L. K. Sahu

Consistency and Traceability of Black Carbon Measurements Made by Laser-Induced Incandescence, Thermal-Optical Transmittance, and Filter-Based Photo-Absorption Techniques

In this study, we show that black carbon (BC) mass concentrations measured by different techniques are consistent and traceable. First, we present the volatilities of 13 organic compounds passed through a heated inlet. These data were used to quantify the interference of organic aerosols on the BC measurement techniques. The masses of the refractory particles that incandesce (m*ref) were used to calibrate BC mass measured by a single-particle soot photometer (SP2), which uses laser-induced incandescence. This calibration was influenced little by refractory organics and agreed well with that of fullerene soot, which indicates the consistency of the standards. We estimated the interference of pyrolyzed refractory organics on the BC measured with a filter-based absorption photometer continuous soot monitoring system (COSMOS) with a heated inlet to be small in Asia. This was also confirmed by the stable mass absorption cross section (MAC) obtained by the high correlations between BC mass concentrations measured by COSMOS (M COSMOS) and those measured by the thermal-optical transmittance method (M TOT) (Kondo et al. 2009). M COSMOS was also compared with total BC mass concentrations measured with an SP2 (M SP2) in Tokyo in 2009. M COSMOS and M SP2 were highly correlated (r 2= 0.97) and agreed to within about 10% on average. These results demonstrate that M SP2, M COSMOS, and M TOT were nearly identical. Use of the masses of incandescing refractory BC particles for calibration of BC mass concentrations determined by different techniques gave consistent results.

Stabilization of the Mass Absorption Cross Section of Black Carbon for Filter-Based Absorption Photometry by the use of a Heated Inlet

In principle, mass concentrations of black carbon (BC) (M BC) can be estimated by the measurement of the light absorption coefficient of BC. Filter-based methods, which quantify the absorption coefficient (b abs) from the change in transmission through a filter loaded with particles, have been widely used to measure M BC. However, reliable determination of M BC has been very difficult because of the large variability in the mass absorption cross section (C abs), which is the conversion factor from b abs to M BC. Coating of BC by volatile compounds and the co-existence of light-scattering particles contribute to the variability of C abs. In order to overcome this difficulty, volatile aerosol components were removed before collection of BC particles on filters by heating a section of the inlet to 400°C. We made simultaneous measurements of b abs by two types of photometers (Particle Soot Absorption Photometer (PSAP) and Continuous Soot Monitoring System (COSMOS)) together with M BC by an EC-OC analyzer to determine C abs at 6 locations in Asia. C abs was stable at 10.5 ± 0.7 m2 g −1 at a wavelength of 565 nm for BC strongly impacted by emissions from vehicles and biomass burning. The stable C abs value provides a firm basis for its use in estimating M BC by COSMOS and PSAP with an accuracy of about 10%. For the quantitative interpretation of the ratio of the C abs to the model-calculated C abs*, we measured C abs for mono-disperse nigrosin particles in the laboratory. The C abs/C abs* ratio was 1.4–1.9 at the 100–200 nm diameters, explaining the ratio of 1.8 for ambient BC.

Anthropogenic aerosols observed in Asian continental outflow at Jeju Island, Korea, in spring 2005

(SO4� ) aerosols were 1.2 ± 0.8 mgC m � 3 , 4.2 ± 1.6 mgC m � 3 , 1.3 ± 1.0 mgC m � 3 , and 4.0 ± 3.4 m gm � 3 , respectively. Almost all species concentrations were highest in Chinese air masses, while they were lowest in marine air masses. The observed DBC/DCO slope of 9.7 ng m � 3 ppbv � 1 in Chinese outflow agrees reasonably with the estimates of the BC/CO emission ratios over northeastern China. The transport efficiencies of SOx (SO2 +S O4� ) are calculated to be 40–45% from the observed SOx-CO correlation. The relationships of the SO4� /BC and WSOC/BC ratios with transport time from the continent suggest that a majority of SO4� and WSOC aerosols were formed by about

