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Laboratory investigation of photochemical oxidation of organic aerosol from wood fires 2: analysis of aerosol mass spectrometer data

Experiments were conducted to investigate the effects of photo-oxidation on organic aerosol (OA) in dilute wood smoke by exposing emissions from soft- and hard-wood fires to UV light in a smog chamber. This paper focuses on changes in OA composition measured using a unit-mass-resolution quadrupole Aerosol Mass Spectrometer (AMS). The results highlight how photochemical processing can lead to considerable evolution of the mass, volatility and level of oxygenation of biomass-burning OA. Photochemical oxidation produced substantial new OA, more than doubling the OA mass after a few hours of aging under typical summertime conditions. Aging also decreased the volatility of the OA and made it progressively more oxygenated. The results also illustrate strengths of, and challenges with, using AMS data for source apportionment analysis. For example, the mass spectra of fresh and aged BBOA are distinct from fresh motor-vehicle emissions. The mass spectra of the secondary OA produced from aging wood smoke are very similar to those of the oxygenated OA (OOA) that dominates ambient AMS datasets, further reinforcing the connection between OOA and OA formed from photo-chemistry. In addition, aged wood smoke spectra are similar to those from OA created by photo-oxidizing dilute diesel exhaust. This demonstrates that the OOA observed in the atmosphere can be produced by photochemical aging of dilute emissions from different types of combustion systems operating on fuels with modern or fossil carbon. Since OOA is frequently the dominant component of ambient OA, the similarity of spectra of aged emissions from different sources represents an important challenge for AMS-based source apportionment studies.
Oxidation capacity of the city air of Santiago, Chile

The oxidation capacity of the highly polluted urban area of Santiago, Chile has been evaluated during a summer measurement campaign carried out from 8–20 March 2005. The hydroxyl (OH) radical budget was evaluated employing a simple quasi-photostationary-state model (PSS) constrained with simultaneous measurements of HONO, HCHO, O3, NO, NO2, j(O1D), j(NO2), 13 alkenes and meteorological parameters. In addition, a zero dimensional photochemical box model based on the Master Chemical Mechanism (MCMv3.1) has been used to estimate production rates and total free radical budgets, including OH, HO2 and RO2. Besides the above parameters, the MCM model has been constrained by the measured CO and volatile organic compounds (VOCs) including alkanes and aromatics. Both models simulate the same OH concentration during daytime indicating that the primary OH sources and sinks included in the simple PSS model predominate. Mixing ratios of the main OH radical precursors were found to be in the range 0.8–7 ppbv (HONO), 0.9–11 ppbv (HCHO) and 0–125 ppbv (O3). The alkenes average mixing ratio was ~58 ppbC accounting for ~12% of the total identified non-methane hydrocarbons (NMHCs). During the daytime (08:00 h–19:00 h), HONO photolysis was shown to be the most important primary OH radical source comprising alone ~55% of the total initial production rate, followed by alkene ozonolysis (~24%) and photolysis of HCHO (~16%) and O3 (~5%). The calculated average and maximum daytime OH production rates from HONO photolysis was 1.7 ppbv h−1 and 3.1 ppbv h−1, respectively. Based on the experimental results a strong photochemical daytime source of HONO is proposed. A detailed analysis of the sources of OH radical precursors has also been carried out.
Hydration of the lower stratosphere by ice crystal geysers over land convective systems

The possible impact of deep convective overshooting over land has been explored by six simultaneous soundings of water vapour, particles and ozone in the lower stratosphere next to Mesoscale Convective Systems (MCSs) during the monsoon season over West Africa in Niamey, Niger in August 2006. The water vapour measurements were carried out using a fast response FLASH-B Lyman-alpha hygrometer. The high vertical resolution observations of the instrument show the presence of accumulation of enhanced water vapour layers between the tropopause at 370 K and the 420 K level. Most of these moist layers are shown connected with overshooting events occurring upwind as identified from satellite IR images over which the air mass probed by the sondes passed during the three previous days. In the case of a local overshoot identified by echo top turrets above the tropopause by the MIT C-band radar also in Niamey, tight coincidence was found between enhanced water vapour, ice crystal and ozone dip layers indicative of fast uplift of tropospheric air across the tropopause. The water vapour mixing ratio in the enriched layers exceeds frequently by 1–3 ppmv the average 6 ppmv saturation ratio at the tropopause and by up to 7 ppmv in the extreme case of local storm in coincidence with the presence of ice crystals. The presence of such layers strongly suggests hydration of the lower stratosphere by geyser-like injection of ice particles over overshooting turrets. The pile-like increase of water vapour up to 19 km seen by the high-resolution hygrometer during the season of maximum temperature of the tropopause, suggests that the above hydration mechanism may contribute to the summer maximum moisture in the lower stratosphere. If this interpretation is correct, hydration by ice geysers across the tropopause might be an important contributor to the stratospheric water vapour budget.
Modelling of cirrus clouds – Part 2: Competition of different nucleation mechanisms

