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Characterization of volatile organic compounds (VOCs) in Asian and north American pollution plumes during INTEX-B: identification of specific Chinese air mass tracers

We present results from the Intercontinental Chemical Transport Experiment – Phase B (INTEX-B) aircraft mission conducted in spring 2006. By analyzing the mixing ratios of volatile organic compounds (VOCs) measured during the second part of the field campaign, together with kinematic back trajectories, we were able to identify five plumes originating from China, four plumes from other Asian regions, and three plumes from the United States. To identify specific tracers for the different air masses we characterized their VOC composition and we compared their background levels with those obtained during the 2004 INTEX-A mission. The Chinese and other Asian air masses were significantly enhanced in carbonyl sulfide (OCS) and methyl chloride (CH3Cl), while all CFC replacement compounds were elevated in US plumes, particularly HFC-134a. Although elevated mixing ratios of Halon-1211 were measured in some Chinese plume samples, several measurements at background levels were also observed. After analyzing the VOC distribution and correlations within the Chinese pollution plumes and applying principal component analysis (PCA), we suggest the use of a suite of species, rather than a single gas, as specific tracers of Chinese air masses (namely OCS, CH3Cl, 1,2-dichloroethane, ethyl chloride, and Halon-1211). In an era of constantly changing halocarbon usage patterns, this suite of gases best reflects new emission characteristics from China.
Characteristics and source apportionment of atmospheric aerosols at the summit of Mount Tai during summertime

To investigate the long-range transport of air pollutants in North China, aerosol samples were collected at the summit of Mount Tai (Shandong province) in June of 2006. Water-soluble ion and metal element concentrations were analyzed using ion chromatography (IC) and inductively coupled plasma-mass spectrometry (ICP-MS), respectively. Results showed three different size distributions for the ions and metal elements characterized, including masses in: (i) the accumulation mode, with a peak at 0.43 to 1.1 μm (SO42−, NH4+, K+, Pb, Zn, Ti); (ii) the coarse particle mode, with a peak at 4.7 to 5.8 μm (Ca2+, Mg2+, Ca, Mg, Fe, Al, Ba, Mn); and (iii) a bimodal distribution, with peaks at 0.43 to 0.65 μm and 4.7 to 5.8 μm (NO3−, Na+, Cl−, Na, Co, Ni, Mo, Cu). When SO42− was in high concentration, the mass median diameter was between 0.5 μm and 0.8 μm, belonging to the "drop mode". The concentrations of SO42−, NO3−, NH4+, and K+ were quite variable. Interestingly, SO42−, NO3−, and NH4+ reached their highest concentrations when the humid air mass was coming from the south. Furthermore, crustal element concentrations increased when the air mass came from the north and pollution element concentrations were elevated when the air mass came from the south.
Information-based mid-upper tropospheric methane derived from Atmospheric Infrared Sounder (AIRS) and its validation

Atmospheric Infrared Sounder (AIRS) measurements of methane (CH4) generally contain about 1.0 degree of freedom and are therefore dependent on a priori assumptions about the vertical methane distribution as well as the temperature lapse rate and the amount of moisture. Thus it requires that interpretation and/or analysis of the CH4 spatial and temporal variation based on the AIRS retrievals need to use the averaging kernels (AK). To simplify the use of satellite retrieved products for scientific analysis, a method based on the information content of the retrievals is developed, in which the AIRS retrieved CH4 in the layer from 50 to 250 hPa below the tropopause is used to characterize the mid-upper tropospheric CH4 in the mid-high latitude regions. The basis of this method is that in the mid-high latitude regions the maximum sensitive layers of AIRS to CH4 have a good correlation with the tropopause heights, and these layers are usually between 50 and 250 hPa below the tropopause. Validation using the aircraft measurements from NOAA/ESRL/GMD and the campaigns INTEX-A and -B indicated that the correlation of AIRS mid-upper tropospheric CH4 with aircraft measurements is ~0.6–0.7, and its the bias and rms difference are less than ±1% and 1.2%, respectively. Further comparison of the CH4 seasonal cycle indicated that the cycle from AIRS mid-upper tropospheric CH4 is in a reasonable agreement with NOAA aircraft measurements. This method provides a simple way to use the thermal infrared sounders data to approximately analyze the spatial and temporal variation CH4 in the upper free tropospere without referring the AK. This method is applicable to derive tropospheric CH4 as well as other trace gases for any thermal infrared sensors.
Dynamical modes associated with the Antarctic ozone hole

