Climatology and Atmospheric Chemistry of Non-Methane Hydrocarbon Emissions over the North Atlantic.

European Geosciences Union (EGU), General Assembly. Viena, Austria, 07 - 12 April 2013.Non-methane hydrocarbons (NMHC) covering the C2 to C7 volatility range have been monitored at the Pico Mountain Observatory, Pico Island, Azores, Portugal, since 2004. The Observatory is located at 2225 m a.s.l. in the caldera of the Pico Mountain volcano, and during most times receives lower free tropospheric air that has been transported across the North Atlantic. The 7-year NMHC record has been analyzed for seasonal behavior of photochemical processing, atmospheric transport time, and source region using ratios of NMHC species as indicators of photochemical aging and HYSPLIT model outputs. Transport conditions resulting in elevated and low NMHC conditions were specifically studied to investigate seasonal pollution transport in the North Atlantic region

A laboratory facility to study gas-aerosol-cloud interactions in a turbulent environment: The Π Chamber

A detailed understanding of interactions of aerosols, cloud droplets/ice crystals, and trace gases within the atmosphere is of prime importance for an accurate understanding of Earth’s weather and climate. One aspect that remains especially vexing is that clouds are ubiquitously turbulent, and therefore thermodynamic and compositional variables, such as water vapor supersaturation, fluctuate in space and time. With these problems in mind, a multiphase, turbulent reaction chamber—called the Π chamber because of the internal volume of 3.14 m3 with the cylindrical insert installed—has been developed. It is capable of pressures ranging from 1,000 to –60 hPa and can sustain temperatures of –55° to 55°C, thereby spanning much of the range of tropospheric clouds. To control the relative humidity in the chamber, it can be operated with a stable, unstable, or neutral temperature difference between the top and bottom surfaces, with or without expansion. A negative temperature difference induces turbulent Rayleigh–Bénard convection and associated supersaturation generation through isobaric mixing. Supporting instrumentation includes a suite of aerosol generation and characterization techniques; temperature, pressure, and humidity sensors; and a phase Doppler interferometer. Initial characterization experiments demonstrate the ability to sustain steady-state turbulent cloud conditions for times greater than 1 day, with droplet diameters typically in the range of 5–40 µm. Typical turbulence has root-mean-square velocity fluctuations on the order of 10 cm s–1 and kinetic energy dissipation rates of 1 × 10–3 W kg–1

Ten Years of Black Carbon Measurements in the North Atlantic at the Pico Mountain Observatory, Azores (2225m asl).

45th annual Fall Meeting, AGU. San Francisco, California, 3-7 December.The Pico Mountain Observatory is located in the summit caldera of the Pico mountain, an inactive volcano on the Pico Island in the Azores, Portugal (38.47°N, 28.40°W, Altitude 2225m asl). The Azores are often impacted by polluted outflows from the North American continent and local sources have been shown to have a negligible influence at the observatory. The value of the station stems from the fact that this is the only permanent mountaintop monitoring station in the North Atlantic that is typically located above the marine boundary layer (average MBL heights are below 1200 m and rarely exceed 1300 m) and often receives air characteristic of the lower free troposphere. Measurements of black carbon (BC) mass have been carried out at the station since 2001, mostly in the summer seasons. Here we discuss the BC decadal dataset (2001-2011) collected at the site by using a seven-wavelength AE31 Magee Aethalometer. Measured BC mass and computed Angstrom exponent (AE) values were analysed to study seasonal and diurnal variations. There was a large day-to-day variability in the BC values due to varied meteorological conditions that resulted in different diurnal patterns for different months. The daily mean BC at this location ranged between 0 and ~430 ngm-3, with the most frequently occurring value in the range 0-100 ngm-3. The overall mean for the 10 year period is ~24 ngm-3, with a coefficient of variation of 150%. The BC values exhibited a consistent annual trend being low in winter months and high in summer months, barring year to year variations. To differentiate between BC and other absorbing particles, we analyzed the wavelength dependence of aerosol absorption coefficient and determined a best-fit exponent i.e., the Ångström exponent, for the whole dataset. Visible Ångström exponent (AE: 470-520-590-660 nm) values ranged between 0 and 3.5, with most frequently occurring values in the range 0.85 to 1.25. By making use of the aethalometer light attenuation measurements at different wavelengths and Hysplit back trajectories, we divided the data into two categories. One for periods characterized by AE values close to 1; these periods are typically correlated with back trajectories originating from Canada, North America or northern Europe, indicating the dominance of BC on the light attenuation. Another characterized by AE values substantially different from 1; these periods correlated with back trajectories originating from dust-prone regions (e.g., the Sahara desert).The above measurements, with the aid of ancillary satellite and ground-based measurements will be employed in estimating the radiaitve effects of BC in the North Atlantic

Measurement of Free Tropospheric Aerosols in the North Atlantic at the Pico Mountain Observatory.