Performance of a newly designed continuous soot monitoring system (COSMOS)

We designed a continuous soot monitoring system (COSMOS) for fully automated, high-sensitivity, continuous measurement of light absorption by black carbon (BC) aerosols. The instrument monitors changes in transmittance across an automatically advancing quartz fiber filter tape using an LED at a 565 nm wavelength. To achieve measurements with high sensitivity and a lower detectable light absorption coefficient, COSMOS uses a double-convex lens and optical bundle pipes to maintain high light intensity and signal data are obtained at 1000 Hz. In addition, sampling flow rate and optical unit temperature are actively controlled. The inlet line for COSMOS is heated to 400 degrees C to effectively volatilize non-refractory aerosol components that are internally mixed with BC. In its current form, COSMOS provides BC light absorption measurements with a detection limit of 0.45 Mm(-1) (0.045 microg m(-3) for soot) for 10 min. The unit-to-unit variability is estimated to be within +/- 1%, demonstrating its high reproducibility. The absorption coefficients determined by COSMOS agreed with those by a particle soot absorption photometer (PSAP) to within 1% (r2 = 0.97). The precision (+/- 0.60 Mm(-1)) for 10 min integrated data was better than that of PSAP and an aethalometer under our operating conditions. These results showed that COSMOS achieved both an improved detection limit and higher precision for the filter-based light absorption measurements of BC compared to the existing methods.

Comparison of Black Carbon Mass Concentrations Observed by Multi-Angle Absorption Photometer (MAAP) and Continuous Soot-Monitoring System (COSMOS) on Fukue Island and in Tokyo, Japan

Reducing uncertainties associated with measurements of black carbon (BC) particles is critical for improved quantification of their impacts on climate and health. We compared BC measurements using a continuous soot-monitoring system (COSMOS) and a multi-angle absorption photometer (MAAP) to assess their uncertainties. We found that measurements by COSMOS and MAAP instruments correlate strongly to each other, and their hourly ratio showed minimal temporal variations, but the MAAP values were systematically higher by a factor of 1.56 ± 0.19 (1σ), based on simultaneous observations on Fukue, a remote island in Japan, for about a year. This factor was almost independent of the air mass origins and seasons. Measurements in central Tokyo for about 2 months also yielded a similar relationship, with a systematic difference factor of ∼1.8. It is likely that the systematic differences are caused by differences in the conditions/protocols in the thermal/optical BC determinations used for calibration of each optical instrument. Based on results from the COSMOS instrument calibrated using an elemental carbon and organic carbon analyzer with thermal/optical transmittance correction, the MAAP absorption cross section (6.6 m2 g−1) needs to be systematically increased to 10.3 m2 g−1 at 639 nm for Fukue when b abs values derived from the built-in software are used. Small temporal fluctuations in the ratios of MAAP-derived BC to COSMOS-derived BC were possibly caused by humidity effects and temporal variations in the optical properties of the measured particles. For MAAP, we also found that low filter-transmittance (0.2–0.5) could either increase or decrease the BC reading. The current best recommendations with the MAAP instrument are to use an increased cross section, to use data with high filter-transmittance (>0.5) only, and to control humidity. Copyright 2012 American Association for Aerosol Research

Seasonal and interannual variability of tropospheric ozone over an urban site in India: A study based on MOZAIC and CCM vertical profiles over Hyderabad

This study is based on the analysis of Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft (MOZAIC) data measured over Hyderabad, India during the years 2006–2008. Tropospheric profiles of O3 show clear seasonality with high and low values during the premonsoon and monsoon seasons, respectively. Analysis of back trajectory and fire count data indicates major roles for long-range transport and biomass burning in the seasonal variation of O3. Typically, lower levels of O3 in the monsoon season were due to the flow of marine air and negligible regional biomass burning, while higher levels in other seasons were due to transport of continental air. In the upper troposphere, relatively low levels of O3 during the monsoon and postmonsoon seasons were associated with deep convection. In the free troposphere, levels of O3 also show year-to-year variability as the values in the premonsoon of 2006 were higher by about 30 ppbv compared to 2008. The year-to-year variations were mainly due to transition from El Nino (2006) to La Nina (2008). The higher and lower levels of O3 were associated with strong and weak wind shears, respectively. Typically, vertical variations of O3 were anticorrelated with the lapse rate profile. The lower O3 levels were observed in the stable layers, but higher values in the midtroposphere were caused by long-range transport. In the PBL region, the mixing ratio of O3 shows strong dependencies on meteorological parameters. The Chemistry Climate Model (CCM2) reasonably reproduced the observed profiles of O3 except for the premonsoon season.