We study the competition of two different freezing mechanisms (homogeneous and heterogeneous freezing) in the same environment for cold cirrus clouds. To this goal we use the recently developed and validated ice microphysics scheme (Spichtinger and Gierens, 2009a) which distinguishes between ice classes according to their formation process. We investigate cases with purely homogeneous ice formation and compare them with cases where background ice nuclei in varying concentration heterogeneously form ice prior to homogeneous nucleation. We perform additionally a couple of sensitivity studies regarding threshold humidity for heterogeneous freezing, uplift speed, and ambient temperature, and we study the influence of random motions induced by temperature fluctuations in the clouds. We find three types of cloud evolution, homogeneously dominated, heterogeneously dominated, and a mixed type where neither nucleation process dominates. The latter case is prone to long–lasting in–cloud ice supersaturation of the order 30% and more.
Light-absorbing secondary organic material formed by glyoxal in aqueous aerosol mimics

Light-absorbing and high-molecular-weight secondary organic products were observed to result from the reaction of glyoxal in mildly acidic (pH=4) aqueous inorganic salt solutions mimicking aqueous tropospheric aerosol particles. High-molecular-weight (500–600 amu) products were observed when ammonium sulfate ((NH4)2SO4) or sodium chloride (NaCl) was present in the aqueous phase. The products formed in (NH4)2SO4 or ammonium nitrate (NH4NO3) solutions absorb light at UV and visible wavelengths. Substantial absorption at 300–400 nm develops within two hours, and absorption between 400–600 nm develops within days. Pendant drop tensiometry measurements show that the products are not surface-active. The experimental results along with ab initio predictions of the UV/Vis absorption of potential products suggest a mechanism involving the participation of the ammonium ion. If similar products are formed in atmospheric aerosol particles, they could change the optical properties of the seed aerosol over its lifetime.
Chemistry and transport of pollution over the Gulf of Mexico and the Pacific: spring 2006 INTEX-B campaign overview and first results

Intercontinental Chemical Transport Experiment-B (INTEX-B) was a major NASA (Acronyms are provided in Appendix A.) led multi-partner atmospheric field campaign completed in the spring of 2006 (<a href="http://cloud1.arc.nasa.gov/intex-b/"target="_blank">http://cloud1.arc.nasa.gov/intex-b/</a>). Its major objectives aimed at (i) investigating the extent and persistence of the outflow of pollution from Mexico; (ii) understanding transport and evolution of Asian pollution and implications for air quality and climate across western North America; and (iii) validating space-borne observations of tropospheric composition. INTEX-B was performed in two phases. In its first phase (1–21 March), INTEX-B operated as part of the MILAGRO campaign with a focus on observations over Mexico and the Gulf of Mexico. In the second phase (17 April–15 May), the main INTEX-B focus was on trans-Pacific Asian pollution transport. Multiple airborne platforms carrying state of the art chemistry and radiation payloads were flown in concert with satellites and ground stations during the two phases of INTEX-B. Validation of Aura satellite instruments (TES, OMI, MLS, HIRDLS) was a key objective within INTEX-B. Satellite products along with meteorological and 3-D chemical transport model forecasts were integrated into the flight planning process to allow targeted sampling of air parcels. Inter-comparisons were performed among and between aircraft payloads to quantify the accuracy of data and to create a unified data set. Pollution plumes were sampled over the Gulf of Mexico and the Pacific several days after downwind transport from source regions. Signatures of Asian pollution were routinely detected by INTEX-B aircraft, providing a valuable data set on gas and aerosol composition to test models and evaluate pathways of pollution transport and their impact on air quality and climate. This overview provides details about campaign implementation and a context within which the present and future INTEX-B/MILAGRO publications can be understood.
Sensitivity of aerosol optical thickness and aerosol direct radiative effect to relative humidity

We present a sensitivity study of the effects of spatial and temporal resolution of atmospheric relative humidity (RH) on calculated aerosol optical thickness (AOT) and the aerosol direct radiative effects (DRE) in a global model. We carry out different modeling experiments using the same aerosol fields simulated in the Global Modeling Initiative (GMI) model at a resolution of 2° latitude by 2.5° longitude, using time-averaged fields archived every three hours by the Goddard Earth Observation System Version 4 (GEOS-4), but we change the horizontal and temporal resolution of the relative humidity fields. We find that, on a global average, the AOT calculated using RH at a 1°×1.25° horizontal resolution is 11% higher than that using RH at a 2°×2.5° resolution, and the corresponding DRE at the top of the atmosphere is 8–9% and 15% more negative (i.e., more cooling) for total aerosols and anthropogenic aerosol alone, respectively, in the finer spatial resolution case. The difference is largest over surface escarpment regions (e.g. >200% over the Andes Mountains) where RH varies substantially with surface terrain. The largest zonal mean AOT difference occurs at 50–60° N (16–21%), where AOT is also relatively larger. A similar impact is also found when the time resolution of RH is increased. This increase of AOT and aerosol cooling with the increase of model resolution is due to the highly non-linear relationship between RH and the aerosol mass extinction efficiency (MEE) at high RH (>80%). Our study is a specific example of the uncertainty in model results highlighted by multi-model comparisons such as AeroCom, and points out one of the many inter-model differences that can contribute to the overall spread among models.
Diffusional and accretional growth of water drops in a rising adiabatic parcel: effects of the turbulent collision kernel

