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We present indirect measurements of size-resolved ultrafine particle composition conducted during the Ocean-Atmosphere-Sea Ice-Snowpack (OASIS) Campaign in Utqiagvik, Alaska, during March 2009. This study focuses on measurements of size-resolved particle hygroscopicity and volatility measured over two periods of the campaign. During a period that represents background conditions in this location, particle hygroscopic growth factors (HGF) at 90% relative humidity ranged from 1.45 to 1.51, which combined with volatility measurements suggest a mixture of ∼30% ammoniated sulfates and ∼70% oxidized organics. Two separate regional ultrafine particle growth events were also observed during this campaign. Event 1 coincided with elevated levels of H2SO4 and solar radiation. These particles were highly hygroscopic (HGF = 2.1 for 35 nm particles), but were almost fully volatilized at 160 °C. The air masses associated with both events originated over the Arctic Ocean. Event 1 was influenced by the upper marine boundary layer (200–350 m AGL), while Event 2 spent more time closer to the surface (50–150 m AGL) and over open ocean leads, suggesting marine influence in growth processes. Event 2 particles were slightly less hygroscopic (HGF = 1.94 for 35 nm and 1.67 for 15 nm particles), and similarly volatile. We hypothesize that particles formed during both events contained 60–70% hygroscopic salts by volume, with the balance for Event 1 being sulfates and oxidized organics for Event 2. These observations suggest that primary sea spray may be an important initiator of ultrafine particle formation events in the Arctic late-winter, but a variety of processes may be responsible for condensational growth.

Sulfuric acid is a key contributor to new particle formation, though measurements of its gaseous concentrations are difficult to make. Several parameterizations to estimate sulfuric acid exist, all of which were constructed using measurements from the Northern Hemisphere. In this work, we report the first measurements of sulfuric acid from the Amazon basin. These measurements are consistent with concentrations measured in Hyytiälä, Finland, though, unlike Hyytiälä, there is no clear correlation of sulfuric acid with global radiation. There was a minimal difference in sulfuric acid observed between the wet and dry seasons in the Amazon basin. We also test the efficacy of existing proxies to estimate sulfuric acid in this region. Our results suggest that nighttime sulfuric acid production is due to both a stabilized Criegee intermediate pathway and oxidation of SO2 by OH, the latter of which is not currently accounted for in existing proxies. These results also illustrate the drawbacks of the common substitution of radiation for OH concentrations. None of the tested proxies effectively estimate sulfuric acid measurements at night. For estimates at all times of day, a recently published proxy based on data from the boreal forest should be used. If only daytime estimates are needed, several recent proxies that do not include the Criegee pathway are sufficient. More investigation of nighttime sulfuric acid production pathways is necessary to close the gap between measurements and estimates with existing proxies.

The Amazon Basin plays key role in atmospheric chemistry, biodiversity and climate change. In this study we applied nanoelectrospray (nanoESI) ultra-high-resolution mass spectrometry (UHRMS) for the analysis of the organic fraction of PM2.5 aerosol samples collected during dry and wet seasons at a site in central Amazonia receiving background air masses, biomass burning and urban pollution. Comprehensive mass spectral data evaluation methods (e.g. Kendrick mass defect, Van Krevelen diagrams, carbon oxidation state and aromaticity equivalent) were used to identify compound classes and mass distributions of the detected species. Nitrogen-and/or sulfur-containing organic species contributed up to 60% of the total identified number of formulae. A large number of molecular formulae in organic aerosol (OA) were attributed to later-generation nitrogen-and sulfur-containing oxidation products, suggesting that OA composition is affected by biomass burning and other, potentially anthropogenic, sources. Isoprene-derived organosulfate (IEPOX-OS) was found to be the most dominant ion in most of the analysed samples and strongly followed the concentration trends of the gas-phase anthropogenic tracers confirming its mixed anthropogenic-biogenic origin. The presence of oxidised aromatic and nitro-aromatic compounds in the samples suggested a strong influence from biomass burning especially during the dry period. Aerosol samples from the dry period and under enhanced biomass burning conditions contained a large number of molecules with high carbon oxidation state and an increased number of aromatic compounds compared to that from the wet period. The results of this work demonstrate that the studied site is influenced not only by biogenic emissions from the forest but also by biomass burning and potentially other anthropogenic emissions from the neighbouring urban environments.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16-36% of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100μgm-3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0±2.0 × 10-13cm3molec-1s-1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 1012molec cm-3s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59±0.33 in SE US and γOH = 0.68±0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