Source identification of VOCs at an urban site of western India: Effect of marathon events and anthropogenic emissions

Ambient volatile organic compounds (VOCs) were measured using a high-resolution proton transfer reaction-time of flight-mass spectrometer at an urban site of Ahmedabad in India during the winter season in 2014. Mixing ratios of VOCs show large diurnal and day-to-day variations. Although strongly influenced by local emissions, periods of higher VOCs were observed during transport from the polluted Indo-Gangetic Plains than those from the cleaner Thar Desert. However with different rates, VOCs decreased exponentially with increasing wind speed. Relative abundance of methanol varied with weather conditions contributing highest and lowest under fog and clear-sky conditions, respectively. Among the compounds reported here, oxygenated VOCs (OVOCs) contribute to a large fraction (67–85%) with methanol being most abundant (40–58%). In spite of predominant vehicular emissions, diurnal distribution and emission ratios (ERs) of several VOCs indicate the role of biogenic and secondary sources. The ratios of isoprene/benzene and OVOCs/benzene show significant enhancements during daytime suggesting their contributions from biogenic and secondary sources. During marathon and cyclothon events, mixing ratios of VOCs were 2–10 times higher compared to a normal Sunday. The ERs of VOCs estimated using the nighttime data on marathon day are well within the range of values reported for several megacities of the world. The average contributions of primary anthropogenic sources to acetaldehyde, acetone, and isoprene were 44 ± 06%, 45 ± 07%, and 63 ± 12%, respectively. During cloudy condition, the increase in anthropogenic contribution to acetaldehyde (~10%), acetone (9%) and isoprene (30%) is due to reduction in biogenic emissions and secondary formation of these VOCs.

Seasonal and interannual variability of carbon monoxide based on MOZAIC observations, MACC reanalysis, and model simulations over an urban site in India

The spatial and temporal variations of carbon monoxide (CO) are analyzed over a tropical urban site, Hyderabad (17°27′N, 78°28′E) in central India. We have used vertical profiles from the Measurement of ozone and water vapor by Airbus in-service aircraft (MOZAIC) aircraft observations, Monitoring Atmospheric Composition and Climate (MACC) reanalysis, and two chemical transport model simulations (Model for Ozone And Related Tracers (MOZART) and MRI global Chemistry Climate Model (MRI-CCM2)) for the years 2006–2008. In the lower troposphere, the CO mixing ratio showed strong seasonality, with higher levels (>300 ppbv) during the winter and premonsoon seasons associated with a stable anticyclonic circulation, while lower CO values (up to 100 ppbv) were observed in the monsoon season. In the planetary boundary layer (PBL), the seasonal distribution of CO shows the impact of both local meteorology and emissions. While the PBL CO is predominantly influenced by strong winds, bringing regional background air from marine and biomass burning regions, under calm conditions CO levels are elevated by local emissions. On the other hand, in the free troposphere, seasonal variation reflects the impact of long-range transport associated with the Intertropical Convergence Zone and biomass burning. The interannual variations were mainly due to transition from El Nino to La Nina conditions. The overall modified normalized mean biases (normalization based on the observed and model mean values) with respect to the observed CO profiles were lower for the MACC reanalysis than the MOZART and MRI-CCM2 models. The CO in the PBL region was consistently underestimated by MACC reanalysis during all the seasons, while MOZART and MRI-CCM2 show both positive and negative biases depending on the season.

