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Winter- and summertime continental influences on tropospheric O3 and CO observed by TES over the western North Atlantic Ocean

The distributions of tropospheric ozone (O3) and carbon monoxide (CO), and the synoptic factors regulating these distributions over the western North Atlantic Ocean during winter and summer were investigated using profile retrievals from the Tropospheric Emission Spectrometer (TES) for 2004–2006. Seasonal composites of TES retrievals, reprocessed to remove the influence of the a priori on geographical and seasonal structure, exhibited strong seasonal differences. At the 681 hPa level during winter months of December, January and February (DJF) the composite O3 mixing ratios were uniformly low (~45 ppbv), but continental export was evident in a channel of enhanced CO (100–110 ppbv) flowing eastward from the US coast. In summer months June, July, and August (JJA) O3 mixing ratios were variable (45–65 ppbv) and generally higher due to increased photochemical production. The summer distribution also featured a channel of enhanced CO (95–105 ppbv) flowing northeastward around an anticyclone and exiting the continent over the Canadian Maritimes around 50° N. Offshore O3-CO slopes were generally 0.15–0.20 mol mol−1 in JJA, indicative of photochemical O3 production. Composites for 4 predominant synoptic patterns or map types in DJF suggested that export to the lower free troposphere (681 hPa level) was enhanced by the warm conveyor belt airstream of mid-latitude cyclones while stratospheric intrusions increased TES O3 levels at 316 hPa. A major finding in the DJF data was that offshore 681 hPa CO mixing ratios behind cold fronts could be enhanced up to >150 ppbv likely by lofting from the surface via shallow convection resulting from rapid destabilization of cold air flowing over much warmer ocean waters. In JJA composites for 3 map types showed that the general export pattern of the seasonal composites was associated with a synoptic pattern featuring the Bermuda High. However, weak cyclones and frontal troughs could enhance offshore 681 hPa CO mixing ratios to >110 ppbv with O3-CO slopes >0.50 mol mol−1 south of 45° N. Intense cyclones, which were not as common in the summer, enhanced export by lofting of boundary layer pollutants from over the US and also provided a possible mechanism for transporting pollutants from boreal fire outflow southward to the US east coast. Overall, for winter and summer the TES retrievals showed substantial evidence of air pollution export to the western North Atlantic Ocean with the most distinct differences in distribution patterns related to strong influences of mid-latitude cyclones in winter and the Bermuda High anticyclone in summer.
Hydroxyl radicals in the tropical troposphere over the Suriname rainforest: airborne measurements

Direct measurements of OH and HO2 over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy), adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO2 mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO2 were encountered in the boundary layer over the rainforest. The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurement-derived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission.
Characterization of oligomers from methylglyoxal under dark conditions: a pathway to produce secondary organic aerosol through cloud processing during nighttime

Aqueous-phase oligomer formation from methylglyoxal, a major atmospheric photooxidation product, has been investigated in a simulated cloud matrix under dark conditions. The aim of this study was to explore an additional pathway producing secondary organic aerosol (SOA) through cloud processes without participation of photochemistry during nighttime. Indeed, atmospheric models still underestimate SOA formation, as field measurements have revealed more SOA than predicted. Soluble oligomers (n = 1–8) formed in the course of acid-catalyzed aldol condensation and acid-catalyzed hydration followed by acetal formation have been detected and characterized by positive and negative ion electrospray ionization mass spectrometry. Aldol condensation proved to be a favorable mechanism under simulated cloud conditions, while hydration/acetal formation was found to strongly depend on the pH of the system and only occurred at a pH<3.5. No evidence was found for formation of organosulfates. The aldol oligomer series starts with a β-hydroxy ketone via aldol condensation, where oligomers are formed by multiple additions of C3H4O2 units (72 Da) to the parent β-hydroxy ketone. Ion trap mass spectrometry experiments were performed to structurally characterize the major oligomer species. A mechanistic pathway for the growth of oligomers under cloud conditions and in the absence of UV-light and OH radicals, which could substantially enhance in-cloud SOA yields, is proposed here for the first time.
Towards closing the gap between hygroscopic growth and CCN activation for secondary organic aerosols – Part 3: Influence of the chemical composition on the hygroscopic properties and volatile fractions of aerosols

