Biogenic Air Research Articles

Sources and Distribution of Light NMHCs in the Marine Boundary Layer of the Northern Indian Ocean During Winter: Implications to Aerosol Formation

AbstractNon‐methane hydrocarbons (NMHCs) are ubiquitous trace gases and profoundly affect the Earth's atmosphere and climate change. Mixing ratios of light NMHCs were measured over the northern Indian Ocean during winter‐2018 as part of the Integrated Campaign for Aerosols, gases, and Radiation Budget (ICARB‐2018). Higher levels of NMHCs over the coastal regions were due to the efficient transport of anthropogenic and biogenic air masses and higher air‐sea exchanges due to the higher biological productivity. Although oceanic emissions dominated the open ocean, the transport of aged continental air also influenced the levels of some NMHCs. The higher and lower propane/ethane ratios of 2.41 ± 0.34 and 1.13 ± 0.78 ppbv ppbv−1 over coastal and open oceans indicated the prevalence of fresh and aged air masses, respectively. Ethene and propene show a strong correlation, but the ethene/propene ratios over open ocean (2.2 ± 0.25 ppbv ppbv−1) were slightly lower than the coastal region (2.5 ± 0.34 ppbv ppbv−1). Principal component analysis reveals the major associated sources identified in this study are from oceanic and nearby anthropogenic sources, explaining nearly 51% and 21% of variance. Light alkenes accounted for ∼70% of the total ozone and secondary organic aerosol formation potential. A higher alkene/alkane ratio, strong correlation of alkene with organic aerosol mass, and new particle formation events highlight the role of alkenes in secondary aerosol formation over the equatorial Indian Ocean. Overall, the levels of NMHCs were much higher than those measured nearly two decades ago during the Indian Ocean Experiment (INDOEX)‐1999.

An Experiment to Study Atmospheric Oxidation Chemistry and Physics of Mixed Anthropogenic–Biogenic Air Masses in the Greater Paris Area

Abstract ACROSS (Atmospheric ChemistRy Of the Suburban foreSt) is an integrative, innovative, multi-scale project within the “Make Our Planet Great Again” (MOPGA) initiative designed to advance understanding of the fate of urban and biogenic air mass mixtures in the Paris region. An ACROSS hypothesis is that the anthropogenic-biogenic air mass mixing leads to changes in the production of oxygenated volatile organic compounds (VOCs) whose properties alter their importance in incorporation into secondary organic aerosols (SOA) and their roles in the production of ozone and other relevant secondary species. A likely important factor is NOx transport to suburban biogenic environments and the resulting modification of key chemical processes. A highlight of ACROSS is an intensive, multi-platform measurement campaign that will take place in the summer of 2022. The campaign will include a 40-meter tower and ground-based measurements in the Rambouillet suburban forest to the southwest of Paris, airborne regional observations across Paris and suburban forested areas, and several other multi-instrumented ground sites located in the urban, rural, and semi-rural Paris region. The data collected from this campaign will provide a unique snapshot of the properties and mixing of urban and biogenic air masses around one of the most populated and polluted European megacities. This new knowledge will advance our understanding at the process level and lead to the ability to represent such complex systems in numerical models, ultimately resulting in improved capability to predict the impacts on air quality, regional climate, and global climate change.

Dynamics of volatile organic compounds in a western Mediterranean oak forest

Volatile organic compounds (VOCs) are emitted from many sources and have important implications for plant fitness, ecological interactions, and atmospheric processes, including photochemistry and ozone formation. Forest ecosystems are strong sources of biogenic VOCs. We aimed to characterize forest below-canopy VOC mixing ratios, monitored by Proton Transfer Reaction Mass Spectrometry (PTR-MS), at Montseny Natural Park, a Mediterranean forest 50 km from the Barcelona urban area. Measurements were taken every 2 min during six months around the maximum emission period of summer. All VOCs had diel cycles with higher mixing ratios during the day, but different patterns over time. Monitored VOCs were grouped as biogenic, oxygenated, or aromatic compounds. Additionally, a positive matrix factorization analysis identified four emission profiles that were attributed to photochemical VOC production, biogenic emissions, mixed VOC emission sources, and traffic emissions. Even though the biogenic source was the strongest source profile at the site, we found a strong influence of anthropogenic air masses infiltrating the forest canopy and altering the biogenic air masses at the site.

