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To explore the feasibility of meeting recently proposed large-scale tree planting targets, a UK wide assessment of land available for afforestation was carried out, considering a range of physical, environmental and policy constraints in three hypothetical planting scenarios. Results show there is sufficient space to meet these targets in all three scenarios, even if planting is prevented on good to moderate quality agricultural land and within protected areas. However, this would require planting on a large proportion of unconstrained land, especially for the more ambitious targets, which is unevenly distributed across the UK. This would limit opportunities for spatially targeting woodland creation, which may restrict the provision of additional ecosystem services such as air pollution control and recreation, and induce widespread negative impacts on landscapes and communities. In order to overcome these limitations, relaxing constraints, such as permitting afforestation of higher quality agricultural land, will need to be considered. Meeting many of the proposed afforestation targets would result in a transformational change in British land cover, which could replace or significantly impact the business models of tens of thousands of farms, and see the replacement of hundreds of thousands to millions of hectares of grassland, arable and horticultural land and other land covers. This would require rates of planting that far exceed those seen historically. Policies and mechanisms that could be used to encourage this planting, both by the state and private sectors, are discussed.

Author(s): Cappa, CD; Zhang, X; Russell, LM; Collier, S; Lee, AKY; Chen, CL; Betha, R; Chen, S; Liu, J; Price, DJ; Sanchez, KJ; McMeeking, GR; Williams, LR; Onasch, TB; Worsnop, DR; Abbatt, J; Zhang, Q | Abstract: Observations from a wintertime and summertime field campaign are used to assess the relationship between black and brown carbon (BC and BrC, respectively) optical properties and particle composition and coating state. The wintertime campaign, in Fresno, CA, was impacted by primary emissions from residential wood burning, secondary organic and inorganic particle formation, and BC from motor vehicles. Two major types of BrC were observed in wintertime. One occurred primarily at night—the result of primary biomass burning emissions. The second was enhanced in daytime and strongly associated with particulate nitrate and the occurrence of fog. The biomass-burning-derived BrC absorbed more strongly than the nitrate-associated BrC but had a weaker wavelength dependence. The wintertime BC-specific mass absorption coefficient (MAC BC ) exhibited limited dependence on the ensemble-average coating-to-BC mass ratio (R coat-rBC ) at all wavelengths, even up to R coat-rBC of ~5. For the summertime campaign, in Fontana, CA, BC dominated the light absorption, with negligible BrC contribution even after substantial photochemical processing. The summertime MAC BC exhibited limited dependence on R coat-rBC , even up to ratios of g10. Based on the four classes of BC-containing particles identified by Lee et al. (2017, https://doi.org/10.5194/acp-17-15055-2017) for the summertime measurements, the general lack of an absorption enhancement can be partly—although not entirely—attributed to an unequal distribution of coating materials between the BC-containing particle types. These observations demonstrate that in relatively near-source environments, even those impacted by strong secondary aerosol production, the ensemble-average, mixing-induced absorption enhancement for BC due to coatings can be quite small.

The valuation of natural capital within individual farms could inform environmentally beneficial land use change and form the basis of agricultural subsidy schemes based on the provision of ecosystem services. Land cover extents can be used in a benefit transfer approach to produce monetary valuations of natural capital rapidly and at low cost. However, the methodology has not before been used within individual farms, and the impact of land cover data characteristics on the accuracy of valuations is uncertain. Here, we apply the approach to five UK farms of contrasting size, configuration and farming style, using three widely available land cover products. Results show that the land cover product used has a substantial impact on valuations, with differences of up to 58%, and the magnitude of this effect varies considerably according to the landscape structure of the farm. At most sites, valuation differences are driven by the extent of woodland recorded in the landscape, with higher resolution land cover products incorporating larger amounts of woodland through inclusion of smaller patches, leading to higher overall valuations. Integrating more accurate land cover data and accounting for the condition, configuration and location of natural capital has potential to improve the accuracy of valuations.

We investigate heterogeneous oxidation kinetics of monolayer-thick, surface-sorbed organics, namely di-n-octyl phthalate (DnOP) and palmitic acid (PA), with gas-phase OH. The pseudo-first order rate constants for organic loss at OH concentrations of 1.6 × 108 molecules/cm3 are: (2.3 ± 0.1) × 10-4 to (4.8 ± 0.8) × 10-4 s-1 , and (1.3 ± 0.5) × 10-4 s-1 for DnOP and PA, respectively. Films developed in indoor office environments over a few weeks are also oxidized using the same OH concentration. Heterogeneous decay rate constants of mass signals from these films, attributed to phthalates (MW = 390.6) and to PA, are similar to those for the single-component films, ie, (1.9 ± 0.4) × 10-4 to (3.4 ± 0.5) × 10-4 s-1 , and (1.1 ± 0.4) × 10-4 s-1 , respectively. These results suggest that the lifetimes for OH heterogeneous oxidation of monolayer-thick indoor organic films will be on the timescale of weeks to months. To support this argument, we present the first analysis of the mass transfer processes that occur when short-lived gas-phase molecules, such as OH, are taken up by reactive indoor surfaces. Due to rapid chemical production, the diffusion limitation to mass transfer is less important for short-lived molecules than for molecules with little chemical production, such as ozone.

Ambient levels of chlorinated gases and aerosol components were measured by on-line chemical ionization and aerosol mass spectrometers after an indoor floor was repeatedly washed with a commercial bleach solution. Gaseous chlorine (Cl_2, 10′s of ppbv) and hypochlorous acid (HOCl, 100′s of ppbv) arise after floor washing, along with nitryl chloride (ClNO_2), dichlorine monoxide (Cl2O) and chloramines (NHCl_2, NCl_3). Much higher mixing ratios would prevail in a room with lower and more commonly encountered air exchange rates than that observed in the study (12.7 h^(−1)). Coincident with the formation of gas-phase species, particulate chlorine levels also rise. Cl_2, ClNO_2, NHCl_2 and NCl_3 exist in the headspace of the bleach solution whereas HOCl was only observed after floor washing. HOCl decays away 1.4 times faster than the air exchange rate, indicative of uptake onto room surfaces and consistent with the well-known chlorinating ability of HOCl. Photochemical box modeling captures the temporal profiles of Cl_2 and HOCl very well, and indicates that the OH, Cl and ClO gas-phase radical concentrations in the indoor environment could be greatly enhanced (> 10^6 and 10^5 cm^(−3) for OH and Cl, respectively) in such washing conditions, dependent on the amount of indoor illumination.

The House Observations of Microbial and Environmental Chemistry (HOMEChem) study is a collaborative field investigation designed to probe how everyday activities influence the emissions, chemical transformations and removal of trace gases and particles in indoor air. Sequential and layered experiments in a research house included cooking, cleaning, variable occupancy, and window-opening. This paper describes the overall design of HOMEChem and presents preliminary case studies investigating the concentrations of reactive trace gases, aerosol particles, and surface films. Cooking was a large source of VOCs, CO2, NOx, and particles. By number, cooking particles were predominantly in the ultrafine mode. Organic aerosol dominated the submicron mass, and, while variable between meals and throughout the cooking process, was dominated by components of hydrocarbon character and low oxygen content, similar to cooking oil. Air exchange in the house ensured that cooking particles were present for only short periods. During unoccupied background intervals, particle concentrations were lower indoors than outdoors. The cooling coils of the house ventilation system induced cyclic changes in water soluble gases. Even during unoccupied periods, concentrations of many organic trace gases were higher indoors than outdoors, consistent with housing materials being potential sources of these compounds to the outdoor environment. Organic material accumulated on indoor surfaces, and exhibited chemical signatures similar to indoor organic aerosol.

