ALBERT

Beschreibung: Chemically resolved atmospheric aerosol data sets from the largest intercomparison of the Aerodyne aerosol chemical speciation monitors (ACSM) performed to date were collected at the French atmospheric supersite SIRTA. In total 13 quadrupole ACSMs (Q-ACSM) from the European ACTRIS ACSM network, one time-of-flight ACSM (ToF-ACSM), and one high-resolution ToF aerosol mass spectrometer (AMS) were operated in parallel for about three weeks in November and December 2013. Part 1 of this study reports on the accuracy and precision of the instruments for all the measured species. In this work we report on the intercomparison of organic components and the results from factor analysis source apportionment by positive matrix factorisation (PMF) utilising the multilinear engine 2 (ME-2). Except for the organic contribution of m/z 44 to the total organics (f44), which varied by factors between 0.6 and 1.3 compared to the mean, the peaks in the organic mass spectra were similar among instruments. The m/z 44 differences in the spectra resulted in a variable f44 in the source profiles extracted by ME-2, but had only a minor influence on the extracted mass contributions of the sources. The presented source apportionment yielded four factors for all 15 instruments: hydrocarbon-like organic aerosol (HOA), cooking-related organic aerosol (COA), biomass burning-related organic aerosol (BBOA) and secondary oxygenated organic aerosol (OOA). Individual application and optimisation of the ME-2 boundary conditions (profile constraints) are discussed together with the investigation of the influence of alternative anchors (reference profiles). A comparison of the ME-2 source apportionment output of all 15 instruments resulted in relative SD from the mean between 13.7 and 22.7% of the source's average mass contribution depending on the factors (HOA: 14.3 ± 2.2%, COA: 15.0 ± 3.4%, OOA: 41.5 ± 5.7%, BBOA: 29.3 ± 5.0%). Factors which tend to be subject to minor factor mixing (in this case COA) have higher relative uncertainties than factors which are recognised more readily like the OOA. Averaged over all factors and instruments the relative first SD from the mean of a source extracted with ME-2 was 17.2%.

Beschreibung: An Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during the Carbonaceous Aerosols and Radiative Effects Study (CARES) that took place in northern California in June 2010. We present results obtained at Cool (denoted as the T1 site of the project) in the foothills of the Sierra Nevada Mountains, where intense biogenic emissions are periodically mixed with urban outflow transported by daytime southwesterly winds from the Sacramento metropolitan area. During this study, the average mass loading of submicrometer particles (PM1) was 3.0 μg m−3, dominated by organics (80%) and sulfate (9.9%). The organic aerosol (OA) had a nominal formula of C1H1.38N0.004OM0.44, thus an average organic mass-to-carbon (OM/OC) ratio of 1.70. Two distinct oxygenated OA factors were identified via Positive matrix factorization (PMF) of the high-resolution mass spectra of organics. The more oxidized MO-OOA (O/C = 0.54) was interpreted as a surrogate for secondary OA (SOA) influenced by biogenic emissions whereas the less oxidized LO-OOA (O/C = 0.42) was found to represent SOA formed in photochemically processed urban emissions. LO-OOA correlated strongly with ozone and MO-OOA correlated well with two 1st generation isoprene oxidation products (methacrolein and methyl vinyl ketone), indicating that both SOAs were relatively fresh. A hydrocarbon like OA (HOA) factor was also identified, representing primary emissions mainly due to local traffic. On average, SOA (= MO-OOA + LO-OOA) accounted for 91% of the total OA mass and 72% of the PM1 mass observed at Cool. Twenty three periods of urban plumes from T0 (Sacramento) to T1 (Cool) were identified using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The average PM1 mass loading was considerably higher in urban plumes than in air masses dominated by biogenic SOA. The change in OA mass relative to CO (ΔOA/ΔCO) varied in the range of 5-196 μg m−3 ppm−1, reflecting large variability in SOA production. The highest ΔOA/ΔCO was reached when air masses were dominated by anthropogenic emissions in the presence of a high concentration of biogenic volatile organic compounds (BVOCs). This ratio, which was 97 μg m−3 ppm−1 on average, was much higher than when urban plumes arrived in a low BVOC environment (~36 μg m−3 ppm−1) or during other periods dominated by biogenic SOA (35 μg m−3 ppm−1). These results demonstrate that SOA formation is enhanced when anthropogenic emissions interact with biogenic precursors.