Environmental life cycle assessment of wheat production using chemical fertilizer, manure compost, and biochar-amended manure compost strategies

Using manure compost (MC) as a substitute for chemical fertilizer (CF) has been regarded as an effective strategy to promote sustainable crop production. The application of biochar in compost production could significantly mitigate the emission of gaseous pollutants and improve compost quality. However, comprehensive investigations of the environmental performance of crop production using CF, MC, and biochar-amended MC strategies are scarce. Therefore, in this study, wheat production using four fertilizer strategies, including CF, MC, and biochar-amended MC with biochar addition rates of 5% (MCB5) and 10% (MCB10), was comparatively assessed in terms of their environmental performance using the life cycle assessment (LCA) method. Compared to the CF strategy, the majority of midpoint impact categories and all assessed damage categories (except for human health and resources in MCB10) were mitigated using the compost strategies. Furthermore, as the biochar application rate increased, the biochar-amended MC strategies remarkably decreased the impacts on the global warming potential, stratospheric ozone depletion, and land use, and greatly increased the impacts on ozone formation (human health), fine particulate matter formation, and terrestrial acidification. Overall, biochar-amended MC with a biochar addition rate of 5% (MCB5) is recommended as the optimal strategy due to its relatively low environmental impact. Moreover, combined with the results of the sensitivity analysis, biogenic air pollutant emissions derived from the compost and biochar production stages were identified as the most important hotspots contributing to the undesirable environmental impacts. These findings advance our understanding of the environmental performance of wheat production using biochar-amended MC.

Exploration of oxidative chemistry and secondary organic aerosol formation in the Amazon during the wet season: explicit modeling of the Manaus urban plume with GECKO-A

Abstract. The GoAmazon 2014/5 field campaign took place in Manaus, Brazil, and allowed the investigation of the interaction between background-level biogenic air masses and anthropogenic plumes. We present in this work a box model built to simulate the impact of urban chemistry on biogenic secondary organic aerosol (SOA) formation and composition. An organic chemistry mechanism is generated with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate the explicit oxidation of biogenic and anthropogenic compounds. A parameterization is also included to account for the reactive uptake of isoprene oxidation products on aqueous particles. The biogenic emissions estimated from existing emission inventories had to be reduced to match measurements. The model is able to reproduce ozone and NOx for clean and polluted situations. The explicit model is able to reproduce background case SOA mass concentrations but does not capture the enhancement observed in the urban plume. The oxidation of biogenic compounds is the major contributor to SOA mass. A volatility basis set (VBS) parameterization applied to the same cases obtains better results than GECKO-A for predicting SOA mass in the box model. The explicit mechanism may be missing SOA-formation processes related to the oxidation of monoterpenes that could be implicitly accounted for in the VBS parameterization.

Composition of Clean Marine Air and Biogenic Influences on VOCs during the MUMBA Campaign

Volatile organic compounds (VOCs) are important precursors to the formation of ozone and fine particulate matter, the two pollutants of most concern in Sydney, Australia. Despite this importance, there are very few published measurements of ambient VOC concentrations in Australia. In this paper, we present mole fractions of several important VOCs measured during the campaign known as MUMBA (Measurements of Urban, Marine and Biogenic Air) in the Australian city of Wollongong (34°S). We particularly focus on measurements made during periods when clean marine air impacted the measurement site and on VOCs of biogenic origin. Typical unpolluted marine air mole fractions during austral summer 2012-2013 at latitude 34°S were established for CO2 (391.0 ± 0.6 ppm), CH4 (1760.1 ± 0.4 ppb), N2O (325.04 ± 0.08 ppb), CO (52.4 ± 1.7 ppb), O3 (20.5 ± 1.1 ppb), acetaldehyde (190 ± 40 ppt), acetone (260 ± 30 ppt), dimethyl sulphide (50 ± 10 ppt), benzene (20 ± 10 ppt), toluene (30 ± 20 ppt), C8H10 aromatics (23 ± 6 ppt) and C9H12 aromatics (36 ± 7 ppt). The MUMBA site was frequently influenced by VOCs of biogenic origin from a nearby strip of forested parkland to the east due to the dominant north-easterly afternoon sea breeze. VOCs from the more distant densely forested escarpment to the west also impacted the site, especially during two days of extreme heat and strong westerly winds. The relative amounts of different biogenic VOCs observed for these two biomes differed, with much larger increases of isoprene than of monoterpenes or methanol during the hot westerly winds from the escarpment than with cooler winds from the east. However, whether this was due to different vegetation types or was solely the result of the extreme temperatures is not entirely clear. We conclude that the clean marine air and biogenic signatures measured during the MUMBA campaign provide useful information about the typical abundance of several key VOCs and can be used to constrain chemical transport model simulations of the atmosphere in this poorly sampled region of the world.