Generalized Maximum Covariance Analysis (GMCA) has been developed and applied to diagnosing the dynamical modes associated with variations in the Antarctic spring ozone hole. GMCA is used to identify the most important patterns of co-variability between interannual ozone mixing ratio variations in the Antarctic region and temperature, zonal, meridional and vertical velocities between 100 and 10 hPa in the same region. The most important two pairs of GMCA time coefficients show large year-to-year variations and trends, which are connected with the growth of the Antarctic Ozone Hole and the increase of ozone depleting substances. The associated spatial patterns of ozone variations may be characterized as being quasi-symmetric and asymmetric about the pole. These patterns of ozone variations are associated with comparable patterns of variations of temperature and winds through most of the vertical domain. The year 2000 is shown to be dominated by the asymmetric mode, whereas the adjacent year 2001 is dominated by the quasi-symmetric mode. A case study, focusing on the asymmetric differences between these two years, shows the magnitude of the ozone mixing ratio, temperature and zonal wind differences to be in the range of 2 e–6 kg/kg, 10°C and 10 m/s, respectively. Budget calculations show that transport processes contribute substantially to the ozone and temperature changes in the middle stratosphere over the Antarctic continent. However, both radiative and chemical processes also play important roles in the changes.
Characterization of organic ambient aerosol during MIRAGE 2006 on three platforms

Submicron atmospheric aerosol particles were collected during the Megacity Initiative: Local and Global Research Observation (MILAGRO) in March 2006 at three platforms located in the Mexico City urban area (at the Mexico City Atmospheric Monitoring System building – SIMAT), at about 60 km south-east of the metropolitan area (Altzomoni in the Cortes Pass), and on board the NCAR C130 aircraft. Organic functional group and elemental composition were measured by FTIR and XRF. The average organic mass (OM) concentration, calculated as the sum of organic functional group concentrations, was 9.9 μg m−3 at SIMAT, 6.6 μg m−3 at Altzomoni, and 5.7 μg m−3 on the C130. Aliphatic saturated C-C-H and carboxylic acid COOH groups dominated OM (more than 60%) at the ground sites. On the C130, a non-acid carbonyl C=O, carboxylic acid COOH, and amine NH2 groups were observed in concentrations above detection limit only outside the Mexico City basin. From the elemental composition of SIMAT samples, we estimated the upper bound of average contribution of biomass burning to the organic carbon (OC) as 33–39%. The average OM/OC ratio was 1.8 at SIMAT, 2.0 at Altzomoni, and 1.6–1.8 on the C130. On the aircraft, higher OM/OC ratios were measured outside of the Mexico City basin, north of the urban area, along the city outflow direction. The average carboxylic acid to aliphatic saturated ratio at SIMAT reflected a local increase of oxidized functional group concentration in aged particles.
Long term particle size distribution measurements at Mount Waliguan, a high-altitude site in inland China

Particle number size distributions in size range 12–570 nm were measured continuously at Mount Waliguan, a remote mountain-top station in inland China. The station is located at the altitude of 3816 m a.s.l., and some 600–1200 m above the surrounding area. The measurement period lasted from September 2005 to May 2007. The measurements were verified with independent CPC measurements at the same site. The average particle concentration in ambient conditions was 2030 cm−3, which is higher than the values measured at similar altitude in other regions of the world. On average, the Aitken mode contributed to roughly half of the particle number concentration. The concentrations were found to be higher during the summer than during the winter. The diurnal variation was also investigated and a clear pattern was found for the nucleation mode during all seasons, so that the nucleation mode particle concentration increased in the afternoon. The same pattern was visible in the Aitken mode during the summer, whereas the accumulation mode did not show any level of diurnal pattern during any season. Excluding the nucleation mode, the average day-time particle concentrations were not significantly higher than those measured at night-time, indicating no systematic pattern of change between planetary boundary layer conditions and free troposphere conditions. In air masses coming from east, the number concentration of particles was higher than in other air masses, which indicates that the air mass might be affected anthropogenic pollution east of the station. Also other factors, such as active new-particle formation, keep aerosol number concentrations high in the area.
Organic composition of single and submicron particles in different regions of western North America and the eastern Pacific during INTEX-B 2006

