ALBERT

Description: A technique for compound specific analysis of stable carbon isotope ratios and concentration of ambient volatile organic compounds (VOC) is presented. It is based on selective VOC sampling onto adsorbent filled cartridges by passing large volumes of air (up to 80 L) through the cartridge. The hydrocarbons are recovered by thermal desorption followed by two step cryogenic trapping and then are separated by gas chromatography in the laboratory. Once separated, individual VOC are subjected to online oxidation in a combustion interface and isotope ratio analysis by isotope ratio mass spectrometry. The method allows measurements of stable carbon isotope ratios of ambient aromatic VOC present in low pptV to ppbV levels with an accuracy of typically better than 0.5‰. The precision of concentration measurements is better than 10%. Examples of measurements conducted as part of a joint Environment Canada-York University (EC-YU) measurement campaign at a semi-rural location demonstrate that the ability to make accurate measurements in air with low VOC mixing ratios is important to avoid bias from an over-representation of samples that are strongly impacted by recent emissions.

Description: Hydrogen peroxide (H2O2) and organic peroxides play important roles in the cycle of oxidants and the formation of secondary aerosols in the atmosphere. Recent field observations suggest that peroxyacetic acid (PAA, CH3C(O)OOH) is one of the most important organic peroxides in the atmosphere, whose budget is potentially related to the aerosols. Here we present the first laboratory measurements of the uptake coefficient of gaseous PAA and H2O2 onto the ambient fine particulate matter (PM2.5) as a function of relative humidity (RH) at 298 K. The results show that the PM2.5, which was collected in an urban area, can take up PAA and H2O2 at the uptake coefficient (γ) of 10−4, and both γPAA and γH2O2 increase with increasing RH. However, γPAA is more sensitive to the RH variation than is γH2O2, which indicates that the enhanced uptake of peroxide compounds on PM2.5 under humid conditions is dominated by chemical processes rather than dissolution. Considering that mineral dust is one of the main components of PM2.5, we also determined the uptake coefficients of gaseous PAA and H2O2 on authentic Asian Dust Storm (ADS) and Arizona Test Dust (ATD) particles. Compared to ambient PM2.5, ADS shows a similar γ value and RH dependence in its uptake coefficient for PAA and H2O2, while ATD gives a negative dependence on RH. The present study indicates that in addition to the mineral dust in PM2.5, other components (e.g., inorganic soluble salts) are also important to the uptake of peroxide compounds. When the heterogeneous reaction of PAA on PM2.5 is considered, its atmospheric lifetime is estimated to be 3.3 h on haze days and 7.6 h on non-haze days, values which agree well with the field observed result.

Description: Organic peroxides, important species in the atmosphere, will promote secondary organic aerosols (SOA) aging, affect HOx radicals cycling, and cause adverse health effects. However, the formation, gas-particle partitioning, and evolution of organic peroxides are extremely complicated and still unclear. In this study, we investigate in the laboratory the production and gas-particle partitioning of peroxides from the ozonolysis of α-pinene, which is one of the major biogenic volatile organic compounds in the atmosphere and is an important precursor for SOA at a global scale. We have determined the molar yields of hydrogen peroxide (H2O2), hydroxymethyl hydroperoxide (HMHP), peroxyformic acid (PFA), peroxyacetic acid (PAA) and total peroxides (TPO, including unknown peroxides) and the fraction of peroxides in SOA. Comparing the gas-phase and particle-phase peroxides, we find that gas-particle partitioning coefficients of PFA and PAA are 104 times higher than theoretical prediction, indicating that organic peroxides play a more important role in the SOA formation than expected previously. Here, we give the partitioning coefficients of TPO as (2–3) × 10-4 m3μg-1. Even so, more than 80 % of the peroxides formed in the reaction remain in the gas phase. Water does not affect the total amount of peroxides in either the gas or particle phase, but can change the distribution of gaseous peroxides. About 18 % gaseous peroxides undergo rapid heterogeneous decomposition on SOA particles in the presence of water vapor, resulting in the additional production of H2O2. This process can partially interpret the unexpected high H2O2 yield under wet conditions. Transformation of organic peroxides to H2O2 also saves OH in the atmosphere, helping to improve the understanding of OH cycling.