Trees provide a multitude of ecosystem services but are vulnerable to failure and limb loss under high winds. This is a natural process which initiates regeneration in forests but tree failures close to critical infrastructure networks lead to disruption to services and financial loss. Hence, network operators tend to apply the precautionary principle and remove all trees close to such infrastructure which leads to unnecessary loss of healthy trees, therefore, a more focussed approach is required. We introduce TREEFALL: an objective and scalable framework to assess tree failure risk. It uses novel approaches to quantify tree geometry, downscale wind parameters, simulate shielding by neighbouring trees and calculate wind-induced failure risk based on meteorological data for previous storms, scenarios or forecasts. Consequently, TREEFALL can identify individual trees which pose the greatest threat to infrastructure networks which can be targeted for field survey and management interventions where necessary. The model has broad potential for application to many different types of infrastructure networks and across the forest and environmental sciences.

The chemical stability of levoglucosan was studied by exploring its isotopic fractionation during the oxidation by hydroxyl radicals. Aqueous solutions as well as mixed (NH4)2SO4-levoglucosan particles were exposed to OH. In both cases, samples experiencing different extents of processing were isotopically analyzed by Thermal Desorption-Gas Chromatography-Isotope Ratio Mass Spectrometry (TD-GC-IRMS). From the dependence of levoglucosan δ13C and concentration on the reaction extent, the kinetic isotope effect (KIE) of the OH oxidation reactions was determined to be 1.00187±0.00027 and 1.00229±0.00018, respectively. Both show good agreement within the uncertainty range. For the heterogeneous oxidation of particulate levoglucosan by gas-phase OH, a reaction rate constant of (2.67±0.03)·10−12 cm3 molecule−1S−1 was derived. The laboratory kinetic data, together with isotopic source and ambient observations, give information on the extent of aerosol chemical processing in the atmosphere.

This study addresses, through two types of experiments, the potential for the oceans to act as a source of atmospheric ice-nucleating particles (INPs). The INP concentration via deposition mode nucleation was measured in situ at a coastal site in British Columbia in August 2013. The INP concentration at conditions relevant to cirrus clouds (i.e., −40 °C and relative humidity with respect to ice, RH ice = 139%) ranged from 0.2 L −1 to 3.3 L −1 . Correlations of the INP concentrations with levels of anthropogenic tracers (i.e., CO, SO 2 , NO x , and black carbon) and numbers of fluorescent particles do not indicate a significant influence from anthropogenic sources or submicron bioaerosols, respectively. Additionally, the INPs measured in the deposition mode showed a poor correlation with the concentration of particles with sizes larger than 500 nm, which is in contrast with observations made in the immersion freezing mode. To investigate the nature of particles that could have acted as deposition INP, laboratory experiments with potential marine aerosol particles were conducted under the ice-nucleating conditions used in the field. At −40 °C, no deposition activity was observed with salt aerosol particles (sodium chloride and two forms of commercial sea salt: Sigma-Aldrich and Instant Ocean), particles composed of a commercial source of natural organic matter (Suwannee River humic material), or particle mixtures of sea salt and humic material. In contrast, exudates from three phytoplankton ( Thalassiosira pseudonana, Nanochloris atomus, and Emiliania huxleyi ) and one marine bacterium ( Vibrio harveyi ) exhibited INP activity at low RH ice values, down to below 110%. This suggests that the INPs measured at the field site were of marine biological origins, although we cannot rule out other sources, including mineral dust.

A growing number of ambient measurements of isocyanic acid (HNCO) are being made, yet little is known about its fate in the atmosphere. To better understand HNCO's loss processes and particularly its atmospheric partitioning behaviour, we measure its effective Henry's Law coefficient KHeff with a bubbler experiment using chemical ionization mass spectrometry as the gas phase analytical technique. By conducting experiments at different pH values and temperature, a Henry's Law coefficient KH of 26 ± 2 M atm−1 is obtained, with an enthalpy of dissolution of −34 ± 2 kJ mol−1, which translates to a KHeff of 31 M atm−1 at 298 K and at pH 3. Our approach also allows for the determination of HNCO's acid dissociation constant, which we determine to be Ka = 2.1 ± 0.2 × 10−4 M at 298 K. Furthermore, by using ion chromatography to analyze aqueous solution composition, we revisit the hydrolysis kinetics of HNCO at different pH and temperature conditions. Three pH-dependent hydrolysis mechanisms are in play and we determine the Arrhenius expressions for each rate to be k1 = (4.4 ± 0.2) × 107 exp(−6000 ± 240∕T) M s−1, k2 = (8.9 ± 0.9) × 106 exp(−6770 ± 450∕T) s−1 and k3 = (7.2 ± 1.5) × 108 exp(−10 900 ± 1400∕T) s−1, where k1 is for HNCO + H++ H2O → NH4++ CO2, k2 is for HNCO + H2O → NH3 + CO2 and k3 is for NCO−+ 2 H2O → NH3+ HCO3−. HNCO's lifetime against hydrolysis is therefore estimated to be 10 days to 28 years at pH values, liquid water contents, and temperatures relevant to tropospheric clouds, years in oceans and months in human blood. In all, a better parameterized Henry's Law coefficient and hydrolysis rates of HNCO allow for more accurate predictions of its concentration in the atmosphere and consequently help define exposure of this toxic molecule.

Information on what aerosol particle types are the major sources of ice nucleating particles (INPs) in the atmosphere is needed for climate predictions. To determine which aerosol particles are the major sources of immersion-mode INPs at a coastal site in Western Canada, we investigated correlations between INP number concentrations and both concentrations of different atmospheric particles and meteorological conditions. We show that INP number concentrations are strongly correlated with the number concentrations of fluorescent bioparticles between −15 and −25 °C, and that the size distribution of INPs is most consistent with the size distribution of fluorescent bioparticles. We conclude that biological particles were likely the major source of ice nuclei at freezing temperatures between −15 and −25 °C at this site for the time period studied. At −30 °C, INP number concentrations are also well correlated with number concentrations of the total aerosol particles ≥ 0.5 μm, suggesting that non-biological particles may have an important contribution to the population of INPs active at this temperature. As we found that black carbon particles were unlikely to be a major source of ice nuclei during this study, these non-biological INPs may include mineral dust. Furthermore, correlations involving chemical tracers of marine aerosols and marine biological activity, sodium and methanesulfonic acid, indicate that the majority of INPs measured at the coastal site likely originated from terrestrial rather than marine sources. Finally, six existing empirical parameterizations of ice nucleation were tested to determine if they accurately predict the measured INP number concentrations. We found that none of the parameterizations selected are capable of predicting INP number concentrations with high accuracy over the entire temperature range investigated. This finding illustrates that additional measurements are needed to improve parameterizations of INPs and their subsequent climatic impacts.