Each year, approximately half a million new cases of multidrug-resistant (MDR) tuberculosis (TB) challenge global health (1,2). MDR TB is caused by Mycobacterium tuberculosis complex (MTBC) strains, resistant to at [...]

Measurements of OH, H2SO4, and MSA at South Pole (SP) Antarctica were recorded as a part of the 2003 Antarctic Chemistry Investigation (ANTCI 2003). The time period 22 November, 2003-2 January, 2004 provided a unique opportunity to observe atmospheric chemistry at SP under both natural conditions as well as those uniquely defined by a solar eclipse event. Results under natural solar conditions generally confirmed those reported previously in the year 2000. In both years the major chemical driver leading to large scale fluctuations in OH was shifts in the concentration levels of NO. Like in 2000, however, the 2003 observational data were systematically lower than model predictions. This can be interpreted as indicating that the model mechanism is still missing a significant HOx sink reaction(s); or, alternatively, that the OH calibration source may have problems. Still a final possibility could involve the integrity of the OH sampling scheme which involved a fixed building site. As expected, during the peak in the solar eclipse both NO and OH showed large decreases in their respective concentrations. Interestingly, the observational OH profile could only be approximated by the model mechanism upon adding an additional HOx radical source in the form of snow emissions of CH2O and/or H2O2. This would lead one to think that either CH2O and/or H2O2 snow emissions represent a significant HOx radical source under summertime conditions at SP. Observations of H2SO4 and MSA revealed both species to be present at very low concentrations (e.g., 5 × 105 and 1 × 105 molec cm-3, respectively), but similar to those reported in 2000. The first measurements of SO2 at SP demonstrated a close coupling with the oxidation product H2SO4. The observed low concentrations of MSA appear to be counter to the most recent thinking by glacio-chemists who have suggested that the plateau's lower atmosphere should have elevated levels of MSA. We speculate here that the absence of MSA may reflect efficient atmospheric removal mechanisms for this species involving either dynamical and/or chemical processes. © 2009 Elsevier Ltd. All rights reserved.

Secondary organic aerosol (SOA) formation from ambient air was studied using an oxidation flow reactor (OFR) coupled to an aerosol mass spectrometer (AMS) during both the wet and dry seasons at the Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) field campaign. Measurements were made at two sites downwind of the city of Manaus, Brazil. Ambient air was oxidized in the OFR using variable concentrations of either OH or O3, over ranges from hours to days (O3) or weeks (OH) of equivalent atmospheric aging. The amount of SOA formed in the OFR ranged from 0 to as much as 10 µg m−3, depending on the amount of SOA precursor gases in ambient air. Typically, more SOA was formed during nighttime than daytime, and more from OH than from O3 oxidation. SOA yields of individual organic precursors under OFR conditions were measured by standard addition into ambient air and were confirmed to be consistent with published environmental chamber-derived SOA yields. Positive matrix factorization of organic aerosol (OA) after OH oxidation showed formation of typical oxidized OA factors and a loss of primary OA factors as OH aging increased. After OH oxidation in the OFR, the hygroscopicity of the OA increased with increasing elemental O : C up to O : C ∼ 1.0, and then decreased as O : C increased further. Possible reasons for this decrease are discussed. The measured SOA formation was compared to the amount predicted from the concentrations of measured ambient SOA precursors and their SOA yields. While measured ambient precursors were sufficient to explain the amount of SOA formed from O3, they could only explain 10–50 % of the SOA formed from OH. This is consistent with previous OFR studies, which showed that typically unmeasured semivolatile and intermediate volatility gases (that tend to lack C = C bonds) are present in ambient air and can explain such additional SOA formation. To investigate the sources of the unmeasured SOA-forming gases during this campaign, multilinear regression analysis was performed between measured SOA formation and the concentration of gas-phase tracers representing different precursor sources. The majority of SOA-forming gases present during both seasons were of biogenic origin. Urban sources also contributed substantially in both seasons, while biomass burning sources were more important during the dry season. This study enables a better understanding of SOA formation in environments with diverse emission sources.