Beschreibung: During the Carbonaceous Aerosols and Radiative Effects Study (CARES), activation fraction of size-resolved aerosol particles and aerosol chemical composition were characterized at the T1 site (~60 km downwind of Sacramento, California) from 10 June to 28 June 2010. The hygroscopicity of cloud condensation nuclei (CCN)-active particles (κCCN) with diameter from 100 to 170 nm, derived from the size-resolved activated fraction, varied from 0.10 to 0.21, with an average of 0.15, which was substantially lower than that proposed for continental sites. The low κCCN value was due to the high organic volume fraction, averaged over 80% at the T1 site. The derived κCCN exhibited little diurnal variation, consistent with the relatively constant organic volume fraction observed. At any time, over 90% of the size-selected particles with diameter between 100 and 171 nm were CCN active, suggesting most particles within this size range were aged background particles. Due to the large organic volume fraction, organic hygroscopicity (κorg) strongly impacted particle hygroscopicity and therefore calculated CCN concentration. For the vast majority of the cases, an increase of κorg from 0.03 to 0.18, which are within the typical range, doubled the calculated CCN concentration. Organic hygroscopicity was derived from κCCN and aerosol chemical composition, and its variations with the fraction of total organic mass spectral signal at m / z 44 (f44) and O : C were compared to results from previous studies. Overall, the relationships between κorg and f44 are quite consistent for organic aerosol (OA) observed during field studies and those formed in a smog chamber. Compared to the relationship between κorg and f44, the relationship between κorg and O : C exhibits more significant differences among different studies, suggesting κorg may be better parameterized using f44. A least squares fit yielded κorg = 2.10(±0.07) × f44 − 0.11(±0.01) with a Pearson R2 value of 0.71. One possible explanation for the stronger correlation between κorg and f44 is that the m / z 44 signal (mostly contributed by the CO2+ ion) is more closely related to organic acids, which may dominate the overall κorg due to their relatively high water solubility and hygroscopicity.

Beschreibung: The CARES campaign was conducted during June, 2010 in the vicinity of Sacramento, California to study aerosol formation and aging in a region where anthropogenic and biogenic emissions regularly mix. Here, we describe measurements from an Aerodyne High Resolution Aerosol Mass Spectrometer (AMS), an Ionicon Proton Transfer Reaction Mass Spectrometer (PTR-MS), and trace gas detectors (CO, NO, NOx) deployed on the G-1 research aircraft to investigate ambient gas- and particle-phase chemical composition. AMS measurements showed that the particle phase is dominated by organic aerosol (OA) (85% on average) with smaller concentrations of sulfate (5%), nitrate (6%) and ammonium (3%) observed. PTR-MS data showed that isoprene dominated the biogenic volatile organic compound concentrations (BVOCs), with monoterpene concentrations generally below the detection limit. Using two different metrics, median OA concentrations and the slope of plots of OA vs. CO concentrations (i.e., ΔOA/ΔCO), we contrast organic aerosol evolution on flight days with different prevailing meteorological conditions to elucidate the role of anthropogenic and biogenic emissions on OA formation. Airmasses influenced predominantly by biogenic emissions had median OA concentrations of 2.2 μg m−3 and near zero ΔOA/ΔCO. Those influenced predominantly by anthropogenic emissions had median OA concentrations of 4.7 μg m−3 and ΔOA/ΔCO ratios of 35–44 μg m−3 ppmv. But, when biogenic and anthropogenic emissions mixed, OA levels were enhanced, with median OA concentrations of 11.4 μg m−3 and ΔOA/ΔCO ratios of 77–157 μg m−3 ppmv. Taken together, our observations show that production of OA was enhanced when anthropogenic emissions from Sacramento mixed with isoprene-rich air from the foothills. After considering several anthropogenic/biogenic interaction mechanisms, we conclude that NOx concentrations play a strong role in enhancing SOA formation from isoprene, though the chemical mechanism for the enhancement remains unclear. If these observations are found to be robust in other seasons and in areas outside of Sacramento, regional and global aerosol modules will need to incorporate more complex representations of NOx-dependent SOA mechanisms and yields into their algorithms. Ultimately, accurately predicting OA mass concentrations and their effect on radiation balance will require a mechanistically-based treatment of the interactions of biogenic and anthropogenic emissions.

Beschreibung: Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program's Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was routinely transported into the forested Sierra Nevada foothills area. Urban aerosols and trace gases experienced significant physical and chemical transformations as they mixed with the reactive biogenic hydrocarbons emitted from the forest. Two heavily-instrumented ground sites – one within the Sacramento urban area and another about 40 km to the northeast in the foothills area – were set up to characterize the evolution of meteorological variables, trace gases, aerosol precursors, aerosol size, composition, and climate-related properties in freshly polluted and "aged" urban air. On selected days, the DOE G-1 aircraft was deployed to make similar measurements upwind and across the evolving Sacramento plume in the morning and again in the afternoon. The NASA B-200 aircraft, carrying remote sensing instruments, was also deployed to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties within and around the plume. This overview provides: (a) the scientific background and motivation for the study, (b) the operational and logistical information pertinent to the execution of the study, (c) an overview of key observations and initial findings from the aircraft and ground-based sampling platforms, and (d) a roadmap of planned data analyses and focused modeling efforts that will facilitate the integration of new knowledge into improved representations of key aerosol processes and properties in climate models.