This paper demonstrates that OH radicals are formed by photolysis of secondary organic aerosol (SOA) material formed by terpene ozonolysis. The SOA is collected on filters, dissolved in water containing a radical trap (benzoic acid), and then exposed to ultraviolet light in a photochemical reactor. The OH formation rates, which are similar for both α-pinene and limonene SOA, are measured from the formation rate of p-hydroxybenzoic acid as measured using offline HPLC analysis. To evaluate whether the OH is formed by photolysis of H2O2 or organic hydroperoxides (ROOH), the peroxide content of the SOA was measured using the horseradish peroxidase-dichlorofluorescein (HRP-DCF) assay, which was calibrated using H2O2. The OH formation rates from SOA are 5 times faster than from the photolysis of H2O2 solutions whose concentrations correspond to the peroxide content of the SOA solutions, assuming that the HRP-DCF signal arises from H2O2 alone. The higher rates of OH formation from SOA are likely due to ROOH photolysis, but we cannot rule out a contribution from secondary processes as well. This result is substantiated by photolysis experiments conducted with t-butyl hydroperoxide and cumene hydroperoxide which produce over 3 times more OH than photolysis of equivalent concentrations of H2O2. Relative to the peroxide level in the SOA and assuming that the peroxides drive most of the ultraviolet absorption, the quantum yield for OH generation from α-pinene SOA is 0.8 ± 0.4. This is the first demonstration of an efficient photolytic source of OH in SOA, one that may affect both cloud water and aerosol chemistry.

Many atmospheric and chemical variables influence the partitioning equilibrium between gas phase and condensed phases of compounds implicated in the formation of secondary organic aerosol (SOA). The large number of factors and their interaction makes it often difficult to assess their relative importance and concerted impact. Here we introduce a two-dimensional space, which maps regions of dominant atmospheric phase distribution within a coordinate system defined by equilibrium partitioning coefficients between the gas phase, an aqueous phase and a water insoluble organic matter (WIOM) phase. Placing compounds formed from the oxidation of n-alkanes, terpenes and mono-aromatic hydrocarbons on the maps based on their predicted partitioning properties allows for a simple graphical assessment of their equilibrium phase distribution behaviour. Specifically, it allows for the simultaneous visualization and quantitative comparison of the impact on phase distribution of changes in atmospheric parameters (such as temperature, salinity, WIOM phase polarity, organic aerosol load, and liquid water content), and chemical properties (such as oxidation state, molecular size, functionalization, and dimerisation). The graphical analysis reveals that the addition of hydroxyl, carbonyl and carboxyl groups increases the affinity of aliphatic, alicyclic and aromatic hydrocarbons for the aqueous phase more rapidly than their affinity for WIOM, suggesting that the aqueous phase may often be relevant even for substances that are considerably larger than the C2 and C3 compounds that are typically believed to be associated with aqueous SOA. In particular, the maps identify some compounds that contribute to SOA formation if partitioning to both WIOM and aqueous phase is considered, but would remain in the gas phase if either condensed phase were neglected. For example, many semi-volatile α-pinene oxidation products will contribute to aqueous SOA under the high liquid water content conditions encountered in clouds, but would remain vapours in wet aerosol. It is conceivable to develop parameterizations of "partitioning basis sets" that group compounds with comparable partitioning properties, which – when combined with data on the abundance of those groups of compounds – could serve in the simulation of SOA formation.

Understanding the impact of atmospheric black carbon (BC)-containing particles on human health and radiative forcing requires knowledge of the mixing state of BC, including the characteristics of the materials with which it is internally mixed. In this study, we examine the mixing state of refractory BC (rBC) and other aerosol components in an urban environment (downtown Toronto) utilizing the Aerodyne soot particle aerosol mass spectrometer equipped with a light scattering module (LS-SP-AMS). k-means cluster analysis was used to classify single particle mass spectra into chemically distinct groups. One resultant particle class is dominated by rBC mass spectral signals (C1+ to C5+) while the organic signals fall into a few major particle classes identified as hydrocarbon-like organic aerosol (HOA), oxygenated organic aerosol (OOA), and cooking emission organic aerosol (COA). A gradual mixing is observed with small rBC particles only thinly coated by HOA (~ 28% by mass on average), while over 90% of the HOA-rich particles did not contain detectable amounts of rBC. Most of the particles classified into other inorganic and organic particle classes were not significantly associated with rBC. The single particle results also suggest that HOA and COA emitted from anthropogenic sources were likely major contributors to organic-rich particles with vacuum aerodynamic diameter (dva) ranging from ~ 200 to 400 nm. The similar temporal profiles and mass spectral features of the organic classes identified by cluster analysis and the factors from a positive matrix factorization (PMF) analysis of the ensemble aerosol data set validate the interpretation of the PMF results.

The soot-particle aerosol mass spectrometer (SP-AMS) uses an intra-cavity infrared laser to vaporize refractory black carbon (rBC) containing particles, making the particle beam–laser beam overlap critical in determining the collection efficiency (CE) for rBC and associated non-refractory particulate matter (NR-PM). This work evaluates the ability of the SP-AMS to quantify rBC and NR-PM mass in internally mixed particles with different thicknesses of organic coating. Using apparent relative ionization efficiencies for uncoated and thickly coated rBC particles, we report measurements of SP-AMS sensitivity to NR-PM and rBC, for Regal Black, the recommended particulate calibration material. Beam width probe (BWP) measurements are used to illustrate an increase in sensitivity for highly coated particles due to narrowing of the particle beam, which enhances the CE of the SP-AMS by increasing the laser beam–particle beam overlap. Assuming complete overlap for thick coatings, we estimate CE for bare Regal Black particles of 0.6 ± 0.1, which suggests that previously measured SP-AMS sensitivities to Regal Black were underestimated by up to a factor of 2. The efficacy of the BWP measurements is highlighted by studies at a busy road in downtown Toronto and at a non-roadside location, which show particle beam widths similar to, but greater than that of bare Regal Black and coated Regal Black, respectively. Further BWP measurements at field locations will help to constrain the range of CE for fresh and aged rBC-containing particles. The ability of the SP-AMS to quantitatively assess the composition of internally mixed particles is validated through measurements of laboratory-generated organic coated particles, which demonstrate that the SP-AMS can quantify rBC and NR-PM over a wide range of particle compositions and rBC core sizes.

Model simulations of an Arctic summer field campaign were carried out. The model results were compared with observational data from both ground-based monitoring and in situ measurements on-board multiple mobile platforms. The model was able to well capture regional sources and transport affecting the Arctic air quality. It is shown that the study area was impacted by North American (NA) regional biomass burning emissions. The model-observation comparison also corroborates previous findings on possible roles of marine-biogenic sources in aerosol production in the Arctic MBL during summertime.

