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Evolution of trace gases and particles emitted by a chaparral fire in California

Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated downwind plume in the first ~4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared spectrometer (AFTIR), aerosol mass spectrometer (AMS), single particle soot photometer (SP2), nephelometer, LiCor CO2 analyzer, a chemiluminescence ozone instrument, and a wing-mounted meteorological probe. Our measurements included: CO2; CO; NOx; NH3; non-methane organic compounds; organic aerosol (OA); inorganic aerosol (nitrate, ammonium, sulfate, and chloride); aerosol light scattering; refractory black carbon (rBC); and ambient temperature, relative humidity, barometric pressure, and three-dimensional wind velocity. The molar ratio of excess O3 to excess CO in the plume (ΔO3/ΔCO) increased from −5.13 (±1.13) × 10−3 to 10.2 (±2.16) × 10−2 in ~4.5 h following smoke emission. Excess acetic and formic acid (normalized to excess CO) increased by factors of 1.73 ± 0.43 and 7.34 ± 3.03 (respectively) over the same time since emission. Based on the rapid decay of C2H4 we infer an in-plume average OH concentration of 5.27 (±0.97) × 106 molec cm−3, consistent with previous studies showing elevated OH concentrations in biomass burning plumes. Ammonium, nitrate, and sulfate all increased over the course of 4 h. The observed ammonium increase was a factor of 3.90 ± 2.93 in about 4 h, but accounted for just ~36% of the gaseous ammonia lost on a molar basis. Some of the gas phase NH3 loss may have been due to condensation on, or formation of, particles below the AMS detection range. NOx was converted to PAN and particle nitrate with PAN production being about two times greater than production of observable nitrate in the first ~4 h following emission. The excess aerosol light scattering in the plume (normalized to excess CO2) increased by a factor of 2.50 ± 0.74 over 4 h. The increase in light scattering was similar to that observed in an earlier study of a biomass burning plume in Mexico where significant secondary formation of OA closely tracked the increase in scattering. In the California plume, however, ΔOA/ΔCO2 decreased sharply for the first hour and then increased slowly with a net decrease of ~20% over 4 h. The fraction of thickly coated rBC particles increased up to ~85% over the 4 h aging period. Decreasing OA accompanied by increased scattering/particle coating in initial aging may be due to a combination of particle coagulation and evaporation processes. Recondensation of species initially evaporated from the particles may have contributed to the subsequent slow rise in OA. We compare our results to observations from other plume aging studies and suggest that differences in environmental factors such as smoke concentration, oxidant concentration, actinic flux, and RH contribute significantly to the variation in plume evolution observations.
Exploring the atmospheric chemistry of nitrous acid (HONO) at a rural site in Southern China

We performed measurements of nitrous acid (HONO) during the PRIDE-PRD2006 campaign in the Pearl River Delta region 60 km north of Guangzhou, China, for 4 weeks in June 2006. HONO was measured by a LOPAP in-situ instrument which was setup in one of the campaign supersites along with a variety of instruments measuring hydroxyl radicals, trace gases, aerosols, and meteorological parameters. Maximum diurnal HONO mixing ratios of 1–5 ppb were observed during the nights. We found that the nighttime build-up of HONO can be attributed to the heterogeneous NO2 to HONO conversion on ground surfaces and the OH + NO reaction. In addition to elevated nighttime mixing ratios, measured noontime values of ≈200 ppt indicate the existence of a daytime source higher than the OH + NO→HONO reaction. Using the simultaneously recorded OH, NO, and HONO photolysis frequency, a daytime additional source strength of HONO (PM) was calculated to be 0.77 ppb h−1 on average. This value compares well to previous measurements in other environments. Our analysis of PM provides evidence that the photolysis of HNO3 adsorbed on ground surfaces contributes to the HONO formation.
Formation of 3-methyl-1,2,3-butanetricarboxylic acid via gas phase oxidation of pinonic acid – a mass spectrometric study of SOA aging

This paper presents the results of mass spectrometric investigations of the OH-initiated oxidative aging of α-pinene SOA under simulated tropospheric conditions at the large aerosol chamber facility AIDA, Karlsruhe Institute of Technology. In particular, the OH-initiated oxidation of pure pinic and pinonic acid, two well-known oxidation products of α-pinene, was investigated. Two complementary analytical techniques were used, on-line atmospheric pressure chemical ionization/mass spectrometry (APCI/MS) and filter sampling followed by liquid chromatography/mass spectrometry (LC/ESI-MS). The results show that 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a very low volatile α-pinene SOA product and a tracer compound for terpene SOA, is formed from the oxidation of pinonic acid and that this oxidation takes place in the gas phase. This finding is confirmed by temperature-dependent aging experiments on whole SOA formed from α-pinene, in which the yield of MBTCA scales with the pinonic acid fraction in the gas phase. Based on the results, several feasible gas-phase radical mechanisms are discussed to explain the formation of MBTCA from OH-initiated pinonic acid oxidation.
Air pollution control and decreasing new particle formation lead to strong climate warming