Volatile organic compounds (VOCs) and carbonaceous aerosol were measured at a sub-urban site near Mexico City in March of 2006 during the MILAGRO study (Megacity Initiative: Local and Global Research Objectives). Diurnal variations of hydrocarbons, elemental carbon (EC) and hydrocarbon-like organic aerosol (HOA) were dominated by a high peak in the early morning when local emissions accumulated in a shallow boundary layer, and a minimum in the afternoon when the emissions were diluted in a significantly expanded boundary layer and, in case of the reactive gases, removed by OH. In comparison, diurnal variations of species with secondary sources such as the aldehydes, ketones, oxygenated organic aerosol (OOA) and watersoluble organic carbon (WSOC) stayed relatively high in the afternoon indicating strong photochemical formation. Emission ratios of many hydrocarbon species relative to CO were higher in Mexico City than in the U. S., but we found similar emission ratios for most oxygenated VOCs and organic aerosol. Secondary formation of acetone may be more efficient in Mexico City than in the U. S., due to higher emissions of alkane precursors from the use of liquefied petroleum gas. Secondary formation of organic aerosol was similar between Mexico City and the U. S. Combining the data for all measured gas and aerosol species, we describe the budget of total observed organic carbon (TOOC), and find that the enhancement ratio of TOOC relative to CO is conserved between the early morning and mid afternoon despite large compositional changes. Finally, the influence of biomass burning is investigated using the measurements of acetonitrile, which was found to correlate with levoglucosan in the particle phase. Diurnal variations of acetonitrile indicate a contribution from local burning sources. Scatter plots of acetonitrile versus CO suggest that the contribution of biomass burning to the enhancement of most gas and aerosol species was not dominant and perhaps not dissimilar from observations in the U.S.

Atmospheric hydroperoxides (ROOH) were measured at Summit, Greenland (72.97° N, 38.77° W) in summer 2003 (SUM03) and spring 2004 (SUM04) and South Pole in December 2003 (SP03). The two dominant hydroperoxides were H 2O2 and CH3OOH (from here on MHP) with average (±1) mixing ratios of 1448 (±688) pptv, 204 (±162) and 278 (±67) for H2O2 and 578 (±377) pptv, 139 (±101) pptv and 138 (±89) pptv for MHP, respectively. In early spring, MHP dominated the ROOH budget and showed night timemaxima and daytime minima, out of phase with the diurnal cycle of H2O2, suggesting that the organic peroxide is controlled by photochemistry, while H2O2 is largely influenced by temperature driven exchange between the atmosphere and snow. Highly constrained photochemical box model runs yielded median ratios between modeled and observed MHP of 52%, 148% and 3% for SUM03, SUM04 and SP03, respectively. At Summit firn air measurements and model calculations suggest a daytime sink of MHP in the upper snow pack, which decreases in strength through the spring season into the summer. Up to 50% of the estimated sink rates of 1-5×1011 moleculesm-3 s-1 equivalent to 24-96 pptv h-1 can be explained by photolysis and reaction with the OH radical in firn air and in the quasi-liquid layer on snow grains. Rapid processing of MHP in surface snow is expected to contribute significantly to a photochemical snow pack source of formaldehyde (CH2O). Conversely, summerlevels of MHP at South Pole are inconsistent with the prevailing high NO concentrations, and cannot be explained currently by known photochemical precursors or transport, thus suggesting a missing source. Simultaneous measurements of H 2O2, MHP and CH2O allow to constrain the NO background today and potentially also in the past using ice cores, although it seems less likely that MHP is preserved in firn and ice.