The influence of varying levels of water mixing ratio, r, during the formation of secondary organic aerosol (SOA) from the ozonolysis of α-pinene on the SOA hygroscopicity and volatility was investigated. The reaction proceeded and aerosols were generated in a mixing chamber and the hygroscopic characteristics of the SOA were determined with the Leipzig Aerosol Cloud Interaction Simulator (LACIS) and a Cloud Condensation Nuclei counter (CCNc). In parallel, a High-Resolution Time-of-Flight Aerodyne Aerosol Mass Spectrometer (HR-ToF-AMS) located downstream of a thermodenuder (TD) sampling from the mixing chamber, to collect mass spectra of particles from the volatile and less-volatile fractions of the SOA. Results showed that both hygroscopic growth and the volatile fraction of the SOA increased with increases in r inside the mixing chamber during SOA generation. An effective density of 1.40 g cm−3 was observed for the generated SOA when the reaction proceeded with r>1 g kg−1. Changes in the concentrations of the fragment CO2+ and the sum of CxHyOz+ (short name CHO) and CxHy+ (short name CH) fragments as measured by the HR-ToF-AMS were used to estimate changes in the oxidation level of the SOA with reaction conditions, using the ratios CO2+ to CH and CHO to CH. Under humid conditions, both ratios increased, corresponding to the presence of more oxygenated functional groups (i.e., multifunctional carboxylic acids). This result is consistent with the α-pinene ozonolysis mechanisms which suggest that water interacts with the stabilized Criegee intermediate. The volatility and the hygroscopicity results show that SOA generation via ozonolysis of α-pinene in the presence of water vapour (r<16.9 g kg−1) leads to the formation of more highly oxygenated compounds that are more hygroscopic and more volatile than compounds formed under dry conditions.
IASI observations of seasonal and day-to-day variations of tropospheric ozone over three highly populated areas of China: Beijing, Shanghai, and Hong Kong

IASI observations of tropospheric ozone over the Beijing, Shanghai and Hong Kong areas during one year (2008) have been analysed, demonstrating the capability of space-borne infrared nadir measurements to probe seasonal and even day-to-day variations of lower tropospheric ozone (0–6 km partial columns) on the regional scale of highly populated areas. The monthly variations of lower tropospheric ozone retrieved from IASI clearly show the influence of the Asian summer monsoon that brings clean air masses from the Pacific during summer. They exhibit indeed a sharp ozone maximum in late spring and early summer (May–June) followed by a summer minimum. The time periods and the intensities of the maxima and of the decreases are latitude-dependent: they are more pronounced in Hong Kong and Shanghai than in Beijing. Moreover, IASI provides the opportunity to follow the spatial variations of ozone over the surroundings of each megacity as well as its daily variability. We show here that the large lower tropospheric ozone amounts (0–6 km partial columns) observed with IASI are mainly downwind the highest populated areas in each region, thus possibly suggesting the anthropogenic origin of the large ozone amounts observed. Finally, an analysis of the mean ozone profiles over each region – for selected days with high ozone events – in association with the analysis of the meteorological situation shows that the high ozone amounts observed during winter are likely related to descents of ozone-rich air from the stratosphere, whereas in spring and summer the tropospheric ozone is likely enhanced by photochemical production in polluted areas and/or in air masses from fire plumes.
Impact of dust on tropospheric chemistry over polluted regions: a case study of the Beijing megacity