Several methods have been presented in the literature to predict an organic chemical's equilibrium partitioning between the water insoluble organic matter (WIOM) component of aerosol and the gas phase, Ki,WIOM, as a function of temperature. They include (i) polyparameter linear free energy relationships calibrated with empirical aerosol sorption data, as well as (ii) the solvation models implemented in SPARC and (iii) the quantum-chemical software COSMOtherm, which predict solvation equilibria from molecular structure alone. We demonstrate that these methods can be used to predict Ki,WIOM for large numbers of individual molecules implicated in secondary organic aerosol (SOA) formation, including those with multiple functional groups. Although very different in their theoretical foundations, these methods give remarkably consistent results for the products of the reaction of normal alkanes with OH, i.e. their partition coefficients Ki,WIOM generally agree within one order of magnitude over a range of more than ten orders of magnitude. This level of agreement is much better than that achieved by different vapour pressure estimation methods that are more commonly used in the SOA community. Also, in contrast to the agreement between vapour pressure estimates, the agreement between the Ki,WIOM estimates does not deteriorate with increasing number of functional groups. Furthermore, these partitioning coefficients Ki,WIOM predicted SOA mass yields in agreement with those measured in chamber experiments of the oxidation of normal alkanes. If a Ki,WIOM prediction method was based on one or more surrogate molecules representing the solvation properties of the mixed OM phase of SOA, the choice of those molecule(s) was found to have a relatively minor effect on the predicted Ki,WIOM, as long as the molecule(s) are not very polar. This suggests that a single surrogate molecule, such as 1-octanol or a hypothetical SOA structure proposed by Kalberer et al. (2004), may often be sufficient to represent the WIOM component of the SOA phase, greatly simplifying the prediction. The presented methods could substitute for vapour-pressure-based methods in studies such as the explicit modelling of SOA formation from single precursor molecules in chamber experiments.

As one aspect of the NETwork on Climate and Aerosols: addressing key uncertainties in Remote Canadian Environments (NETCARE), measurements of the cloud condensation nucleation properties of 50 and 100 nm aerosol particles were conducted at Ucluelet on the west coast of Vancouver Island in August 2013. The overall hygroscopicity parameter of the aerosol (κambient) exhibited a wide variation, ranging from 0.14 ± 0.05 to 1.08 ± 0.40 (where the uncertainty represents the systematic error). The highest κ values arose when the organic-to-sulfate ratio of the aerosol was lowest and when winds arrived from the west after transport through the marine boundary layer. The average κambient during this time was 0.57 ± 0.16, where the uncertainty represents the standard deviation. At most other times, the air was predominantly influenced by both marine and continental emissions, which had lower average PM1 κambient values (max value, 0.41 ± 0.08). The two-day average aerosol ionic composition also showed variation, but was consistently acidic and dominated by ammonium (18–56% by mole) and sulfate (19–41% by mole), with only minor levels of sodium or chloride. Average κorg (hygroscopicity parameter for the aerosol's organic component) values were estimated using PM1 aerosol composition data and by assuming that the ratio of aerosol organic to sulfate mass is related directly to the composition of the size-selected particles.

Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (−2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M−1 s−1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44–f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.

The ice nucleation abilities of fresh, water-soluble, internally mixed, and photochemically oxidized α-pinene secondary organic aerosol (SOA) particles were investigated at cirrus cloud temperatures in a continuous flow diffusion chamber. SOA sampled from a flow tube (SOA-fresh-FT) mimicked freshly generated particles, while the water-soluble organic compound fraction from a FT and smog chamber (SOA-WSOC-FT, SOA-WSOC-SC) mimicked cloud-processed particles. SOA-fresh-FT, SOA-WSOC-FT, and SOA-WSOC-SC particles were not highly active at nucleating ice between 233 K and 213 K, with activation onsets (i.e., 0.1% of particles forming ice) at or slightly above the theoretical homogeneous freezing line. A significant increase in the O/C of SOA-WSOC-SC via aqueous phase OH oxidation did not modify the ice nucleation abilities, indicating that the detailed composition of the particles is not of paramount importance to their ice nucleating abilities. Instead, precooling the SOA-WSOC-FT and SOA-WSOC-SC particles to 233 K dropped their ice nucleation onsets by up to 20% relative humidity with respect to ice, with lower temperatures likely driving the particles to be more viscous and solid-like. However, it is possible that preactivation contributed to the reduction of the ice nucleation onsets. Particles composed of both SOA-WSOC and ammonium sulfate (AS) were significantly less active in the deposition nucleation mode than pure, solid AS particles.

Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acid (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air–seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transfer-reaction mass spectrometry (PTR-MS) and light-emitting diode cavity enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon-carbon double bonds in the PUFA molecules. In addition, two highly reactive di-carbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78%, 29%, 4% and

Mineral dusts are well known to be efficient ice nuclei, where the source of this efficiency has typically been attributed to the presence of clay minerals such as illite and kaolinite. However, the ice nucleating abilities of the more minor mineralogical components have not been as extensively examined. As a result, the deposition ice nucleation abilities of 24 atmospherically relevant mineral samples have been studied, using a continuous flow diffusion chamber at −40.0 ± 0.3 °C and particles size-selected at 200 nm. By focussing on using the same experimental procedure for all experiments, a relative ranking of the ice nucleating abilities of the samples was achieved. In addition, the ice nucleation behaviour of the pure minerals is compared to that of complex mixtures, such as Arizona Test Dust (ATD) and Mojave Desert Dust (MDD), and to lead iodide, which has been previously proposed for cloud seeding. Lead iodide was the most efficient ice nucleus (IN), requiring a critical relative humidity with respect to ice (RHi) of 122.0 ± 2.0% to activate 0.1% of the particles. MDD (RHi) 126.3 ± 3.4%) and ATD (RHi 129.5 ± 5.1%) have lower but comparable activity. From a set of clay minerals (kaolinite, illite, montmorillonite), non-clay minerals (e.g. hematite, magnetite, calcite, cerussite, quartz), and feldspar minerals (orthoclase, plagioclase) present in the atmospheric dusts, it was found that the feldspar minerals (particularly orthoclase) and some clays (particularly kaolinite) were the most efficient ice nuclei. Orthoclase and plagioclase were found to have critical RHi values of 127.1 ± 6.3% and 136.2 ± 1.3%, respectively. The presence of feldspars (specifically orthoclase) may play a significant role in the IN behaviour of mineral dusts despite their lower percentage in composition relative to clay minerals.

The activation of reactive halogen species – particularly Cl2 – from sea ice and snow surfaces is not well understood. In this study, we used a photochemical snow reactor coupled to a chemical ionization mass spectrometer to investigate the production of Br2, BrCl and Cl2 from NaCl/NaBr-doped artificial snow samples. At temperatures above the NaCl-water eutectic, illumination of samples (λ > 310 nm) in the presence of gas phase O3 led to the accelerated release of Br2, BrCl and the release of Cl2 in a process that was significantly enhanced by acidity, high surface area and additional gas phase Br2. Cl2 production was only observed when both light and ozone were present. The total halogen release depended on [ozone] and pre-freezing [NaCl]. Our observations support a "halogen explosion" mechanism occurring within the snowpack, which is initiated by heterogeneous oxidation and propagated by Br2 or BrCl photolysis and by recycling of HOBr and HOCl into the snowpack. Our study implicates this important role of active chemistry occurring within the interstitial air of aged (i.e. acidic) snow for halogen activation at polar sunrise.

Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox-active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. These results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10−4 m3 μg−1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. Also, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs) via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear-magnetic-resonance (1H NMR) spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS). Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, and methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water, but it may also be present in the mM level in aerosol liquid water (ALW), where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

[1] The ice nucleation abilities of submicron aerosol particles of two Martian regolith analogs, the Mojave Mars simulant and Johnson Space Center Mars-1, were investigated with the University of Toronto continuous flow diffusion chamber. The temperature range studied (> 200 K) is relevant to low-altitude water ice cloud formation in the Martian atmosphere and the aerosol particles were suspended in air, in contrast to previous experiments. Both simulants were found to be active ice nuclei in the deposition nucleation mode between 223 K and 203 K. The Mojave Mars simulant particles were found to be better ice nuclei than the Johnson Space Center Mars-1 particles requiring lower supersaturations to nucleate ice. It was observed that the critical supersaturation (Scrit) to activate 1% of the particles increased with decreasing temperature in accord with previous low-temperature studies, rising to a value of above 1.7 at 203 K. This corroborates literature results that there is a substantial barrier to ice nucleation at low temperatures, underlining the need for incorporating this effect in Martian cloud microphysical models. It was also found that Scrit did not change when the size of the Mojave Mars simulant particles was increased from 240 to 400 nm. Comparison of the Martian simulants with other mineral dusts shows that the Johnson Space Center Mars-1 analog behaves similarly to the well-known terrestrial ice nuclei such as kaolinite and Arizona test dust particles, whereas the Mojave Mars simulant behaves closer to another clay, montmorillonite. The wettability parameter, m, was calculated to range from 0.955 to 0.959.

The SPectrometer for Ice Nuclei (SPIN) is a commercially available ice nucleating particle (INP) counter manufactured by Droplet Measurement Technologies in Boulder, CO. The SPIN is a continuous flow diffusion chamber with parallel plate geometry based on the Zurich Ice Nucleation Chamber and the Portable Ice Nucleation Chamber. This study presents a standard description for using the SPIN instrument and also highlights methods to analyze measurements in more advanced ways. It characterizes and describes the behavior of the SPIN chamber, reports data from laboratory measurements, and quantifies uncertainties associated with the measurements. Experiments with ammonium sulfate are used to investigate homogeneous freezing of deliquesced haze droplets and droplet breakthrough. Experiments with kaolinite, NX illite, and silver iodide are used to investigate heterogeneous ice nucleation. SPIN nucleation results are compared to those from the literature. A machine learning approach for analyzing depolarization data from the SPIN optical particle counter is also presented (as an advanced use). Overall, we report that the SPIN is able to reproduce previous INP counter measurements., Atmospheric Measurement Techniques, 9 (7), ISSN:1867-1381, ISSN:1867-8548

Observations from the 2007 Border Air Quality and Meteorology Study (BAQS-Met 2007) in Southern Ontario, Canada, were used to evaluate predictions of primary organic aerosol (POA) and two other carbonaceous species, black carbon (BC) and carbon monoxide (CO), made for this summertime period by Environment Canada's AURAMS regional chemical transport model. Particle component-based factor analysis was applied to aerosol mass spectrometer measurements made at one urban site (Windsor, ON) and two rural sites (Harrow and Bear Creek, ON) to derive hydrocarbon-like organic aerosol (HOA) factors. A novel diagnostic model evaluation was performed by investigating model POA bias as a function of HOA mass concentration and indicator ratios (e.g. BC/HOA). Eight case studies were selected based on factor analysis and back trajectories to help classify model bias for certain POA source types. By considering model POA bias in relation to co-located BC and CO biases, a plausible story is developed that explains the model biases for all three species. At the rural sites, daytime mean PM1 POA mass concentrations were under-predicted compared to observed HOA concentrations. POA under-predictions were accentuated when the transport arriving at the rural sites was from the Detroit/Windsor urban complex and for short-term periods of biomass burning influence. Interestingly, the daytime CO concentrations were only slightly under-predicted at both rural sites, whereas CO was over-predicted at the urban Windsor site with a normalized mean bias of 134%, while good agreement was observed at Windsor for the comparison of daytime PM1 POA and HOA mean values, 1.1 μg m−3 and 1.2 μg m−3, respectively. Biases in model POA predictions also trended from positive to negative with increasing HOA values. Periods of POA over-prediction were most evident at the urban site on calm nights due to an overly-stable model surface layer. This model behaviour can be explained by a combination of model under-estimation of vertical mixing at the urban location, under-representation of PM emissions for on-road traffic exhaust along major urban roads and highways, and a more structured allocation of area POA sources such as food cooking and dust emissions to urban locations. A downward trend in POA bias was also observed at the urban site as a function of the BC/HOA indicator ratio, suggesting a possible association of POA under-prediction with under-representation of diesel combustion sources. An investigation of the emission inventories for the province of Ontario and the nearby US state of Indiana also suggested that the top POA area emission sources (food cooking, organic-bound to dust, waste disposal burning) dominated over mobile and point sources, again consistent with a mobile under-estimation. We conclude that more effort should be placed at reducing uncertainties in the treatment of several large POA emission sources, in particular food cooking, fugitive dust, waste disposal burning, and on-road traffic sources, and especially their spatial surrogates and temporal profiles. This includes using higher spatial resolution model grids to better resolve the urban road network and urban food cooking locations. We also recommend that additional sources of urban-scale vertical mixing in the model, such as a stronger urban heat island effect and vehicle-induced turbulence, would help model predictions at urban locations, especially at night time.

The water-soluble fractions of aerosol filter samples and cloud water collected during the Whistler Aerosol and Cloud Study (WACS 2010) were analyzed using an Aerodyne aerosol mass spectrometer (AMS). This is the first study to report AMS organic spectra of re-aerosolized cloud water, and to make direct comparison between the AMS spectra of cloud water and aerosol samples collected at the same location. In general, the mass spectra of aerosol were very similar to those of less volatile cloud organics. By using a photochemical reactor to oxidize both aerosol filter extracts and cloud water, we find evidence that fragmentation of water-soluble organics in aerosol increases their volatility during photochemical oxidation. By contrast, enhancement of AMS-measurable organic mass by up to 30% was observed during the initial stage of oxidation of cloud water organics, which was followed by a decline at the later stages of oxidation. These observations are in support of the general hypothesis that cloud water oxidation is a viable route for SOA formation. In particular, we propose that additional SOA material was produced by functionalizing dissolved organics via OH oxidation, where these dissolved organics are sufficiently volatile that they are not usually part of the aerosol. This work demonstrates that water-soluble organic compounds of intermediate volatility (IVOC), such as cis-pinonic acid, produced via gas-phase oxidation of monoterpenes, can be important aqueous-phase SOA precursors in a biogenic-rich environment.