Experiments were performed at Summit, Greenland (72°34′ N, 38°29′ W) to investigate hydroxyl mixing ratios in the sunlit surface snowpack (or firn). We added a carefully selected mixture of hydrocarbon gases (with a wide range of hydroxyl reactivities) to a UV and visible light transparent flow chamber containing undisturbed natural firn. The relative decrease in mixing ratios of these gases allowed estimation of the lower limit mixing ratio of hydroxyl radicals in the near-surface firn pore spaces. Hydroxyl mixing ratios in the firn air followed a diurnal cycle in summer 2003 (10-12 July), with peak values of more than 3.2×106 molecules cm-3 between 13:00 and 16:00 local time. The minimum value estimated was 1.1×106 molecules cm-3 at 20:00 local time. Results during spring of 2004 showed lower, but rapidly increasing, peak hydroxyl mixing ratios of 1.1×106 molecules cm-3 in the early afternoon on 15 April and 1.5×106 molecules cm-3 on 1 May. Our firn hydroxyl estimates were similar to directly measured above-snow ambient levels during the spring field season, but were only about 30% of ambient levels during summer. © 2007 Elsevier Ltd. All rights reserved.

The first measurements of peroxy (HO2+RO2) and hydroxyl (OH) radicals above the arctic snowpack were collected during the summer 2003 campaign at Summit, Greenland. The median measured number densities for peroxy and hydroxyl radicals were 2.2×108 mol cm-3 and 6.4×106 mol cm-3, respectively. The observed peroxy radical values are in excellent agreement (R2 = 0.83, M / O = 1.06) with highly constrained model predictions. However, calculated hydroxyl number densities are consistently more than a factor of 2 lower than the observed values. These results indicate that our current understanding of radical sources and sinks is in accord with our observations in this environment but that there may be a mechanism that is perturbing the (HO2+RO2)/OH ratio. This observed ratio was also found to depend on meteorological conditions especially during periods of high winds accompanied by blowing snow. Backward transport model simulations indicate that these periods of high winds were characterized by rapid transport (1-2 days) of marine boundary layer air to Summit. These data suggest that the boundary layer photochemistry at Summit may be periodically impacted by halogens. © 2007.

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100 µg m−3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0 ± 2.0 × 10−13 cm3 molec−1 s−1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 1012 molec cm−3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59 ± 0.33 in SE US and γOH = 0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

Substantial biogenic secondary organic aerosol (BSOA) formation was investigated in a coniferous forest mountain region in Whistler, British Columbia. A largely biogenic aerosol growth episode was observed, providing a unique opportunity to investigate BSOA formation chemistry in a forested environment with limited influence from anthropogenic emissions. Positive matrix factorization of aerosol mass spectrometry (AMS) measurement identified two types of BSOA (BSOA-1 and BSOA-2), which were primarily generated by gas-phase oxidation of monoterpenes and perhaps sesquiterpenes. The temporal variations of BSOA-1 and BSOA-2 can be explained by gas–particle partitioning in response to ambient temperature and the relative importance of different oxidation mechanisms between day and night. While BSOA-1 arises from gas-phase ozonolysis and nitrate radical chemistry at night, BSOA-2 is likely less volatile than BSOA-1 and consists of products formed via gas-phase oxidation by OH radical and ozone during the day. Organic nitrates produced through nitrate radical chemistry can account for 22–33 % of BSOA-1 mass at night. The mass spectra of BSOA-1 and BSOA-2 have higher values of the mass fraction of m/z 91 (f91) compared to the background organic aerosol. Using f91 to evaluate BSOA formation pathways in this unpolluted, forested region, heterogeneous oxidation of BSOA-1 is a minor production pathway of BSOA-2.