Accumulation‐mode aerosol number concentrations in the Arctic during the ARCTAS aircraft campaign: Long‐range transport of polluted and clean air from the Asian continent

[1] We evaluate the impact of transport from midlatitudes on aerosol number concentrations in the accumulation mode (light‐scattering particles (LSP) with diameters >180 nm) in the Arctic during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. We focus on transport from the Asian continent. We find marked contrasts in the number concentration (NLSP), transport efficiency (TEN_LSP, the fraction transported from sources to the Arctic), size distribution, and the chemical composition of aerosols between air parcels from anthropogenic sources in East Asia (Asian AN) and biomass burning sources in Russia and Kazakhstan (Russian BB). Asian AN air had lower NLSP and TEN_LSP (25 cm �3 and 18% in spring and 6.2 cm �3 and 3.0% in summer) than Russian BB air (280 cm �3 and 97% in spring and 36 cm �3 and 7.6% in summer) due to more efficient wet scavenging during transport from East Asia. Russian BB in this spring is the most important source of accumulation‐mode aerosols over the Arctic, and BB emissions are found to be the primary source of aerosols within all the data in spring during ARCTAS. On the other hand, the contribution of Asian AN transport had a negligible effect on the accumulation‐mode aerosol number concentration in the Arctic during ARCTAS. Compared with background air, NLSP was 2.3–4.7 times greater for Russian BB air but 2.4–2.6 times less for Asian AN air in both spring and summer. This result shows that the transport of Asian AN air decreases aerosol number concentrations in the Arctic, despite the large emissions of aerosols in East Asia. The very low aerosol number concentrations in Asian AN air were caused by wet removal during vertical transport in association with warm conveyor belts (WCBs). Therefore, this cleansing effect will be prominent for air transported via WCBs from other midlatitude regions and seasons. The inflow of clean midlatitude air can potentially have an important impact on accumulation‐mode aerosol number concentrations in the Arctic. Citation: Matsui, H., et al. (2011), Accumulation‐mode aerosol number concentrations in the Arctic during the ARCTAS aircraft campaign: Long‐range transport of polluted and clean air from the Asian continent, J. Geophys. Res., 116, D20217, doi:10.1029/2011JD016189.

Distributions of ozone and related trace gases at an urban site in western India

Continuous in-situ measurements of surface ozone (O3), carbon monoxide (CO) and oxides of nitrogen (NOx) were conducted at Udaipur city in India during April 2010 to March 2011. We have analyzed the data to investigate both diurnal and seasonal variations in the mixing ratios of trace gases. The diurnal distribution of O3 showed highest values in the afternoon hours and lower values from evening till early morning. The mixing ratios of CO and NOx showed a sharp peak in the morning hours but lowest in the afternoon hours. The daily mean data of O3, CO and NOx varied in the ranges of 5–51 ppbv, 145–795 ppbv and 3–25 ppbv, respectively. The mixing ratios of O3 were highest of 28 ppbv and lowest 19 ppbv during the pre-monsoon and monsoon seasons, respectively. While the mixing ratios of both CO and NOx showed highest and lowest values during the winter and monsoon seasons, respectively. The diurnal pattern of O3 is mainly controlled by the variations in photochemistry and planetary boundary layer (PBL) depth. On the other hand, the seasonality of O3, CO and NOx were governed by the long-range transport associated mainly with the summer and winter monsoon circulations over the Indian subcontinent. The back trajectory data indicate that the seasonal variations in trace gases were caused mainly by the shift in long-range transport pattern. In monsoon season, flow of marine air and negligible presence of biomass burning in India resulted in lowest O3, CO and NOx values. The mixing ratios of CO and NOx show tight correlations during winter and pre-monsoon seasons, while poor correlation in the monsoon season. The emission ratio of ∆CO/∆NOx showed large seasonal variability but values were lower than those measured over the Indo Gangetic Plains (IGP). The mixing ratios of CO and NOx decreased with the increase in wind speed, while O3 tended to increase with the wind speed. Effects of other meteorological parameters in the distributions of trace gases were also noticed.