The number concentration of cloud droplets determines several climatically relevant cloud properties. A major cause for the high uncertainty in the indirect aerosol forcing is the availability of cloud condensation nuclei (CCN), which in turn is highly sensitive to atmospheric new particle formation. Here we present the effect of new particle formation on anthropogenic aerosol forcing in present-day (year 2000) and future (year 2100) conditions. The present-day total aerosol forcing is increased from −1.0 W m−2 to −1.6 W m−2 when nucleation is introduced into the model. Nucleation doubles the change in aerosol forcing between years 2000 and 2100, from +0.6 W m−2 to +1.4 W m−2. Two climate feedbacks are studied, resulting in additional negative forcings of −0.1 W m−2 (+10% DMS emissions in year 2100) and −0.5 W m−2 (+50% BVOC emissions in year 2100). With the total aerosol forcing diminishing in response to air pollution control measures taking effect, warming from increased greenhouse gas concentrations can potentially increase at a very rapid rate.
Corrigendum to "Accumulation of aerosols over the Indo-Gangetic plains and southern slopes of the Himalayas: distribution, properties and radiative effects during the 2009 pre-monsoon season" published in Atmos. Chem. Phys., 11, 12841–12863, 2011
Corrigendum to "Simulated enhancement of ENSO-related rainfall variability due to Australian dust" published in Atmos. Chem. Phys., 11, 6575–6592, 2011
Atmospheric greenhouse gases retrieved from SCIAMACHY: comparison to ground-based FTS measurements and model results

SCIAMACHY onboard ENVISAT (launched in 2002) enables the retrieval of global long-term column-averaged dry air mole fractions of the two most important anthropogenic greenhouse gases carbon dioxide and methane (denoted XCO2 and XCH4). In order to assess the quality of the greenhouse gas data obtained with the recently introduced v2 of the scientific retrieval algorithm WFM-DOAS, we present validations with ground-based Fourier Transform Spectrometer (FTS) measurements and comparisons with model results at eight Total Carbon Column Observing Network (TCCON) sites providing realistic error estimates of the satellite data. Such validation is a prerequisite to assess the suitability of data sets for their use in inverse modelling. It is shown that there are generally no significant differences between the carbon dioxide annual increases of SCIAMACHY and the assimilation system CarbonTracker (2.00 &pm; 0.16 ppm yr−1 compared to 1.94 &pm; 0.03 ppm yr−1 on global average). The XCO2 seasonal cycle amplitudes derived from SCIAMACHY are typically larger than those from TCCON which are in turn larger than those from CarbonTracker. The absolute values of the northern hemispheric TCCON seasonal cycle amplitudes are closer to SCIAMACHY than to CarbonTracker and the corresponding differences are not significant when compared with SCIAMACHY, whereas they can be significant for a subset of the analysed TCCON sites when compared with CarbonTracker. At Darwin we find discrepancies of the seasonal cycle derived from SCIAMACHY compared to the other data sets which can probably be ascribed to occurrences of undetected thin clouds. Based on the comparison with the reference data, we conclude that the carbon dioxide data set can be characterised by a regional relative precision (mean standard deviation of the differences) of about 2.2 ppm and a relative accuracy (standard deviation of the mean differences) of 1.1–1.2 ppm for monthly average composites within a radius of 500 km. For methane, prior to November 2005, the regional relative precision amounts to 12 ppb and the relative accuracy is about 3 ppb for monthly composite averages within the same radius. The loss of some spectral detector pixels results in a degradation of performance thereafter in the spectral range currently used for the methane column retrieval. This leads to larger scatter and lower XCH4 values are retrieved in the tropics for the subsequent time period degrading the relative accuracy. As a result, the overall relative precision is estimated to be 17 ppb and the relative accuracy is in the range of about 10–20 ppb for monthly averages within a radius of 500 km. The derived estimates show that the SCIAMACHY XCH4 data set before November 2005 is suitable for regional source/sink determination and regional-scale flux uncertainty reduction via inverse modelling worldwide. In addition, the XCO2 monthly data potentially provide valuable information in continental regions, where there is sparse sampling by surface flask measurements.
Observation and modelling of OH and HO2 concentrations in the Pearl River Delta 2006: a missing OH source in a VOC rich atmosphere