Little is known about risk factors for violence among individuals with autism spectrum disorder (ASD). This study uses data from Swedish longitudinal registers for all 422 individuals hospitalized with autistic disorder or Asperger syndrome during 1988-2000 and compares those committing violent or sexual offenses with those who did not. Thirty-one individuals with ASD (7%) were convicted of violent nonsexual crimes and two of sexual offenses. Violent individuals with ASD are more often male and diagnosed with Asperger syndrome rather than autistic disorder. Furthermore, comorbid psychotic and substance use disorders are associated with violent offending. We conclude that violent offending in ASD is related to similar co-occurring psychopathology as previously found among violent individuals without ASD. Although this study does not answer whether ASDs are associated with increased risk of violent offending compared with the general population, careful risk assessment and management may be indicated for some individuals with Asperger syndrome. (Contains 2 tables.)

Submicron aerosol particles collected simultaneously at the mountain peak (2182 m a.s.l.) and at a forested mid-mountain site (1300 m a.s.l.) on Whistler Mountain, British Columbia, Canada, during June and July 2010 were analyzed by Fourier transform infrared (FTIR) spectroscopy for quantification of organic functional groups. Positive matrix factorization (PMF) was applied to the FTIR spectra. Three PMF factors associated with (1) combustion, (2) biogenics, and (3) vegetative detritus were identified at both sites. The biogenic factor was correlated with both temperature and several volatile organic compounds (VOCs). The combustion factor dominated the submicron particle mass during the beginning of the campaign, when the temperature was lower and advection was from the Vancouver area, but as the temperature started to rise in early July, the biogenic factor came to dominate as a result of increased emissions of biogenic VOCs, and thereby increased formation of secondary organic aerosol (SOA). On average, the biogenic factor represented 69% and 49% of the submicron organic particle mass at Whistler Peak and at the mid-mountain site, respectively. The lower fraction at the mid-mountain site was a result of more vegetative detritus there, and also higher influence from local combustion sources. The biogenic factor was strongly correlated (r~0.9) to number concentration of particles with diameter (Dp)> 100 nm, whereas the combustion factor was better correlated to number concentration of particles with Dpr~0.4). The number concentration of cloud condensation nuclei (CCN) was correlated (r~0.7) to the biogenic factor for supersaturations (S) of 0.2% or higher, which indicates that particle condensational growth from biogenic vapors was an important factor in controlling the CCN concentration for clouds where S≥0.2%. Both the number concentration of particles with Dp>100 nm and numbers of CCN for S≥0.2% were correlated to temperature. Considering the biogenic influence, these results indicate that temperature was a primary factor controlling these CCN concentrations at 0.2% supersaturation.

Tularemia is a zoonotic disease that causes geographically confined and seasonal outbreaks in many locations in the Northern Hemisphere (1-3). The highly infectious causative bacterial agent, Francisella tularensis, comprises 4 [...]

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.

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.

Formaldehyde measurements can provide useful information about photochemical activity in ambient air, given that HCHO is formed via numerous oxidation processes. Proton transfer reaction mass spectrometry (PTR-MS) is an online technique that allows measurement of VOCs at the sub-ppbv level with good time resolution. PTR-MS quantification of HCHO is hampered by the humidity dependence of the instrument sensitivity, with higher humidity leading to loss of PTR-MS signal. In this study we present an analytical, first principles approach to correct the PTR-MS HCHO signal according to the concentration of water vapor in sampled air. The results of the correction are validated by comparison of the PTR-MS results to those from a Hantzsch fluorescence monitor which does not have the same humidity dependence. Results are presented for an intercomparison made during a field campaign in rural Ontario at Environment Canada's Centre for Atmospheric Research Experiments.