The box model MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere) is extended by incorporating detailed heterogeneous chemistry occurring on mineral aerosol surfaces. The model is used to investigate the impact of dust on tropospheric photochemistry, when the dust is transported to a polluted region, focusing on the example of Beijing. The impacts of dust via heterogeneous removal of gases are analyzed for different hypothetical transport rates, which are described by four different exchange rate coefficients Kt in the model. Along with the dust, airmasses with trace gas levels characteristic for regions upwind of Beijing are transported with the same rate (Kt). Substantial impacts are found for many gases, including Ox (O3+O(3P)), NOx (NO+NO2) and OH. The Ox daily average mixing ratio decreases due to heterogeneous reactions on dust. The change ranges from −2.5 to −18.4 nmol mol−1, and is larger for faster mixing with upwind air masses (i.e. greater Kt). This translates into a large relative change in Ox, ranging from −44% to −55%, depending on Kt. By assuming an artificial 50% decrease of all photolysis rates, the impacts of dust via perturbation of the photolysis rates in the polluted region are also estimated. Furthermore, the uncertainties in the results due to the uncertainties in the uptake coefficients are evaluated. It is found that for all gases which are heterogeneously removed, the self-removal results in the largest uncertainty (e.g. −49% for O3, −76% for NO2, −47% for HNO3, −92% for HCHO, −64% for CH3OH and −93% for SO2). The heterogeneous removal of NO2 is found to be particularly important, because it results in significant levels of uncertainty not only for itself, but also for OH (340%) and HO2 (365%). Moreover, the heterogeneous removal rates of HCHO and O3 also have farther-reaching effects on the OH concentration (resulting in changes of −55% and 45%, respectively), and the heterogeneous removal of HCHO results in an uncertainty of −38% in the HO2 concentration. The limitations of MECCA due to its missing oxidation mechanism for aromatics and other higher VOC species has also been considered, and shown to be potentially important in the quantitative results, though not likely to change the qualitative results of this study.
Ozone response to emission changes: a modeling study during the MCMA-2006/MILAGRO Campaign

The sensitivity of ozone production to precursor emissions was investigated under five different meteorological conditions in the Mexico City Metropolitan Area (MCMA) during the MCMA-2006/MILAGRO field campaign using the gridded photochemical model CAMx driven by observation-nudged WRF meteorology. Precursor emissions were constrained by the comprehensive data from the field campaign and the routine ambient air quality monitoring network. Simulated plume mixing and transport were examined by comparing with measurements from the G-1 aircraft during the campaign. The observed concentrations of ozone precursors and ozone were reasonably well reproduced by the model. The effects of reducing precursor emissions on urban ozone production were performed for three representative emission control scenarios. A 50% reduction in VOC emissions led to 7 to 22 ppb decrease in daily maximum ozone concentrations, while a 50% reduction in NOx emissions leads to 4 to 21 ppb increase, and 50% reductions in both NOx and VOC emission decrease the daily maximum ozone concentrations up to 10 ppb. These results along with a chemical indicator analysis using the chemical production ratios of H2O2 to HNO3 demonstrate that the MCMA urban core region is VOC-limited for all meteorological episodes, which is consistent with the results from MCMA-2003 field campaign; however the degree of the VOC-sensitivity is higher during MCMA-2006 due to lower VOCs, lower VOC reactivity and moderately higher NOx emissions. Ozone formation in the surrounding mountain/rural area is mostly NOx-limited, but can be VOC-limited, and the range of the NOx-limited or VOC-limited areas depends on meteorology.
Temperature effect on physical and chemical properties of secondary organic aerosol from m-xylene photooxidation

The chemical and physical differences of secondary organic aerosol (SOA) formed at select isothermal temperatures (278 K, 300 K, and 313 K) are explored with respect to density, particle volatility, particle hygroscopicity, and elemental chemical composition. A transition point in SOA density, volatility, hygroscopicity and elemental composition is observed near 290–292 K as SOA within an environmental chamber is heated from 278 K to 313 K, indicating the presence of a thermally labile compound. No such transition points are observed for SOA produced at 313 K or 300 K and subsequently cooled to 278 K. The SOA formed at the lowest temperatures (278 K) is more than double the SOA formed at 313 K. SOA formed at 278 K is less hydrophilic and oxygenated while more volatile and dense than SOA formed at 300 K or 313 K. The properties of SOA formed at 300 K and 313 K when reduced to 278 K did not match the properties of SOA initially formed at 278 K. This study demonstrates that it is insufficient to utilize the enthalpy of vaporization when predicting SOA temperature dependence.
Probabilistic model of shattering effect on in-cloud measurements