Beschreibung: The CARES campaign was conducted during June 2010 in the vicinity of Sacramento, California to study aerosol formation and aging in a region where anthropogenic and biogenic emissions regularly mix. Here, we describe measurements from an Aerodyne High Resolution Aerosol Mass Spectrometer (AMS), an Ionicon Proton Transfer Reaction Mass Spectrometer (PTR-MS), and trace gas detectors (CO, NO, NOx) deployed on the G-1 research aircraft to investigate ambient gas- and particle-phase chemical composition. AMS measurements showed that the particle phase is dominated by organic aerosol (OA) (85% on average) with smaller concentrations of sulfate (5%), nitrate (6%) and ammonium (3%) observed. PTR-MS data showed that isoprene dominated the biogenic volatile organic compound concentrations (BVOCs), with monoterpene concentrations generally below the detection limit. Using two different metrics, median OA concentrations and the slope of plots of OA vs. CO concentrations (i.e. ΔOA/ΔCO), we contrast organic aerosol evolution on flight days with different prevailing meteorological conditions to elucidate the role of anthropogenic and biogenic emissions on OA formation. Airmasses influenced predominantly by biogenic emissions had median OA concentrations of 2.2 μg m−3 and near zero ΔOA/ΔCO. Those influenced predominantly by anthropogenic emissions had median OA concentrations of 4.7 μg m−3 and ΔOA/ΔCO ratios of 35–44 μg m−3 ppmv−1. But, when biogenic and anthropogenic emissions mixed, OA levels were dramatically enhanced, with median OA concentrations of 11.4 μg m−3 and ΔOA/ΔCO ratios of 77–157 μg m−3 ppmv−1. Taken together, our observations show that production of OA was enhanced when anthropogenic emissions from Sacramento mixed with isoprene-rich air from the foothills. A strong, non-linear dependence of SOA yield from isoprene is the explanation for this enhancement most consistent with both the gas- and particle-phase data. If these observations are found to be robust in other seasons and in areas outside of Sacramento, regional and global aerosol modules will need to incorporate more complex representations of NOx-dependent SOA yields into their algorithms. Ultimately, accurately predicting OA mass concentrations and their effect on radiation balance will require a mechanistically-based treatment of the interactions of biogenic and anthropogenic emissions.

Beschreibung: Measurements of the effect of water uptake on particulate light extinction or scattering made at two locations during the 2010 CARES study around Sacramento, CA are reported. The observed influence of water uptake, characterized through the dimensionless optical hygroscopicity parameter γ, is compared with calculations constrained by observed particle size distributions and size-dependent particle composition. A closure assessment has been carried out that allowed for determination of the average hygroscopic growth factors (GF) at 85% relative humidity and the dimensionless hygroscopicity parameter κ for oxygenated organic aerosol (OA) and for supermicron particles, yielding κ = 0.1–0.15 and 0.9–1.0, respectively. The derived range of oxygenated OA κ values are in line with previous observations. The relatively large values for supermicron particles is consistent with substantial contributions of sea salt-containing particles in this size range. Analysis of time-dependent variations in the supermicron particle hygroscopicity suggest that atmospheric processing, specifically chloride displacement by nitrate and the accumulation of secondary organics on supermicron particles, can lead to substantial depression of the observed GF.

Beschreibung: During the Carbonaceous Aerosols and Radiative Effects Study (CARES), activation fraction of size-resolved aerosol particles and aerosol chemical composition were characterized at the T1 site (~60 km downwind of Sacramento, California) from 10 June to 28 June 2010. The hygroscopicity of CCN-active particles (κCCN) with diameter from 100 to 171 nm, derived from the size-resolved activated fraction, varied from 0.10 to 0.21, with an average of 0.15, which was substantially lower than that proposed for continental sites in earlier studies. The low κCCN value was due to the high organic volume fraction, averaged over 80% at the T1 site. The derived κCCN exhibited little diurnal variation, consistent with the relatively constant organic volume fraction observed. At any time, over 90% of the size selected particles with diameter between 100 and 171 nm were CCN active, suggesting most particles within this size range were aged background particles. Due to the large organic volume fraction, organic hygroscopicity (κorg) strongly impacted particle hygroscopicity and therefore calculated CCN concentration. For vast majority of the cases, an increase of κorg from 0.03 to 0.18, which are within the typical range, doubled the calculated CCN concentration. Organic hygroscopicity was derived from κCCN and aerosol chemical composition, and its variations with the fraction of total organic mass spectral signal at m/z 44 (f44) and O : C were compared to results from previous studies. Overall, the relationships between κorg and f44 are quite consistent for organic aerosol (OA) observed during field studies and those formed in smog chamber. Compared to the relationship between κorg and f44, the relationship between κorg and O : C exhibits more significant differences among different studies, suggesting κorg may be better parameterized using f44. A least squares fit yielded κorg = 2.04 (± 0.07) × f44 − 0.11 (± 0.01) with the Pearson R2 value of 0.71. One possible explanation for the stronger correlation between κorg and f44 is that the m/z 44 signal (mostly contributed by the CO2+ ion) is more closely related to organic acids, which may dominate the overall κorg due to their relatively high water solubility and hygroscopicity.