A large set of rising adiabatic parcel simulations is executed to investigate the combined diffusional and accretional growth of cloud droplets in maritime and continental conditions, and to assess the impact of enhanced droplet collisions due to small-scale cloud turbulence. The microphysical model applies the droplet number density function to represent spectral evolution of cloud and rain/drizzle drops, and various numbers of bins in the numerical implementation, ranging from 40 to 320. Simulations are performed applying two traditional gravitational collection kernels and two kernels representing collisions of cloud droplets in the turbulent environment, with turbulent kinetic energy dissipation rates of 100 and 400 cm2 s−3. The overall result is that the rain initiation time significantly depends on the number of bins used, with earlier initiation of rain when the number of bins is low. This is explained as a combination of the increase of the width of activated droplet spectrum and enhanced numerical spreading of the spectrum during diffusional and collisional growth when the number of model bins is low. Simulations applying around 300 bins seem to produce rain at times which no longer depend on the number of bins, but the activation spectra are unrealistically narrow. These results call for an improved representation of droplet activation in numerical models of the type used in this study. Despite the numerical effects that impact the rain initiation time in different simulations, the turbulent speedup factor, the ratio of the rain initiation time for the turbulent collection kernel and the corresponding time for the gravitational kernel, is approximately independent of aerosol characteristics, parcel vertical velocity, and the number of bins used in the numerical model. The turbulent speedup factor is in the range 0.75–0.85 and 0.60–0.75 for the turbulent kinetic energy dissipation rates of 100 and 400 cm2 s−3, respectively.
Dispersion of traffic-related exhaust particles near the Berlin urban motorway – estimation of fleet emission factors

Atmospheric particle number size distributions of airborne particles (diameter range 10–500 nm) were collected over ten weeks at three sites in the vicinity of the A100 urban motorway in Berlin, Germany. The A100 carries about 180 000 vehicles on a weekday. The roadside particle distributions showed a number maximum between 20 and 60 nm clearly related to the motorway emissions. The average total number concentration at roadside was 28 000 cm−3 with a total range of 1200–168 000 cm−3. At distances of 80 and 400 m from the motorway the concentrations decreased to mean levels of 11 000 and 9000 cm−3, respectively. An obstacle-resolving dispersion model was applied to simulate the 3-D flow field and traffic tracer transport in the urban environment around the motorway. By inverse modelling, vehicle emission factors were derived that are representative of a fleet with a relative share of 6% lorry-like vehicles, and driving at a speed of 80 km h−1. Three different calculation approaches were compared, which differ in the choice of the experimental winds driving the flow simulation. The average emission factor per vehicle was 2.1 (±0.2) · 1014 km−1 for particle number and 0.077 (±0.01) · 1014 cm3 km−1 for particle volume. Regression analysis suggested that lorry-like vehicles emit 123 (±28) times more particle number than passenger car-like vehicles, and lorry-like vehicles account for about 91% of particulate number emissions on weekdays. Our work highlights the increasing applicability of 3-D flow models in urban microscale environments and their usefulness for determining traffic emission factors.
Performance evaluation of a high-resolution parallel-plate differential mobility analyzer

A high-resolution differential mobility analyzer (DMA), specially designed for (i) the measurement of ion mobility spectra, and (ii) the generation of a continuous stream of monomobile ions, has been developed and tested. The apparatus consists of two parallel-plate electrodes between which an electric field is applied. The test ion stream flows into the instrument through a narrow rectangular slit made in one of the electrodes, and migrates toward the other electrode driven by the applied field, while being transported by a stream of clean air which flows parallel to the plates at Reynolds number between 2×104 and 9×104 in laminar flow conditions. The collector electrode contains also a narrow slit through which ions of the desired mobility are withdrawn out of DMA. The classified ion current is measured with a high-sensitivity electrometer having a noise level around 0.1 fA. The theory behind the DMA operation is first discussed, focusing on the special case of parallel-plate geometry. Some generic results showing the stability and repeatability of the measurements and the resolving power of the instrument are presented next. The last part of the paper deals with the application of the apparatus to the study of the effect of humidity and aging time on the mobility spectra of air ions generated by a low-activity 241Am source.