Evaluation of Regional Air Quality Models over Sydney and Australia: Part 1—Meteorological Model Comparison

The ability of meteorological models to accurately characterise regional meteorology plays a crucial role in the performance of photochemical simulations of air pollution. As part of the research funded by the Australian government’s Department of the Environment Clean Air and Urban Landscape hub, this study set out to complete an intercomparison of air quality models over the Sydney region. This intercomparison would test existing modelling capabilities, identify any problems and provide the necessary validation of models in the region. The first component of the intercomparison study was to assess the ability of the models to reproduce meteorological observations, since it is a significant driver of air quality. To evaluate the meteorological component of these air quality modelling systems, seven different simulations based on varying configurations of inputs, integrations and physical parameterizations of two meteorological models (the Weather Research and Forecasting (WRF) and Conformal Cubic Atmospheric Model (CCAM)) were examined. The modelling was conducted for three periods coinciding with comprehensive air quality measurement campaigns (the Sydney Particle Studies (SPS) 1 and 2 and the Measurement of Urban, Marine and Biogenic Air (MUMBA)). The analysis focuses on meteorological variables (temperature, mixing ratio of water, wind (via wind speed and zonal wind components), precipitation and planetary boundary layer height), that are relevant to air quality. The surface meteorology simulations were evaluated against observations from seven Bureau of Meteorology (BoM) Automatic Weather Stations through composite diurnal plots, Taylor plots and paired mean bias plots. Simulated vertical profiles of temperature, mixing ratio of water and wind (via wind speed and zonal wind components) were assessed through comparison with radiosonde data from the Sydney Airport BoM site. The statistical comparisons with observations identified systematic overestimations of wind speeds that were more pronounced overnight. The temperature was well simulated, with biases generally between ±2 °C and the largest biases seen overnight (up to 4 °C). The models tend to have a drier lower atmosphere than observed, implying that better representations of soil moisture and surface moisture fluxes would improve the subsequent air quality simulations. On average the models captured local-scale meteorological features, like the sea breeze, which is a critical feature driving ozone formation in the Sydney Basin. The overall performance and model biases were generally within the recommended benchmark values (e.g., ±1 °C mean bias in temperature, ±1 g/kg mean bias of water vapour mixing ratio and ±1.5 m s−1 mean bias of wind speed) except at either end of the scale, where the bias tends to be larger. The model biases reported here are similar to those seen in other model intercomparisons.

Particle Formation in a Complex Environment

A field aerosol measurement campaign as part of the Measurements of Urban, Marine and Biogenic Air (MUMBA) campaign was conducted between 16 January 2013 and 15 February 2013 in the coastal city of Wollongong, Australia. The objectives of this research were to study the occurrence frequency, characteristics and factors that influence new particle formation processes. Particle formation and growth events were observed from particle number size distribution data in the range of 14 nm–660 nm measured using a scanning particle mobility sizer (SMPS). Four weak Class I particle formation and growth event days were observed, which is equivalent to 13% of the total observation days. The events occurred during the day, starting after 8:30 Australian Eastern Standard time with an average duration of five hours. The events also appeared to be positively linked to the prevailing easterly to north easterly sea breezes that carry pollutants from sources in and around Sydney. This suggests that photochemical reactions and a combination of oceanic and anthropogenic air masses are among the factors that influenced these events.