A probabilistic model of the ice shattering effects on in-cloud measurements performed with instruments designed with inlets, which have the circular cross-section, is presented. Applications are made for the Polar Nephelometer and PMS FSSP instruments. The model provides rough estimates of the effects on microphysical measurements and assigns the key parameters that govern the efficiency of ice shattering. It is shown that experimental data are less affected by the shattering for clouds that have a lower proportion of large particles. The effects on derived integral microphysical parameters are shown to be very sensitive to the effective diameter of the ice fragments. The smaller the fragments from a given cloud particle are, the higher their effects are. Errors on Polar Nephelometer measurements were evaluated. It is shown that the ice particle shattering leads to the overestimation of the extinction coefficient. For example, for a given distribution with the effective diameter of 68 μm and with fragment effective diameters of 10 μm the extinction is overestimated by 25%. With larger particles having an effective diameter of 89 μm, the error increases up to 37%. As for the FSSP-300 instrument, under the same conditions the extinction coefficient is overrated by 17% and the number particle concentration is overestimated by 30%. The discussion of the results points out the main hypothesis which may seriously limit the reliability of the modelling results. Nevertheless, the magnitudes of the errors on extinction and particle concentration are of the same orders of those reported in the literature from experimental assessments.
Effects of relative humidity on aerosol light scattering in the Arctic

Aerosol particles experience hygroscopic growth in the ambient atmosphere. Their optical properties – especially the aerosol light scattering – are therefore strongly dependent on the ambient relative humidity (RH). In-situ light scattering measurements of long-term observations are usually performed under dry conditions (RH>30–40%). The knowledge of this RH effect is of eminent importance for climate forcing calculations or for the comparison of remote sensing with in-situ measurements. This study combines measurements and model calculations to describe the RH effect on aerosol light scattering for the first time for aerosol particles present in summer and fall in the high Arctic. For this purpose, a field campaign was carried out from July to October 2008 at the Zeppelin station in Ny-Ålesund, Svalbard. The aerosol light scattering coefficient σsp(λ) was measured at three distinct wavelengths (λ=450, 550, and 700 nm) at dry and at various, predefined RH conditions between 20% and 95% with a recently developed humidified nephelometer (WetNeph) and with a second nephelometer measuring at dry conditions with an average RH<10% (DryNeph). In addition, the aerosol size distribution and the aerosol absorption coefficient were measured. The scattering enhancement factor f(RH, λ) is the key parameter to describe the RH effect on σsp(λ) and is defined as the RH dependent σsp(RH, λ) divided by the corresponding dry σsp(RHdry, λ). During our campaign the average f(RH=85%, λ=550 nm) was 3.24±0.63 (mean ± standard deviation), and no clear wavelength dependence of f(RH, λ) was observed. This means that the ambient scattering coefficients at RH=85% were on average about three times higher than the dry measured in-situ scattering coefficients. The RH dependency of the recorded f(RH, λ) can be well described by an empirical one-parameter equation. We used a simplified method to retrieve an apparent hygroscopic growth factor g(RH), defined as the aerosol particle diameter at a certain RH divided by the dry diameter, using the WetNeph, the DryNeph, the aerosol size distribution measurements and Mie theory. With this approach we found, on average, g(RH=85%) values to be 1.61±0.12 (mean±standard deviation). No clear seasonal shift of f(RH, λ) was observed during the 3-month period, while aerosol properties (size and chemical composition) clearly changed with time. While the beginning of the campaign was mainly characterized by smaller and less hygroscopic particles, the end was dominated by larger and more hygroscopic particles. This suggests that compensating effects of hygroscopicity and size determined the temporal stability of f(RH, λ). During sea salt influenced periods, distinct deliquescence transitions were observed. At the end we present a method on how to transfer the dry in-situ measured aerosol scattering coefficients to ambient values for the aerosol measured during summer and fall at this location.