This paper presents measurements of the single-particle composition of ice nuclei (IN) in downtown Toronto, Canada, made at 239 ± 1 K, 134 ± 2% relative humidity with respect to ice (RHi). IN were activated within the University of Toronto Continuous-Flow Diffusion Chamber (UT-CFDC), separated from background aerosol using a pumped counterflow virtual impactor (PCVI), and analyzed using a dual-polarity single-particle mass spectrometer (ATOFMS). To account for particles leaked by the PCVI, the ratio of particles observed at high RHi to low RHi was calculated. This ratio was greater than unity for EC (elemental carbon), BB (biomass burning) and dust particles, however only the increase in EC was statistically significant (1σ level) due to a low number of detected particles. The remaining particle categories were: metal-rich organic carbon (M/OC), potassium-rich OC (K/OC), OC potentially mixed with EC (OC/EC) and “other”, none of which were enhanced in number at high RHi. To complement the direct PCVI observations and enhance the number of spectra available, a second study was performed where particle composition and IN concentrations (CIN) were measured in parallel. IN concentrations were regressed against the same categories as above, and dust, BB and EC particles were identified as the best predictors of CIN. Consistency between these two methods provides increased confidence in their individual results and encourages additional study of these potential IN.

Aqueous-phase processing of glyoxal (GLY) and methylglyoxal (MG) produces highly oxygenated, less volatile organic acids that can contribute to SOA formation and aging. In this study, aerosol chemical ionization mass spectrometry (aerosol CIMS) is employed to monitor aqueous-phase photooxidation of GLY and MG. Using iodide (I(-)) as the reagent ion, aerosol CIMS can simultaneously detect important species involved in the reactions: organic acids, peroxides, and aldehydes, so that the reconstructed total organic carbon (TOC) concentrations from aerosol CIMS data agree well with offline TOC analysis. This study also reports the first direct detection of hydroxyhydroperoxide (HHP) formation from the reaction of H(2)O(2) with GLY or MG. The formation of HHPs is observed to be reversible and an estimate of their equilibrium constants is made to be between 40 and 200 M(-1). Results of this study suggest that HHPs can form additional formic acid and acetic acid via photooxidation and regenerate GLY or MG during photooxidation, compensating their loss. HHP formation needs to be further studied for inclusion in aqueous-phase chemical models given that it may affect the aqueous partitioning of carbonyls in the atmosphere.

Aqueous-phase chemistry of glyoxal may play an important role in the formation of highly oxidized secondary organic aerosol (SOA) in the atmosphere. In this work, we use a novel design of photochemical reactor that allows for simultaneous photo-oxidation and atomization of a bulk solution to study the aqueous-phase OH oxidation of glyoxal. By employing both online aerosol mass spectrometry (AMS) and offline ion chromatography (IC) measurements, glyoxal and some major products including formic acid, glyoxylic acid, and oxalic acid in the reacting solution were simultaneously quantified. This is the first attempt to use AMS in kinetics studies of this type. The results illustrate the formation of highly oxidized products that likely coexist with traditional SOA materials, thus, potentially improving model predictions of organic aerosol mass loading and degree of oxidation. Formic acid is the major volatile species identified, but the atmospheric relevance of its formation chemistry needs to be further investigated. While successfully quantifying low molecular weight organic oxygenates and tentatively identifying a reaction product formed directly from glyoxal and hydrogen peroxide, comparison of the results to the offline total organic carbon (TOC) analysis clearly shows that the AMS is not able to quantitatively monitor all dissolved organics in the bulk solution. This is likely due to their high volatility or low stability in the evaporated solution droplets. This experimental approach simulates atmospheric aqueous phase processing by conducting oxidation in the bulk phase, followed by evaporation of water and volatile organics to form SOA.

An aerosol time-of-flight mass spectrometer (ATOFMS) was deployed at a semi-rural site in Southern Ontario to characterize the size and chemical composition of individual particles. Particle-type-based receptor modelling of these data was used to investigate the determinants of aerosol chemical composition in this region. Individual particles were classified into particle-types and positive matrix factorization (PMF) was applied to their temporal trends to separate and cross-apportion particle-types to factors. The extent of chemical processing for each factor was assessed by evaluating the internal and external mixing state of the characteristic particle-types. The nine factors identified helped to elucidate the coupled interactions of these determinants. Nitrate-laden dust was found to be the dominant type of locally emitted particles measured by ATOFMS. Several factors associated with aerosol transported to the site from intermediate local-to-regional distances were identified: the Organic factor was associated with a combustion source to the north-west; the ECOC Day factor was characterized by nearby local-to-regional carbonaceous emissions transported from the south-west during the daytime; and the Fireworks factor consisted of pyrotechnic particles from the Detroit region following holiday fireworks displays. Regional aerosol from farther emissions sources were reflected through three factors: two biomass burning factors and a highly chemically processed long range transport factor. The biomass burning factors were separated by PMF due to differences in chemical processing which were caused in part by the passage of two thunderstorm gust fronts with different air mass histories. The remaining two factors, ECOC Night and Nitrate Background, represented the night-time partitioning of nitrate to pre-existing particles of different origins. The distinct meteorological conditions observed during this month-long study in the summer of 2007 provided a unique range of temporal variability, enabling the elucidation of the determinants of aerosol chemical composition, including source emissions, chemical processing, and transport, at the Canada-US border. This paper presents the first study to characterize the coupled influences of these determinants on temporal variability in aerosol chemical composition using single particle-type-based receptor modelling.

We report simultaneous measurements of volatile organic compound (VOC) mixing ratios including C6 to C8 aromatics, isoprene, monoterpenes, acetone and organic aerosol mass loadings at a rural location in southwestern Ontario, Canada by Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) and Aerosol Mass Spectrometry (AMS), respectively. During the three-week-long Border Air Quality and Meteorology Study in June–July 2007, air was sampled from a range of sources, including aged air from the polluted US Midwest, direct outflow from Detroit 50 km away, and clean air with higher biogenic input. After normalization to the diurnal profile of CO, a long-lived tracer, diurnal analyses show clear photochemical loss of reactive aromatics and production of oxygenated VOCs and secondary organic aerosol (SOA) during the daytime. Biogenic VOC mixing ratios increase during the daytime in accord with their light- and temperature-dependent sources. Long-lived species, such as hydrocarbon-like organic aerosol and benzene show little to no photochemical reactivity on this timescale. From the normalized diurnal profiles of VOCs, an estimate of OH concentrations during the daytime, measured O3 concentrations, and laboratory SOA yields, we calculate integrated local organic aerosol production amounts associated with each measured SOA precursor. Under the assumption that biogenic precursors are uniformly distributed across the southwestern Ontario location, we conclude that such precursors contribute significantly to the total amount of SOA formation, even during the period of Detroit outflow. The importance of aromatic precursors is more difficult to assess given that their sources are likely to be localized and thus of variable impact at the sampling location.

Regional-scale chemical transport model predictions of urban organic aerosol to date tend to be biased low relative to observations, a limitation with important implications for applying such models to human exposure health studies. We used a nested version of Environment Canada's AURAMS model (42- to- 15- to- 2.5-km nested grid spacing) to predict organic aerosol concentrations for a temporal and spatial domain corresponding to the Border Air Quality and Meteorology Study (BAQS-Met), an air-quality field study that took place in the southern Great Lakes region in the summer of 2007. The use of three different horizontal grid spacings allowed the influence of this parameter to be examined. A domain-wide average for the 2.5-km domain and a matching 15-km subdomain yielded very similar organic aerosol averages (4.8 vs. 4.3 μg m−3, respectively). On regional scales, secondary organic aerosol dominated the organic aerosol composition and was adequately resolved by the 15-km model simulation. However, the shape of the organic aerosol concentration histogram for the Windsor urban station improved for the 2.5-km simulation relative to those from the 42- and 15-km simulations. The model histograms for the Bear Creek and Harrow rural stations were also improved in the high concentration "tail" region. As well the highest-resolution model results captured the midday 4 July organic-aerosol plume at Bear Creek with very good temporal correlation. These results suggest that accurate simulation of urban and large industrial plumes in the Great Lakes region requires the use of a high-resolution model in order to represent urban primary organic aerosol emissions, urban VOC emissions, and the secondary organic aerosol production rates properly. The positive feedback between the secondary organic aerosol production rate and existing organic mass concentration is also represented more accurately with the highest-resolution model. Not being able to capture these finer-scale features may partly explain the consistent negative bias reported in the literature when urban-scale organic aerosol evaluations are made using coarser-scale chemical transport models.