Multiscale Applications of Two Online-Coupled Meteorology-Chemistry Models during Recent Field Campaigns in Australia, Part II: Comparison of WRF/Chem and WRF/Chem-ROMS and Impacts of Air-Sea Interactions and Boundary Conditions

Air-sea interactions play an important role in atmospheric circulation and boundary layer conditions through changing convection processes and surface heat fluxes, particularly in coastal areas. These changes can affect the concentrations, distributions, and lifetimes of atmospheric pollutants. In this Part II paper, the performance of the Weather Research and Forecasting model with chemistry (WRF/Chem) and the coupled WRF/Chem with the Regional Ocean Model System (ROMS) (WRF/Chem-ROMS) are intercompared for their applications over quadruple-nested domains in Australia during the three following field campaigns: The Sydney Particle Study Stages 1 and 2 (SPS1 and SPS2) and the Measurements of Urban, Marine, and Biogenic Air (MUMBA). The results are used to evaluate the impact of air-sea interaction representation in WRF/Chem-ROMS on model predictions. At 3, 9, and 27 km resolutions, compared to WRF/Chem, the explicit air-sea interactions in WRF/Chem-ROMS lead to substantial improvements in simulated sea-surface temperature (SST), latent heat fluxes (LHF), and sensible heat fluxes (SHF) over the ocean, in terms of statistics and spatial distributions, during all three field campaigns. The use of finer grid resolutions (3 or 9 km) effectively reduces the biases in these variables during SPS1 and SPS2 by WRF/Chem-ROMS, whereas it further increases these biases for WRF/Chem during all field campaigns. The large differences in SST, LHF, and SHF between the two models lead to different radiative, cloud, meteorological, and chemical predictions. WRF/Chem-ROMS generally performs better in terms of statistics and temporal variations for temperature and relative humidity at 2 m, wind speed and direction at 10 m, and precipitation. The percentage differences in simulated surface concentrations between the two models are mostly in the range of ±10% for CO, OH, and O3, ±25% for HCHO, ±30% for NO2, ±35% for H2O2, ±50% for SO2, ±60% for isoprene and terpenes, ±15% for PM2.5, and ±12% for PM10. WRF/Chem-ROMS at 3 km resolution slightly improves the statistical performance of many surface and column concentrations. WRF/Chem simulations with satellite-constrained boundary conditions (BCONs) improve the spatial distributions and magnitudes of column CO for all field campaigns and slightly improve those of the column NO2 for SPS1 and SPS2, column HCHO for SPS1 and MUMBA, and column O3 for SPS2 at 3 km over the Greater Sydney area. The satellite-constrained chemical BCONs reduce the model biases of surface CO, NO, and O3 predictions at 3 km for all field campaigns, surface PM2.5 predictions at 3 km for SPS1 and MUMBA, and surface PM10 predictions at all grid resolutions for all field campaigns. A more important role of chemical BCONs in the Southern Hemisphere, compared to that in the Northern Hemisphere reported in this work, indicates a crucial need in developing more realistic chemical BCONs for O3 in the relatively clean SH.

Multiscale Applications of Two Online-Coupled Meteorology-Chemistry Models during Recent Field Campaigns in Australia, Part I: Model Description and WRF/Chem-ROMS Evaluation Using Surface and Satellite Data and Sensitivity to Spatial Grid Resolutions