Cloud condensation nuclei (CCN) concentrations were measured at Egbert, a rural site in Ontario, Canada during the spring of 2007. The CCN concentrations were compared to values predicted from the aerosol chemical composition and size distribution using κ-Köhler theory, with the specific goal of this work being to determine the hygroscopic parameter (κ) of the oxygenated organic component of the aerosol, assuming that oxygenation drives the hygroscopicity for the entire organic fraction of the aerosol. The hygroscopicity of the oxygenated fraction of the organic component, as determined by an Aerodyne aerosol mass spectrometer (AMS), was characterised by two methods. First, positive matrix factorization (PMF) was used to separate oxygenated and unoxygenated organic aerosol factors. By assuming that the unoxygenated factor is completely non-hygroscopic and by varying κ of the oxygenated factor so that the predicted and measured CCN concentrations are internally consistent and in good agreement, κ of the oxygenated organic factor was found to be 0.22±0.04 for the suite of measurements made during this five-week campaign. In a second, equivalent approach, we continue to assume that the unoxygenated component of the aerosol, with a mole ratio of atomic oxygen to atomic carbon (O/C) ≈ 0, is completely non-hygroscopic, and we postulate a simple linear relationship between κorg and O/C. Under these assumptions, the κ of the entire organic component for bulk aerosols measured by the AMS can be parameterised as κorg=(0.29±0.05)·(O/C), for the range of O/C observed in this study (0.3 to 0.6). These results are averaged over our five-week study at one location using only the AMS for composition analysis. Empirically, our measurements are consistent with κorg generally increasing with increasing particle oxygenation, but high uncertainties preclude us from testing this hypothesis. Lastly, we examine select periods of different aerosol composition, corresponding to different air mass histories, to determine the generality of the campaign-wide findings described above.

Atmospheric hydroperoxides (ROOH) were measured at Summit, Greenland (72.97° N, 38.77° W) in summer 2003 (SUM03) and spring 2004 (SUM04) and South Pole in December 2003 (SP03). The two dominant hydroperoxides were H2O2 and CH3OOH (from here on MHP) with average (±1σ) mixing ratios of 1448 (±688) pptv, 204 (±162) and 278 (±67) for H2O2 and 578 (±377) pptv, 139 (±101) pptv and 138 (±89) pptv for MHP, respectively. In early spring, MHP dominated the ROOH budget and showed night time maxima and daytime minima, out of phase with the diurnal cycle of H2O2, suggesting that the organic peroxide is controlled by photochemistry, while H2O2 is largely influenced by temperature driven exchange between the atmosphere and snow. Highly constrained photochemical box model runs yielded median ratios between modeled and observed MHP of 52%, 148% and 3% for SUM03, SUM04 and SP03, respectively. At Summit firn air measurements and model calculations suggest a daytime sink of MHP in the upper snow pack, which decreases in strength through the spring season into the summer. Up to 50% of the estimated sink rates of 1–5×1011 molecules m−3 s−1 equivalent to 24–96 pptv h−1 can be explained by photolysis and reaction with the OH radical in firn air and in the quasi-liquid layer on snow grains. Rapid processing of MHP in surface snow is expected to contribute significantly to a photochemical snow pack source of formaldehyde (CH2O). Conversely, summer levels of MHP at South Pole are inconsistent with the prevailing high NO concentrations, and cannot be explained currently by known photochemical precursors or transport, thus suggesting a missing source. Simultaneous measurements of H2O2, MHP and CH2O allow to constrain the NO background today and potentially also in the past using ice cores, although it seems less likely that MHP is preserved in firn and ice.

Investigates the influx of western-style eating disorders into India, Asia, and the southern Pacific region. Predicted Australian students would have more eating disorder symptoms, but instead, the Indian students showed more symptoms. Concludes substantial evidence of western-style eating disorders appear in the privileged socioeconomic class of the Indian populace. (CMK)