As part of the BAQS-Met 2007 field campaign, Aerodyne time-of-flight aerosol mass spectrometers (ToF-AMS) were deployed at two sites in southwestern Ontario from 17 June to 11 July 2007. One instrument was located at Harrow, ON, a rural, agriculture-dominated area approximately 40 km southeast of the Detroit/Windsor/Windsor urban area and 5 km north of Lake Erie. The second instrument was located at Bear Creek, ON, a rural site approximately 70 km northeast of the Harrow site and 50 km east of Detroit/Windsor. Positive matrix factorization analysis of the combined organic mass spectral dataset yields factors related to secondary organic aerosol (SOA), direct emissions, and a factor tentatively attributed to the reactive uptake of isoprene and/or condensation of its early generation reaction products. This is the first application of PMF to simultaneous AMS measurements at different sites, an approach which allows for self-consistent, direct comparison of the datasets. Case studies are utilized to investigate processing of SOA from (1) fresh emissions from Detroit/Windsor and (2) regional aerosol during periods of inter-site flow. A strong correlation is observed between SOA/excess CO and photochemical age as represented by the NOx/NOy ratio for Detroit/Windsor outflow. Although this correlation is not evident for more aged air, measurements at the two sites during inter-site transport nevertheless show evidence of continued atmospheric processing by SOA production. However, the rate of SOA production decreases with airmass age from an initial value of ~10.1 μg m−3 ppmvCO−1 h−1 for the first ~10 h of plume processing to near-zero in an aged airmass (i.e. after several days). The initial SOA production rate is comparable to the observed rate in Mexico City over similar timescales.

The formation kinetics of gas-phase bromine (Br(2)) from interaction of gas-phase ozone (O(3)) with frozen and liquid solutions of NaCl (0.55 M) and NaBr (largely from 1.7 to 8.5 mM) have been studied from -40 to 0 °C in a coated-wall flow tube coupled to a chemical ionization mass spectrometer. The reactive uptake coefficient for O(3) is deduced from the product formation rate and then studied as a function of experimental conditions. In particular, for both the liquid and frozen solutions, we find that the uptake coefficient is inversely dependent on the gas-phase O(3) concentration in a manner that is quantitatively consistent with both surface- and bulk-phase kinetics. The reaction is fastest on acidic media (pH of the starting solution down to 2) but also proceeds at an appreciable rate on neutral substrates. Above 253 K, the uptake coefficient increases with increasing temperature on frozen solutions, consistent with an increasing brine content. The similarity of the absolute magnitude and form of the kinetics on the frozen and liquid substrates suggests that the reaction on the frozen solution is occurring with the associated brine, and not with the ice bulk or a quasi-liquid layer existing on the ice. The implications of these results to bromine activation in the tropospheric boundary layer are made.

The University of Toronto continuous flow diffusion chamber (UT-CFDC) was used to study heterogeneous ice nucleation at the International Workshop on Comparing Ice Nucleation Measuring Systems (ICIS 2007) which also represented the 4-th ice nucleation workshop, on 14–28 September 2007. One goal of the workshop was to inter-compare different ice nucleation measurement techniques using the same aerosol sample source and preparation method. The aerosol samples included four types of desert mineral dust, graphite soot particles, and live and dead bacterial cells (Snomax®). This paper focuses on the UT-CFDC results, with a comparison to techniques of established heritage including the Colorado State CFDC and the AIDA expansion chamber. Good agreement was found between the different instruments with a few specific differences, especially at low temperatures, perhaps due to the variation in how onset of ice formation is defined between the instruments and the different inherent residence times. It was found that when efficiency of ice formation is based on the lowest onset relative humidity, Snomax® particles were most efficient followed by the desert dusts and then soot. For all aerosols, deposition mode freezing was only observed for T

Ultrafine particle (UFP) number and size distributions were simultaneously measured at five urban and rural sites in Southern Ontario, Canada as part of the Border Air Quality and Meteorology Study (BAQS-Met 2007). Particle formation and growth events at these five sites were classified based on their strength and persistence as well as the variation in geometric mean diameter. Regional nucleation and growth events and local short-lived strong nucleation events were frequently observed at the near-border rural sites, upwind of industrial sources. Surprisingly, the particle number concentrations at one of these sites were higher than the concentrations at a downtown site in a major city, despite its high traffic density. Regional nucleation and growth events were favored at intense solar irradiance and less polluted cooler drier air. The most distinctive regional particle nucleation and growth event during the campaign was observed simultaneously at all five sites, which were up to 350 km apart. Although the ultrafine particle concentrations and size distributions generally were spatially heterogeneous across the region, a more uniform spatial distribution of UFP across the five areas was observed during this regional nucleation event. Thus, nucleation events can cover large regions, contributing to the burden of UFP in cities and potentially to the associated health impacts on urban populations. In addition, particle formation in southwestern Ontario appears to more often be related to anthropogenic gaseous emissions, although biogenic emissions may at times contribute. Local short-lived nucleation events at the near-border sites during this three-week campaign were associated with high SO2, which likely originated from US and Canadian industrial sources. These particle formation events may contribute to the production of cloud condensation nuclei, thus potentially influencing regional climate. Longer-term studies are needed to help resolve the relative contributions of anthropogenic and biogenic emissions to nucleation and growth in this region.

Submicron particles collected at Whistler, British Columbia, at 1020 m a.s.l. during May and June 2008 on Teflon filters were analyzed by Fourier transform infrared (FTIR) and X-ray fluorescence (XRF) techniques for organic functional groups (OFG) and elemental composition. Organic mass (OM) concentrations ranged from less than 0.5 to 3.1 μg m−3, with a project mean and standard deviation of 1.3±1.0 μg m−3 and 0.21±0.16 μg m−3 for OM and sulfate, respectively. On average, organic hydroxyl, alkane, and carboxylic acid groups represented 34%, 33%, and 23% of OM, respectively. Ketone, amine and organosulfate groups constituted 6%, 5%, and

Measurements of aerosol composition, volatile organic compounds, and CO are used to determine biogenic secondary organic aerosol (SOA) concentrations at a rural site 70 km north of Toronto. These biogenic SOA levels are many times higher than past observations and occur during a period of increasing temperatures and outflow from Northern Ontario and Quebec forests in early summer. A regional chemical transport model approximately predicts the event timing and accurately predicts the aerosol loading, identifying the precursors as monoterpene emissions from the coniferous forest. The agreement between the measured and modeled biogenic aerosol concentrations contrasts with model underpredictions for polluted regions. Correlations of the oxygenated organic aerosol mass with tracers such as CO support a secondary aerosol source and distinguish biogenic, pollution, and biomass burning periods during the field campaign. Using the Master Chemical Mechanism, it is shown that the levels of CO observed during the biogenic event are consistent with a photochemical source arising from monoterpene oxidation. The biogenic aerosol mass correlates with satellite measurements of regional aerosol optical depth, indicating that the event extends across the eastern Canadian forest. This regional event correlates with increased temperatures, indicating that temperature-dependent forest emissions can significantly affect climate through enhanced direct optical scattering and higher cloud condensation nuclei numbers.