Air pollution and associated human exposure are important research areas in Greater Sydney, Australia. Several field campaigns were conducted to characterize the pollution sources and their impacts on ambient air quality including the Sydney Particle Study Stages 1 and 2 (SPS1 and SPS2), and the Measurements of Urban, Marine, and Biogenic Air (MUMBA). In this work, the Weather Research and Forecasting model with chemistry (WRF/Chem) and the coupled WRF/Chem with the Regional Ocean Model System (ROMS) (WRF/Chem-ROMS) are applied during these field campaigns to assess the models’ capability in reproducing atmospheric observations. The model simulations are performed over quadruple-nested domains at grid resolutions of 81-, 27-, 9-, and 3-km over Australia, an area in southeastern Australia, an area in New South Wales, and the Greater Sydney area, respectively. A comprehensive model evaluation is conducted using surface observations from these field campaigns, satellite retrievals, and other data. This paper evaluates the performance of WRF/Chem-ROMS and its sensitivity to spatial grid resolutions. The model generally performs well at 3-, 9-, and 27-km resolutions for sea-surface temperature and boundary layer meteorology in terms of performance statistics, seasonality, and daily variation. Moderate biases occur for temperature at 2-m and wind speed at 10-m in the mornings and evenings due to the inaccurate representation of the nocturnal boundary layer and surface heat fluxes. Larger underpredictions occur for total precipitation due to the limitations of the cloud microphysics scheme or cumulus parameterization. The model performs well at 3-, 9-, and 27-km resolutions for surface O3 in terms of statistics, spatial distributions, and diurnal and daily variations. The model underpredicts PM2.5 and PM10 during SPS1 and MUMBA but overpredicts PM2.5 and underpredicts PM10 during SPS2. These biases are attributed to inaccurate meteorology, precursor emissions, insufficient SO2 conversion to sulfate, inadequate dispersion at finer grid resolutions, and underprediction in secondary organic aerosol. The model gives moderate biases for net shortwave radiation and cloud condensation nuclei but large biases for other radiative and cloud variables. The performance of aerosol optical depth and latent/sensible heat flux varies for different simulation periods. Among all variables evaluated, wind speed at 10-m, precipitation, surface concentrations of CO, NO, NO2, SO2, O3, PM2.5, and PM10, aerosol optical depth, cloud optical thickness, cloud condensation nuclei, and column NO2 show moderate-to-strong sensitivity to spatial grid resolutions. The use of finer grid resolutions (3- or 9-km) can generally improve the performance for those variables. While the performance for most of these variables is consistent with that over the U.S. and East Asia, several differences along with future work are identified to pinpoint reasons for such differences.

Urban Air Quality in a Coastal City: Wollongong during the MUMBA Campaign

We present findings from the Measurements of Urban, Marine and Biogenic Air (MUMBA) campaign, which took place in the coastal city of Wollongong in New South Wales, Australia. We focus on a few key air quality indicators, along with a comparison to regional scale chemical transport model predictions at a spatial resolution of 1 km by 1 km. We find that the CSIRO chemical transport model provides accurate simulations of ozone concentrations at most times, but underestimates the ozone enhancements that occur during extreme temperature events. The model also meets previously published performance standards for fine particulate matter less than 2.5 microns in diameter (PM2.5), and the larger aerosol fraction (PM10). We explore the observed composition of the atmosphere within this urban air-shed during the MUMBA campaign and discuss the different influences on air quality in the city. Our findings suggest that further improvements to our ability to simulate air quality in this coastal city can be made through more accurate anthropogenic and biogenic emissions inventories and better understanding of the impact of extreme temperatures on air quality. The challenges in modelling air quality within the urban air-shed of Wollongong, including difficulties in accurate simulation of the local meteorology, are likely to be replicated in many other coastal cities in the Southern Hemisphere.

Characteristics of airborne particle number size distributions in a coastal-urban environment

Particle number size distributions are among the most important parameters in trying to understand the characteristics of particle population. Atmospheric particles were measured in an interaction of mixed environments in the Southeastern coastal city of Wollongong, Australia, during a comprehensive field campaign known as Measurements of Urban, Marine and Biogenic Air (MUMBA). MUMBA ran in summer season between 21st December 2012 and 15th February 2013. Particle number concentrations measured during this campaign were indicative of the interplay between marine environments and urban air which met the objective of this campaign. Particle number size distributions ranging from 14 nm to 660 nm in diameter, as measured by Scanning Mobility Particle Sizer (SMPS) in this study, were grouped using Principal Component Analysis. Based on strong component loadings (value ≥ 0.75), three different factors were identified (i) Small Factor (NS): 15 nm < Dp < 50 nm, (ii) Medium Factor (NM): 60 nm < Dp < 150 nm and (iii) Large Factor (NL): 210 nm < Dp < 450 nm. The three factors describe 89% of the dataset cumulative variance. Particles in this region are dependent upon the interaction between the sources, and cannot be viewed as a simple mixture of biogenic and anthropogenic sources associated with various mechanical processes. The particles observed in the morning were found to be influenced by combustion emissions, presumably primarily from traffic, which is most obvious in NL. The particle population during the day was found to be influenced by a mixture of marine sources and secondary aerosols production initiated by photochemical oxidation. The local steel works and the urban environment were the major contributors of particles at night. Secondary organic aerosols were identified in this study by the mass ratio of organic carbon to elemental carbon (OC/EC). Biogenic sources influenced secondary organic aerosols formation as a moderate correlation (R2 = 0.6) was observed between secondary organic aerosols mass and biogenic isoprene. The processes described in this paper are likely repeated at other coastal urban environments worldwide.

