsic ROS activity (per mass basis) of exhaust PM with use of most control technologies, the overall ROS activity (expressed per km or per h) was substantially reduced for retrofitted configurations compared to the baseline vehicle. Chelex treatment of DEPs water extracts removed a substantial (≥70%) and fairly consistent fraction of the ROS activity, which ascertains the dominant role of water-soluble metals in PM-induced cellular oxidative stress. However, relatively lower removal of the activity in few vehicle-configurations (V-SCRT, DPX and school bus idle), despite a large aggregate metals removal, indicated that not all species were associated with the measured activity. A univariate regression analysis identified several transition metals (Fe, Cr, Co and Mn) as significantly correlated (R > 0.60; p < 0.05) with the ROS activity. Multivariate linear regression model incorporating Fe, Cr and Co explained 90% of variability in ROS levels, with Fe accounting for the highest (84%) fraction of the variance.