Description: We determine and interpret fine particulate matter (PM2.5) concentrations in East China for January to December 2013 at a horizontal resolution of 6 km from aerosol optical depth (AOD) retrieved from the Korean Geostationary Ocean Color Imager (GOCI) satellite instrument. We implement a set of filters to minimize cloud contamination in GOCI AOD. Evaluation of filtered GOCI AOD with AOD from the Aerosol Robotic Network (AERONET) indicates significant agreement with mean fractional bias (MFB) in Beijing of 6.7 % and northern Taiwan of −1.2 %. We use a global chemical transport model (GEOS-Chem) to relate the total column AOD to the near-surface PM2.5. The simulated PM2.5/AOD ratio exhibits high consistency with ground-based measurements (MFB = −0.52–8.0 %). We evaluate the satellite-derived PM2.5 vs. the ground-level PM2.5 in 2013 measured by the China Environmental Monitoring Center. Significant agreement is found between GOCI-derived PM2.5 and in-situ observations in both annual averages (r = 0.81, N = 494) and monthly averages (MFB = 13.1 %), indicating GOCI provides valuable data for air quality studies in Northeast Asia. The GEOS-Chem simulated chemical speciation of GOCI-derived PM2.5 reveals that secondary inorganics (SO42−, NO3−, NH4+) and organic matter are the most significant components. Biofuel emissions in northern China for heating are responsible for an increase in the concentration of organic matter in winter. The population-weighted GOCI-derived PM2.5 over East China for 2013 is 53.8 μg m−3, threatening the health and life expectancy of its 600 million residents.

Description: A method to quantify concentrations and stable carbon isotope ratios of secondary organic aerosols (SOA) has been applied to study atmospheric nitrophenols in Toronto, Canada. The sampling of five nitrophenols, all primarily formed from the photo-oxidation of aromatic volatile organic compounds (VOC), in the gas phase and particulate matter (PM) together and PM alone was conducted. Since all of the target compounds are secondary products, their concentrations in the atmosphere are in the low ng m−3 range and consequently a large volume of air (〉 1000 m3) is needed to analyze samples for stable carbon isotope ratios, resulting in sampling periods of typically 24 h. While this extended sampling period increases the representativeness of average values, it at the same time reduces possibilities to identify meteorological conditions or atmospheric pollution levels determining nitrophenol concentrations and isotope ratios. Average measured carbon isotope ratios of the different nitrophenols are between −34 and −33‰, which is well within the range predicted by mass balance calculations. However, the observed carbon isotope ratios cover a range of nearly 9‰, and approximately 20% of the isotope ratios of the products have isotope ratios lower than predicted from the kinetic isotope effect of the first step of the reaction mechanism and the isotope ratio of the precursor. This can be explained by isotope fractionation during reaction steps following the initial reaction of the precursor VOCs with the OH radical. Limited evidence for local production of nitrophenols is observed since sampling was done in the Toronto area, an urban centre with significant anthropogenic emission sources. Strong evidence for significant local formation of nitrophenols is only found for samples collected in summer. On average, the difference in carbon isotope ratios between nitrophenols in the particle phase and in the gas phase is insignificant, but for a limited number of observations in summer, a substantial difference is observed. This indicates that at high OH radical concentrations, photochemical formation or removal of nitrophenols can be faster than exchange between the two phases. The dependence between the concentrations and isotope ratios of the nitrophenols and meteorological conditions as well as pollution levels (NO2, O3, SO2 and CO) demonstrate that the influence of precursor concentrations on nitrophenol concentrations is far more important than the extent of photochemical processing.

Description: Atmospheric Brown Carbon (BrC) is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report a series of laboratory studies of photochemical processing of BrC in the aqueous phase, by direct photolysis and OH oxidation. Solutions of ammonium sulfate mixed with glyoxal (GLYAS) or methylglyoxal (MGAS) are used as surrogates for a class of secondary BrC mediated by imine intermediates. Three nitrophenol species, namely 4-nitrophenol, 5-nitroguaiacol and 4-nitrocatechol, were investigated as a class of water soluble BrC originating from biomass burning. Photochemical processing induced significant changes in the absorptive properties of BrC. The imine-mediated BrC solutions exhibited rapid photo-bleaching with both direct photolysis and OH oxidation, with atmospheric half-lives of minutes to a few hours. The nitrophenol species exhibited photo-enhancement in the visible range during direct photolysis and the onset of OH oxidation, but rapid photo-bleaching was induced by further OH exposure on an atmospheric timescale of an hour or less. To illustrate atmospheric relevance of this work, we also performed direct photolysis experiments on water soluble organic carbon extracted from biofuel combustion samples and observed rapid changes in optical properties of these samples as well. Overall, these experiments indicate that atmospheric models need to incorporate representations of atmospheric processing of BrC species to accurately model their radiative impacts.

Description: The existence and importance of peroxyformic acid (PFA) in the atmosphere has been under controversy. We present here, for the first time, the observation data for PFA from four field measurements carried out in China. These data provided powerful evidence that PFA can stay in the atmosphere, typically in dozens of pptv level. The relationship between PFA and other detected peroxides was examined. The results showed that PFA had a strong positive correlation with its homolog, peroxyacetic acid, due to their similar sources and sinks. Through an evaluation of PFA production and removal rates, we proposed that the reactions between peroxyformyl radical (HC(O)O2) and formaldehyde or the hydroperoxyl radical (HO2) were likely to be the major source and degradation into formic acid (FA) was likely to be the major sink for PFA. Based on a box model evaluation, we proposed that the HC(O)O2 and PFA chemistry was a major source for FA under low NOx conditions. Furthermore, it is found that the impact of the HC(O)O2 and PFA chemistry on radical cycling was dependent on the yield of HC(O)O2 radical from HC(O) + O2 reaction. When this yield exceeded 50%, the HC(O)O2 and PFA chemistry should not be neglected for calculating the radical budget. To make clear the exact importance of HC(O)O2 and PFA chemistry in the atmosphere, further kinetic, field and modeling studies are required.