Particle growth in an isoprene-rich forest: Influences of urban, wildfire, and biogenic air masses

Growth of freshly nucleated particles is an important source of cloud condensation nuclei (CCN) and has been studied within a variety of environments around the world. However, there remains uncertainty regarding the sources of the precursor gases leading to particle growth, particularly in isoprene-rich forests. In this study, particle growth events were observed from the 14 total events (31% of days) during summer measurements (June 24 – August 2, 2014) at the Program for Research on Oxidants PHotochemistry, Emissions, and Transport (PROPHET) tower within the forested University of Michigan Biological Station located in northern Michigan. Growth events were observed within long-range transported air masses from urban areas, air masses impacted by wildfires, as well as stagnant, forested/regional air masses. Growth events observed during urban-influenced air masses were prevalent, with presumably high oxidant levels, and began midday during periods of high solar radiation. This suggests that increased oxidation of biogenic volatile organic compounds (BVOCs) likely contributed to the highest observed particle growth in this study (8 ± 2 nm h−1). Growth events during wildfire-influenced air masses were observed primarily at night and had slower growth rates (3 ± 1 nm h−1). These events were likely influenced by increased SO2, O3, and NO2 transported within the smoke plumes, suggesting a role of NO3 oxidation in the production of semi-volatile compounds. Forested/regional air mass growth events likely occurred due to the oxidation of regionally emitted BVOCs, including isoprene, monoterpenes, and sesquiterpenes, which facilitated multiday growth events also with slower rates (3 ± 2 nm h−1). Intense sulfur, carbon, and oxygen signals in individual particles down to 20 nm, analyzed by transmission electron microscopy with energy dispersive X-ray spectroscopy (TEM-EDX), suggest that H2SO4 and secondary organic aerosol contributed to particle growth. Overall, aerosol growth was frequently observed in a range of air masses (urban, wildfire, forested) and oxidant conditions (day vs. night), with rates ranging from 0.8 to 10.2 nm h−1.

The MUMBA campaign: measurements of urban, marine and biogenic air

Abstract. The Measurements of Urban, Marine and Biogenic Air (MUMBA) campaign took place in Wollongong, New South Wales (a small coastal city approximately 80 km south of Sydney, Australia) from 21 December 2012 to 15 February 2013. Like many Australian cities, Wollongong is surrounded by dense eucalyptus forest, so the urban airshed is heavily influenced by biogenic emissions. Instruments were deployed during MUMBA to measure the gaseous and aerosol composition of the atmosphere with the aim of providing a detailed characterisation of the complex environment of the ocean–forest–urban interface that could be used to test the skill of atmospheric models. The gases measured included ozone, oxides of nitrogen, carbon monoxide, carbon dioxide, methane and many of the most abundant volatile organic compounds. The aerosol characterisation included total particle counts above 3 nm, total cloud condensation nuclei counts, mass concentration, number concentration size distribution, aerosol chemical analyses and elemental analysis.The campaign captured varied meteorological conditions, including two extreme heat events, providing a potentially valuable test for models of future air quality in a warmer climate. There was also an episode when the site sampled clean marine air for many hours, providing a useful additional measure of the background concentrations of these trace gases within this poorly sampled region of the globe. In this paper we describe the campaign, the meteorology and the resulting observations of atmospheric composition in general terms in order to equip the reader with a sufficient understanding of the Wollongong regional influences to use the MUMBA datasets as a case study for testing a chemical transport model. The data are available from PANGAEA (http://doi.pangaea.de/10.1594/PANGAEA.871982).