Ambient particulate matter (PM) samples were collected on quartz filters at a rural site in central Ontario during an intensive study in 2007. The concentrations of organic carbon (OC), pyrolysis organic carbon (POC), and elemental carbon (EC) were determined by thermal analysis. The concentrations are compared to the organic aerosol mass concentration (OM) measured with an Aerodyne C-ToF Aerosol Mass Spectrometer (AMS) and to the particle absorption coefficient (basp) obtained from a Radiance Research Particle Soot Absorption Photometer (PSAP). The total organic mass to organic carbon ratios (OM/OC) and specific attenuation coefficients (SAC=basp/EC) are derived. Proportionality of the POC mass with the oxygen mass in the aerosols estimated from the AMS offers a potential means to estimate OM/OC from thermal measurements only. The mean SAC for the study is 3.8±0.3 m2 g−1. It is found that the SAC is independent of or decrease with increasing particle mass loading, depending on whether or not the data are separated between aerosols dominated by more recent anthropogenic input and aerosols dominated by longer residence time or biogenic components. There is no evidence to support an enhancement of light absorption by the condensation of secondary material to particles, suggesting that present model simulations built on such an assumption may overestimate atmospheric warming by BC.

During the winter component of the SPORT (Seasonal Particle Observations in the Region of Toronto) field campaign, particulate non-refractory chemical composition and concentration of selected volatile organic compounds (VOCs) were measured by an Aerodyne time-of-flight aerosol mass spectrometer (AMS) and a proton transfer reaction-mass spectrometer (PTR-MS), respectively. Sampling was performed in downtown Toronto ~15 m from a major road. The mass spectra from the AMS and PTR-MS were combined into a unified dataset, which was analysed using positive matrix factorization (PMF). The two instruments were given balanced weight in the PMF analysis by the application of a scaling factor to the uncertainties of each instrument. A residual based metric, Δesc, was used to evaluate the instrument relative weight within each solution. The PMF analysis yielded a 6-factor solution that included factors characteristic of regional transport, local traffic emissions, charbroiling and oxidative processing. The unified dataset provides information on emission sources (particle and VOC) and atmospheric processing that cannot be obtained from the datasets of the individual instruments: (1) apportionment of oxygenated VOCs to either direct emission sources or secondary reaction products; (2) improved correlation of oxygenated aerosol factors with photochemical age; and (3) increased detail regarding the composition of oxygenated organic aerosol factors. This analysis represents the first application of PMF to a unified AMS/PTR-MS dataset.

Growth rates of water droplets were measured with a static diffusion cloud condensation chamber in May–June 2007 at a rural field site in Southern Ontario, Canada, 70 km north of Toronto. The observations include periods when the winds were from the south and the site was impacted by anthropogenic air from the U.S. and Southern Ontario as well as during a 5-day period of northerly wind flow when the aerosol was dominated by biogenic sources. The growth of droplets on anthropogenic size-selected particles centred at 0.1 μm diameter and composed of approximately 40% organic and 60% ammonium sulphate (AS) by mass, was delayed by on the order of 1 s compared to a pure AS aerosol. Simulations of the growth rate on monodisperse particles indicate that a lowering of the water mass accommodation coefficient from αc=1 to an average of αc=0.04 is needed (assuming an insoluble organic with hygroscopicity parameter, κorg, of zero). Simulations of the initial growth rate on polydisperse anthropogenic particles agree best with observations for αc=0.07. In contrast, the growth rate of droplets on size-selected aerosol of biogenic character, consisting of >80% organic, was similar to that of pure AS. Simulations of the predominantly biogenic polydisperse aerosol show agreement between the observations and simulations when κorg=0.2 (with upper and lower limits of 0.5 and 0.07, respectively) and αc=1. Inhibition of water uptake by the anthropogenic organic applied to an adiabatic cloud parcel model in the form of a constant low αc increases the number of droplets in a cloud compared to pure AS. If the αc is assumed to increase with increasing liquid water on the droplets, then the number of droplets decreases which could diminish the indirect climate forcing effect. The slightly lower κorg in the biogenic case decreases the number of droplets in a cloud compared to pure AS.

The modification of cloud condensation nucleus (CCN) activity of saturated organic particles resulting from heterogeneous oxidation by OH radicals was studied. Submicron Bis-2-ethylhexyl sebacate (BES) and stearic acid particles were exposed to OH radicals in a reactor flow tube and CCN activity was monitored. The hygroscopicity parameter, κ, for monodisperse stearic acid and BES particles of 145–150 nm in size increased from

Water soluble inorganic particles components (Cl−, SO42−, NO3−, and NH4+) and concentrations of their associated precursor gases (HCl, SO2, HNO3, NH3) were semi-continuously measured using the Dionex Gas Particle Ion Chromatography (GPIC) system. Sampling was conducted adjacent to a high traffic street in downtown Toronto, Canada from June 2006 to March 2007. This study evaluated the precision and accuracy of field sampling measurements with the GPIC both relative to filter based measurements and other co-located semi-continuous instruments (R&P 8400N Nitrate Monitor, API Fluorescent SO2 Gas Analyzer, and Aerodyne C-ToF-AMS). High temporal resolution PM2.5 mass reconstruction is presented by combining GPIC measured inorganic species concentrations and Sunset Laboratory OCEC Analyzer determined organics concentrations. Field sampling results were also examined for seasonal and diurnal variations. HNO3 and particulate nitrate exhibited diurnal variation and strong partitioning to the gas phase was observed during the summer. Ammonia and particulate ammonium also demonstrated seasonal differences in their diurnal profiles. However, particulate sulphate and SO2 showed no diurnal variation regardless of season suggesting dominant transport from regional sources throughout the year.

Although heterogeneous reactions of polycyclic aromatic hydrocarbons (PAHs) with atmospheric oxidants may be important loss processes for PAHs, our understanding of their kinetics and products is incomplete. A product study of the reaction of two PAHs (i.e., anthracene and pyrene) and n-hexane soot with NO3 and N2O5 using a variety of analytical techniques (XPS, DRIFTS, GC–MS, optical absorption) was undertaken. The goal was to characterize the products of these heterogeneous nitration reactions to aid in reaction mechanism development. NitroPAHs were found to be the products of the nitration of anthracene and pyrene whereas evidence of both nitro and carbonyl functional groups were observed on the surface of n-hexane soot samples following exposure to a mixed flow of NO3 and N2O5. Absorption experiments indicate that the nitration of PAHs alter the optical properties of the particles to which they are adsorbed, giving rise to absorption intensity in the near UV and visible portions of the spectrum.