Ambient OH and HO2 concentrations were measured by laser induced fluorescence (LIF) during the PRIDE-PRD2006 (Program of Regional Integrated Experiments of Air Quality over the Pearl River Delta, 2006) campaign at a rural site downwind of the megacity of Guangzhou in Southern China. The observed OH concentrations reached daily peak values of (15–26) × 106 cm−3 which are among the highest values so far reported for urban and suburban areas. The observed OH shows a consistent high correlation with j(O1D) over a broad range of NOx conditions. The correlation cannot be reproduced by model simulations, indicating that OH stabilizing processes are missing in current models. The observed OH exhibited a weak dependence on NOx in contrast to model predictions. While modelled and measured OH agree well at NO mixing ratios above 1 ppb, a continuously increasing underprediction of the observed OH is found towards lower NO concentrations, reaching a factor of 8 at 0.02 ppb NO. A dependence of the modelled-to-measured OH ratio on isoprene cannot be concluded from the PRD data. However, the magnitude of the ratio fits into the isoprene dependent trend that was reported from other campaigns in forested regions. Hofzumahaus et al. (2009) proposed an unknown OH recycling process without NO, in order to explain the high OH levels at PRD in the presence of high VOC reactivity and low NO. Taking a recently discovered interference in the LIF measurement of HO2 into account, the need for an additional HO2 → OH recycling process persists, but the required source strength may be up to 20% larger than previously determined. Recently postulated isoprene mechanisms by Lelieveld et al. (2008) and Peeters and Müller (2010) lead to significant enhancements of OH expected for PRD, but an underprediction of the observed OH by a factor of two remains at low NO (0.1–0.2 ppb). If the photolysis of hydroperoxy aldehydes from isoprene is as efficient as proposed by Peeters and Müller (2010), the corresponding OH formation at PRD would be more important than the primary OH production from ozone and HONO. While the new isoprene mechanisms need to be confirmed by laboratory experiments, there is probably need for other, so far unidentified chemical processes to explain entirely the high OH levels observed in Southern China.
Mean winds, temperatures and the 16- and 5-day planetary waves in the mesosphere and lower thermosphere over Bear Lake Observatory (42° N, 111° W)

Atmospheric temperatures and winds in the mesosphere and lower thermosphere have been measured simultaneously using the Aura satellite and a meteor radar at Bear Lake Observatory (42° N, 111° W), respectively. The data presented in this study is from the interval March 2008 to July 2011. The mean winds observed in the summer-time over Bear Lake Observatory show the meridional winds to be equatorward at meteor heights during April−August and to reach monthly-mean velocities of −12 m s−1. The mean winds are closely related to temperatures in this region of the atmosphere and in the summer the coldest mesospheric temperatures occur about the same time as the strongest equatorward meridional winds. The zonal winds are eastward through most of the year and in the summer strong eastward zonal wind shears of up to ~4.5 m s−1 km−1 are present. However, westward winds are observed at the upper heights in winter and sometimes during the equinoxes. Considerable inter-annual variability is observed in the mean winds and temperatures. Comparisons of the observed winds with URAP and HWM-07 reveal some large differences. Our radar zonal wind observations are generally more eastward than predicted by the URAP model zonal winds. Considering the radar meridional winds, in comparison to HWM-07 our observations reveal equatorward flow at all meteor heights in the summer whereas HWM-07 suggests that only weakly equatorward, or even poleward flows occur at the lower heights. However, the zonal winds observed by the radar and modelled by HWM-07 are generally similar in structure and strength. Signatures of the 16- and 5-day planetary waves are clearly evident in both the radar-wind data and Aura-temperature data. Short-lived wave events can reach large amplitudes of up to ~15 m s−1 and 8 K and 20 m s−1 and 10 K for the 16- and 5-day waves, respectively. A clear seasonal and short-term variability are observed in the 16- and 5-day planetary wave amplitudes. The 16-day wave reaches largest amplitude in winter and is also present in summer, but with smaller amplitudes. The 5-day wave reaches largest amplitude in winter and in late summer. An inter-annual variability in the amplitude of the planetary waves is evident in the four years of observations. Some 41 episodes of large-amplitude wave occurrence are identified. Temperature and wind amplitudes for these episodes, AT and AW, that passed the Student T-test were found to be related by, AT = 0.34 AW and AT = 0.62 AW for the 16- and 5-day wave, respectively.
Revised identification of tropical oceanic cumulus congestus as viewed by CloudSat

Congestus cloud convective features are examined in one year of tropical oceanic cloud observations from the CloudSat/CALIPSO instruments. Two types of convective clouds (cumulus and deep convective, based on classification profiles from radar), and associated differences in radar reflectivity and radar/lidar cloud-top height are considered. Congestus convective features are defined as contiguous convective clouds with heights between 3 and 9 km. Three criteria were used in previous studies to identify congestus: (1) CloudSat and CALIPSO cloud-top heights less than 1 km apart; (2) CloudSat 0 dBZ echo-top height less than 1 km from CloudSat cloud-top height, and (3) CloudSat 10 dBZ echo-top height less than 2 km from CloudSat cloud-top height. A majority of congestus convective features satisfy the second and third requirements. However, over 40% of convective features identified had no associated CALIPSO cloud-top height, predominantly due to the extinguishment of the lidar beam above the CloudSat-reported convective cloud. For the remaining cells, approximately 56% of these satisfy all three requirements; when considering the lidar beam-extinction issue, only 31% of congestus convective features are identified using these criteria. This implies that while previous methods used to identify congestus clouds may be accurate in finding vigorous convection (such as transient congestus rising toward the tropopause), these criteria may miss almost 70% of the total observed congestus convective features, suggesting a more general approach should be used to describe congestus and its surrounding environment.