Biogenic cloud nuclei in the central Amazon during the transition from wet to dry season

Abstract. The Amazon basin is a vast continental area in which atmospheric composition is relatively unaffected by anthropogenic aerosol particles. Understanding the properties of the natural biogenic aerosol particles over the Amazon rainforest is key to understanding their influence on regional and global climate. While there have been a number of studies during the wet season, and of biomass burning particles in the dry season, there has been relatively little work on the transition period – the start of the dry season in the absence of biomass burning. As part of the Brazil–UK Network for Investigation of Amazonian Atmospheric Composition and Impacts on Climate (BUNIAACIC) project, aerosol measurements, focussing on unpolluted biogenic air masses, were conducted at a remote rainforest site in the central Amazon during the transition from wet to dry season in July 2013. This period marks the start of the dry season but before significant biomass burning occurs in the region. Median particle number concentrations were 266 cm−3, with size distributions dominated by an accumulation mode of 130–150 nm. During periods of low particle counts, a smaller Aitken mode could also be seen around 80 nm. While the concentrations were similar in magnitude to those seen during the wet season, the size distributions suggest an enhancement in the accumulation mode compared to the wet season, but not yet to the extent seen later in the dry season, when significant biomass burning takes place. Submicron nonrefractory aerosol composition, as measured by an aerosol chemical speciation monitor (ACSM), was dominated by organic material (around 81 %). Aerosol hygroscopicity was probed using measurements from a hygroscopicity tandem differential mobility analyser (HTDMA), and a quasi-monodisperse cloud condensation nuclei counter (CCNc). The hygroscopicity parameter, κ, was found to be low, ranging from 0.12 for Aitken-mode particles to 0.18 for accumulation-mode particles. This was consistent with previous studies in the region, but lower than similar measurements conducted in Borneo, where κ ranged 0.17–0.37. A wide issue bioaerosol sensor (WIBS-3M) was deployed at ground level to probe the coarse mode, detecting primary biological aerosol by fluorescence (fluorescent biological aerosol particles, or FBAPs). The mean FBAP number concentration was 400 ± 242 L−1; however, this ranged from around 200 L−1 during the day to as much as 1200 L−1 at night. FBAPs dominated the coarse-mode particles, comprising between 55 and 75 % of particles during the day to more than 90 % at night. Non-FBAPs did not show a strong diurnal pattern. Comparison with previous FBAP measurements above canopy at the same location suggests there is a strong vertical gradient in FBAP concentrations through the canopy. Cluster analysis of the data suggests that FBAPs were dominated (around 70 %) by fungal spores. Further, long-term measurements will be required in order to fully examine the seasonal variability and distribution of primary biological aerosol particles through the canopy. This is the first time that such a suite of measurements has been deployed at this site to investigate the chemical composition and properties of the biogenic contributions to Amazonian aerosol during the transition period from the wet to the dry season, and thus provides a unique comparison to the aerosol properties observed during the wet season in previous similar campaigns. This was also the first deployment of a WIBS in the Amazon rainforest to study coarse-mode particles, particularly primary biological aerosol particles, which are likely to play an important role as ice nuclei in the region.

Measurement of loss rates of organic compounds in snow using in situ experiments and isotopically labelled compounds

Organic molecular marker compounds are widely used to identify emissions from anthropogenic and biogenic air pollution sources in atmospheric samples and in deposition. Specific organic compounds have been detected in polar regions, but their fate after deposition to snow is poorly characterized. Within this context, a series of exposure experiments were carried out to observe the post-depositional processing of organic compounds under real-world conditions in snow on the surface of the Greenland Ice Sheet, at the Summit research station. Snow was prepared from water spiked with isotopically labelled organic compounds, representative of typical molecular marker compounds emitted from anthropogenic activities. Reaction rate constants and reaction order were determined based on a decrease in concentration to a stable, non-zero, threshold concentration. Fluoranthene- d 10 , docosane- d 46 , hexadecanoic acid- d 31 , docosanoic acid- d 43 and azelaic acid- d 14 were estimated to have first order loss rates within surface snow with reaction rate constants of 0.068, 0.040, 0.070, 0.067 and 0.047 h -1 , respectively. No loss of heptadecane- d 36 was observed. Overall, these results suggest that organic contaminants are archived in polar snow, although significant post-depositional losses of specific organic compounds occur. This has implications for the environmental fate of organic contaminants, as well as for ice-core studies that seek to use organic molecular markers to infer past atmospheric loadings, and source emissions. Keywords: Snow; photochemistry; air pollution; Greenland; Arctic To access the supplementary material to this article: 'Supplementary Figures & Table' and 'Supplementary File', please see Supplementary files in the column to the right (under Article Tools). (Published: 26 July 2012) Citation: Polar Research 2012, 31 , 11597, http://dx.doi.org/10.3402/polar.v31i0.11597