Description: The concentrations of sulfate, black carbon (BC) and other aerosols in the Arctic are characterized by high values in late winter and spring (so-called Arctic Haze) and low values in summer. Models have long been struggling to capture this seasonality and especially the high concentrations associated with Arctic Haze. In this study, we evaluate sulfate and BC concentrations from eleven different models driven with the same emission inventory against a comprehensive pan-Arctic measurement data set over a time period of two years (2008–2009). The set of models consisted of one Lagrangian particle dispersion model, four chemistry-transport models (CTMs), one atmospheric chemistry-weather forecast model and five chemistry-climate models (CCMs), of which two were nudged to meteorological analyses and three were running freely. The measurement data set consisted of surface measurements of equivalent BC (eBC) from five stations (Alert, Barrow, Pallas, Tiksi and Zeppelin), elemental carbon (EC) from Station Nord and Alert and aircraft measurements of refractory BC (rBC) from six different campaigns. We find that the models generally captured the measured eBC/rBC and sulfate concentrations quite well, compared to past comparisons. However, the aerosol seasonality at the surface is still too weak in most models. Concentrations of eBC and sulfate averaged over three surface sites are underestimated in winter/spring in all but one model (model means for January-March underestimated by 59 and 37% for BC and sulfate, respectively), whereas concentrations in summer are overestimated in the model mean (by 88 and 44% for July–September), but with over- as well as underestimates present in individual models. The most pronounced eBC underestimates, not included in the above multi-site average, are found for the station Tiksi in Siberia where the measured annual mean eBC concentration is three times higher than the average annual mean for all other stations. This suggests an underestimate of BC sources in Russia in the emission inventory used. Based on the campaign data, biomass burning was identified as another cause of the modelling problems. For sulfate, very large differences were found in the model ensemble, with an apparent anti-correlation between modeled surface concentrations and total atmospheric columns. There is a strong correlation between observed sulfate and eBC concentrations with consistent sulfate/eBC slopes found for all Arctic stations, indicating that the sources contributing to sulfate and BC are similar throughout the Arctic and that the aerosols are internally mixed and undergo similar removal. However, only three models reproduced this finding, whereas sulfate and BC are weakly correlated in the other models. Overall, no class of models (e.g., CTMs, CCMs) performed better than the others and differences are independent of model resolution.

Description: To examine seasonal and size-dependent variations in the phytoplankton growth and microzooplankton grazing in oligotrophic tropical waters under the influence of seasonal reversing monsoon, dilution experiments were conducted during the summer 2009 (21 May to 9 June) and winter 2010 (9 to 18 November) in the southern South China Sea (SSCS). The results showed that environmental variables, phytoplankton biomass, phytoplankton growth rate (μ), microzooplankton grazing rate (m), and correlationship (coupling) between the μ and m, but the microzooplankton grazing impact on phytoplankton (m/μ) significantly varied between the two seasons. Higher relative preference index (RPI) for and m on the larger-sized (〉3 μm) phytoplankton than pico-phytoplankton (

Description: To examine seasonal and size-dependent variations in the phytoplankton growth and microzooplankton grazing in oligotrophic tropical waters under the influence of seasonal reversing monsoon, dilution experiments were conducted during the summer of 2009 (21 May to 9 June) and winter 2010 (9 to 18 November) in the southern South China Sea (SSCS). The results showed that environmental variables, phytoplankton biomass, phytoplankton growth rate (μ), microzooplankton grazing rate (m), and correlationship (coupling) between the μ and m, rather than the microzooplankton grazing impact on phytoplankton (m/μ) significantly varied between the two seasons. Higher relative preference index (RPI) for the larger-sized (〉 3 μm) phytoplankton than pico-phytoplankton (〈 3 μm), indicating significant size-selective grazing by microzooplankton on the larger-sized phytoplankton, were also observed. The μ and m were significantly correlated with seawater salinity and temperature, and phytoplankton biomass, which indicated that salient seasonal variations in the phytoplankton growth and microzooplankton grazing in the SSCS were closely related to the environmental variables under the influence of the East Asian monsoon. We propose that intermittent arrivals of the northeast winter monsoon could lead to the low μ and m, and the decoupling between the μ and m in the SSCS, through influencing nutrient supply to the surface water, and inducing surface seawater salinity decrease. The low m/μ (〈 50 % on average) indicates low remineralization of organic matter mediated by microzooplankton and mismatch between the μ and m, and thus probably accounts for part of the high vertical biogenic particle fluxes in the prevailing periods of the monsoons in the SSCS. The size-selective grazing suggests that microzooplankton grazing partially contributes to the pico-phytoplankton dominance in the oligotrophic tropical waters such as that of the SSCS.