AAAR 31st Annual Conference. Minneapolis, Minnesota, October 8-12, 2012.The Pico Mountain Observatory is located at 2225 m amsl on an inactive volcano at Pico Island in the Azores archipelago in the North Atlantic ~3900 km east and downwind of North America (38º28'15''N; 28º24’'14''W). The unique location of the Observatory enables sampling of free tropospheric air transported over long, intercontinental distances and is rarely affected by local emissions. The Observatory is affected mainly by North American outflow after its trans-Atlantic transport. Therefore, its location is ideal for observations of long-range transported pollutants emitted from anthropogenic and biogenic continental sources. The composition of continental pollution outflow is altered during transport by mixing, chemical reactions, phase changes, and removal processes. Thus, the properties of aerosol and trace gases in downwind regions are impacted by the outflow of pollutants, their chemical transformation, and sinks. In previous work, the sampled air-mass measurements (including CO, O3, NOx, NOy, NMHC, black carbon and aerosol optical size) and the simulations of their dispersion indicated outflow of North American tropospheric ozone and its precursors. Although the measurements have been crucial in explaining the evolution of North American gaseous pollution, little is known regarding the nature of the aged aerosol. New work is currently underway at the Observatory to provide chemical characterization of the intercepted free tropospheric aerosols. Here, we show the preliminary results of the free tropospheric aerosol composition and its physical properties. Samples were collected using high-volume filter samplers with quartz filters and analyzed for organic and elemental carbon (OC and EC, respectively). We compare the observed OC and EC values to the collocated measurements of gas- and particle-phase species, meteorological parameters and to the values found in current literature. We highlight the future work in which we will select filter samples based on the arrival of highly polluted air masses from anthropological or biomass burning emissions for further detailed analysis

Molecular insights on aging and aqueous-phase processing from ambient biomass burning emissions-influenced Po Valley fog and aerosol

To study the influence of regional biomass burning emissions and secondary processes, ambient samples of fog and aerosol were collected in the Po Valley (Italy) during the 2013 Supersito field campaign. After the extent of fresh vs. aged biomass burning influence was estimated from proton nuclear magnetic resonance (1H NMR) and high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), two samples of fog water and two samples of PM1 aerosol were selected for ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Molecular compositions indicated that the water-soluble organic matter was largely non-polymeric without clearly repeating units. The selected samples had an atypically large frequency of molecular formulas containing nitrogen and sulfur (not evident in the NMR composition) attributed to multifunctional organonitrates and organosulfates. Higher numbers of organonitrates were observed in aerosol, and higher numbers of organosulfates were observed in fog water. Consistent with the observation of an enhanced aromatic proton signature in the 1H-NMR analysis, the average molecular formula double-bond equivalents and carbon numbers were higher in the fresh biomass-burning-influenced samples. The average O:C and H:C values from FT-ICR MS were higher in the samples with an aged influence (O:C = 0.50–0.58, and H:C = 1.31–1.37) compared to those with fresh influence (O:C = 0.43–0.48, and H:C = 1.13–1.30). The aged fog had a large set of unique highly oxygenated CHO fragments in the HR-ToF-AMS, which reflects an enrichment of carboxylic acids and other compounds carrying acyl groups, highlighted by the NMR analysis. Fog compositions were more oxidized and SOA (secondary organic aerosol)-like than aerosols as indicated by their NMR measured acyl-to-alkoxyl ratios and the observed molecular formula similarity between the aged aerosol and fresh fog, implying that fog nuclei must be somewhat aged. Overall, functionalization with nitrate and sulfate moieties, in addition to aqueous oxidation, triggers an increase in the molecular complexity in this environment, which is apparent in the FT-ICR MS results. This study demonstrates the significance of the aqueous phase in transforming the molecular chemistry of atmospheric organic matter and contributing to secondary organic aerosol

Ice cloud formation potential by free tropospheric particles from long-range transport over the Northern Atlantic Ocean

Long-range transported free tropospheric particles can play a significant role on heterogeneous ice nucleation. Using optical and electron microscopy we examine the physicochemical characteristics of ice nucleating particles (INPs). Particles were collected on substrates from the free troposphere at the remote Pico Mountain Observatory in the Azores Islands, after long-range transport and aging over the Atlantic Ocean. We investigate four specific events to study the ice formation potential by the collected particles with different ages and transport patterns. We use single-particle analysis, as well as bulk analysis to characterize particle populations. Both analyses show substantial differences in particle composition between samples from the four events; in addition, single-particle microscopy analysis indicates that most particles are coated by organic material. The identified INPs contained mixtures of dust, aged sea salt and soot, and organic material acquired either at the source or during transport. The temperature and relative humidity (RH) at which ice formed, varied only by 5% between samples, despite differences in particle composition, sources, and transport patterns. We hypothesize that this small variation in the onset RH may be due to the coating material on the particles. This study underscores and motivates the need to further investigate how long-range transported and atmospherically aged free tropospheric particles impact ice cloud formatio