Air mass classification in coastal New England and its relationship to meteorological conditions

The dominant air mass types along coastal New England during summer 2004 were classified and their relationship to synoptic meteorological conditions investigated as a component of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign. Representative air mass types were defined on the basis of variability in the occurrence of volatile organic compounds (VOCs), and they were further grouped into distinct source‐related categories. Emissions from nearby anthropogenic sources were found to govern the total variance of the data set (58% at Appledore Island (AI) and 56% at Thompson Farm (TF)), whereas long‐distance transport was much less dominant (15% on AI and 17% at TF). This result indicates frequent influence from recent anthropogenic emissions at TF and AI, with periodic inputs of aged/processed pollutants. The fractional time periods dominated by anthropogenic (recent and aged/processed) and marine biogenic air masses were almost the same at TF and AI (36% versus 30% and 14% versus 16% respectively), clearly showing the strong impact of continental outflow on the nearshore marine atmosphere and a surprising persistent influence of marine biogenic emissions at an inland site. Empirical orthogonal function (EOF) analysis suggested that the most important circulation pattern during summer 2004 was characterized by a low trough positioned along coastal New England, leaving this region under the control of northwesterly flow from central Canada. This result helps explain why New England in summer 2004 was less polluted compared to previous years.

Epithelial and inflammatory responses in the airways of laboratory rats coexposed to ozone and biogenic substances: Enhancement of toxicant-induced airway injury

People are often concurrently exposed to more than one air pollutant whether they are in outdoor or indoor environments. Therefore, inhalation studies that are designed to examine the toxicity of coexposures to two or more airborne toxicants may be more relevant for assessing human health risks than those studies that investigate the toxic effects of only one airborne toxicant at a time. Furthermore, airborne biogenic substances such as pollens, bacteria, fungi, and microbial toxins often coexist with common air pollutants in the ambient air, and when inhaled may also cause specific adverse effects on the respiratory tract. One such biogenic substance, bacterial endotoxin, is a potent stimulus of airway inflammation and is commonly found in domestic, agricultural, and industrial settings. Little is known about the interaction of exposures to biogenic substances and common air pollutants, such as ozone or airborne particulate matter. In the last few years, we have performed a series of in vivo studies using laboratory rodents that examined how airway surface epithelial cells are altered by coexposure to ozone and a biogenic substance, either bacterial endotoxin or a commonly used experimental aeroallergen (ovalbumin). Results from these studies indicate that the ozone-induced epithelial and inflammatory responses in laboratory rodents may be markedly enhanced by coexposure to an inhaled biogenic substance. Conversely, the adverse airway alterations caused by exposure to biogenic substances may be enhanced by coexposure to ozone. The results from these initial studies have also suggested some of the cellular and molecular mechanisms underlying the phenotypic epithelial alterations induced by these coexposures. Many more studies are needed to fully elucidate the potential risk to human health from coexposure to air pollutants and airborne biogenic substances.

Glass surface deactivants for sulfur-containing gases

In gas chromatographic technique for measuring reduced sulfur-containing gases in biogenic air fluxes, the major problem seemed to be the irreversible adsorption of the polar sulfur compounds on the glass surfaces of the cryogenic sampling traps. This article discusses the comparative degrees of Pyrex glass surface passivation for over 25 chemical deactivants and their related pretreatment procedures. Since H/sub 2/S was discovered to be the sulfur compound with a consistently lower recovery efficiency than COS, CH/sub 3/SH, CH/sub 3/SCH, CS/sub 2/ or CH/sub 3/SSCH/sub 3/, the percent recovery for H/sub 2/S was employed as the indicator of effectiveness for the various deactivation treatments. Tables are presented summarizing the mean H/sub 2/S recoveries for chlorosilane deactivants and for the mean H/sub 2/S recoveries for different pyrex surface pretreatments with an octadecyltrialkoxysilane deactivation. The general conclusion of this investigation is that the relative degree of passivation for glass surfaces by present deactivation techniques is dependent on the types of analyzed compounds and the nature of the glass surface.