Single particles were collected from an aircraft platform as part of the Intercontinental Chemical Transport Experiment – Phase B (INTEX-B) conducted over the eastern Pacific and western North America. Single particle spectra were obtained using scanning transmission X-ray microscopy-near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS). Bulk submicron particles were also collected and organic functional group and elemental concentrations were quantified with Fourier transform infrared (FTIR) spectroscopy and X-ray fluorescence (XRF). Single particle spectra were classified into metaclasses associated with different sources and atmospheric processing. Particles with spectra indicative of secondary organic aerosol production and combustion sources were found at several locations and a range of altitudes. At lower altitudes, particles with spectra resembling soil dust and biomass burning fingerprints were commonly observed. The types of particle spectra most commonly observed aloft were similar to those observed during a previous study over the northwestern Pacific, indicating that long-range transport may have been an important particle source. Single particle spectra provided evidence that condensation and surface-limited oxidation contributed to particle growth. Organic mass (OM) concentrations ranged from 1 to 7 μg m−3 and averaged 2.4–4.1 μg m−3. Alkane functional groups were the largest fraction of OM, averaging 1.9–2.1 μg m−3 or 50–76% of OM, followed by alcohol functional groups (0.35–0.39 μg m−3, 9–14%). Organic and elemental concentrations are compared within and among geographical air mass regions: "Pacific" free troposphere, "Continental" free troposphere, "Seattle" metropolitan region, and the California "Central Valley". OM concentrations were highest and most variable in the Central Valley (3.5±2 μg m−3). Oxygen-to-carbon ratios were relatively constant in the Central Valley but variable for the Continental air masses. Overall, the OM concentrations showed greater variability within air mass categories as compared to averages among them, suggesting sampled air mass regions included a variety of sources and processing of organic aerosol.
Implementation and testing of a simple data assimilation algorithm in the regional air pollution forecast model, DEOM

A simple data assimilation algorithm based on statistical interpolation has been developed and coupled to a long-range chemistry transport model, the Danish Eulerian Operational Model (DEOM), applied for air pollution forecasting at the National Environmental Research Institute (NERI), Denmark. In this paper, the algorithm and the results from experiments designed to find the optimal setup of the algorithm are described. The algorithm has been developed and optimized via eight different experiments where the results from different model setups have been tested against measurements from the EMEP (European Monitoring and Evaluation Programme) network covering a half-year period, April–September 1999. The best performing setup of the data assimilation algorithm for surface ozone concentrations has been found, including the combination of determining the covariances using the Hollingsworth method, varying the correlation length according to the number of adjacent observation stations and applying the assimilation routine at three successive hours during the morning. Improvements in the correlation coefficient in the range of 0.1 to 0.21 between the results from the reference and the optimal configuration of the data assimilation algorithm, were found. The data assimilation algorithm will in the future be used in the operational THOR integrated air pollution forecast system, which includes the DEOM.
Implications of Lagrangian transport for simulations with a coupled chemistry-climate model

For the first time a purely Lagrangian transport algorithm is applied in a fully coupled chemistry-climate model (CCM). We use the numerically non-diffusive Lagrangian scheme ATTILA instead of the operational semi-Lagrangian scheme for the transport of water vapour, cloud water and chemical trace species in the CCM E39C. The new model version including the Lagrangian scheme is referred to as E39C-A. The implications of the Lagrangian transport scheme for stratospheric model dynamics and tracer distributions in E39C-A are evaluated by comparison with observations and results of the previous model version E39C. We found in a previous paper that several deficiencies in stratospheric dynamics in E39C originate from a pronounced modelled wet bias and an associated cold bias in the extra-tropical lowermost stratosphere. Contrary to the semi-Lagrangian scheme ATTILA shows a largely reduced meridional transport of water vapour from the tropical upper troposphere into the extratropical lowermost stratosphere. The reduction of the moisture and temperature bias in E39C-A leads to a significant advancement of stratospheric dynamics in terms of the mean state as well as annual and interannual variability. In this study we show that as a consequence of both, the favourable numerical characteristics of the Lagrangian transport scheme and the improved model dynamics, E39C-A generally shows more realistic distributions of chemical trace species: Compared to E39C high stratospheric chlorine (Cly) concentrations extend further downward. Therefore E39C-A realistically covers the altitude of maximum ozone depletion in the stratosphere. The location of the ozonopause, i.e. the transition from low tropospheric to high stratospheric ozone values, is also clearly improved in E39C-A. Not only the spatial distribution but also the temporal evolution of stratospheric Cly in the past is realistically reproduced in E39C-A which is an important step towards a more reliable projection of future changes, especially of stratospheric ozone. Despite a large number of improvements there are still remaining model deficiencies like a general overestimation of total column ozone.
In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry

We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 7.6% to the overall ozone-olefin loss rate above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 6–32% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.1% to the total ozone-olefin loss rate above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models.