Modelling the hygroscopic growth factors of aerosol material containing a large water-soluble organic fraction, collected at the Storm Peak Laboratory

The compositions of six aggregated aerosol samples from the Storm Peak site have been comprehensively analysed (Hallar et al., 2013), focusing particularly on the large water-extractable organic fraction which consists of both high molecular weight organic compounds and a range of acids and sugar-alcohols. The contribution of the soluble organic fraction of atmospheric aerosols to their hygroscopicity is hard to quantify, largely because of the lack of a detailed knowledge of both composition and the thermodynamic properties of the functionally complex compounds and structures the fraction contains. In this work we: (i) develop a means of predicting the relative solubility of the compounds in the water-extractable organic material from the Storm Peak site, based upon what is known about their chemical composition; (ii) derive the probable soluble organic fraction from comparisons of model predictions with the measured hygroscopicity; (iii) test a model of the water uptake of the total aerosol (inorganic plus total water-extractable organic compounds). Using a novel UNIFAC-based method, different assignments of functional groups to the high molecular weight water soluble organic compounds (WSOC) were explored, together with their effects on calculated hygroscopic growth factors, constrained by the known molecular formulae and the double bond equivalents associated with each molecule. The possible group compositions were compared with the results of ultrahigh resolution mass spectrometry measurements of the organic material, which suggest large numbers of alcohol (–OH) and acid (–COOH) groups. A hygroscopicity index (HI) was developed. The measured hygroscopic growth is found to be consistent with a dissolution of the WSOC material that varies approximately linearly with RH, such that the dissolved fraction is about 0.45–0.85 at 90% relative humidity when ordering by HI, depending on the assumptions made. This relationship, if it also applies to other types of organic aerosol material, provides a simple approach to calculating both water uptake and CCN activity (and the κ parameter for hygroscopic growth). The hygroscopicity of the total aerosol was modelled using a modified Zdanovskii-Stokes-Robinson approach as the sum of that of the three analysed fractions: inorganic ions (predicted), individual organic acids and “sugar alcohols” (predicted), and the high molecular weight WSOC fraction (measured). The calculated growth factors broadly agree with the measurements, and validate the approach taken. The insights into the dissolution of the organic material seem likely to apply to other largely biogenic aerosols from similar remote locations

Hygroscopic growth of water soluble organic carbon isolated from atmospheric aerosol collected at US national parks and Storm Peak Laboratory

Due to the atmospheric abundance and chemical complexity of water soluble organic carbon (WSOC), its contribution to the hydration behavior of atmospheric aerosol is both significant and difficult to assess. For the present study, the hygroscopicity and CCN activity of isolated atmospheric WSOC particulate matter was measured without the compounding effects of common, soluble inorganic aerosol constituents. WSOC was extracted with high purity water from daily high-volume PM2.5 filter samples and separated from water soluble inorganic constituents using solid-phase extraction. The WSOC filter extracts were concentrated and combined to provide sufficient mass for continuous generation of the WSOC-only aerosol over the combined measurement time of the tandem differential mobility analyzer and coupled scanning mobility particle sizer–CCN counter used for the analysis. Aerosol samples were taken at Great Smoky Mountains National Park during the summer of 2006 and fall–winter of 2007–2008; Mount Rainier National Park during the summer of 2009; Storm Peak Laboratory (SPL) near Steamboat Springs, Colorado, during the summer of 2010; and Acadia National Park during the summer of 2011. Across all sampling locations and seasons, the hygroscopic growth of WSOC samples at 90 % RH, expressed in terms of the hygroscopicity parameter, κ, ranged from 0.05 to 0.15. Comparisons between the hygroscopicity of WSOC and that of samples containing all soluble materials extracted from the filters implied a significant modification of the hydration behavior of inorganic components, including decreased hysteresis separating efflorescence and deliquescence and enhanced water uptake between 30 and 70 % RH

Measurement of Aerosols and Trace Gases in the Free Troposphere at the Pico Mountain Observatory in the Azores.

European Geosciences Union (EGU), General Assembly. Viena, Austria, 07 - 12 April 2013.Here, we present an overview of gas and aerosol data measured at the Pico Mountain Station. The primary objective of these measurements are to enhance our knowledge of anthropogenic and biomass burning emissions from North America and their relative impact on atmospheric composition and radiative forcing in the free troposphere of the North Atlantic