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Determining the spatial and seasonal variability in OM/OC ratios across the US using multiple regression

Data from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network are used to estimate organic mass to organic carbon (OM/OC) ratios across the United States by extending previously published multiple regression techniques. Our new methodology addresses common pitfalls of multiple regression including measurement uncertainty, colinearity of covariates, dataset selection, and model selection. As expected, summertime OM/OC ratios are larger than wintertime values across the US with all regional median OM/OC values tightly confined between 1.80 and 1.95. Further, we find that OM/OC ratios during the winter are distinctly larger in the eastern US than in the West (regional medians are 1.58, 1.64, and 1.85 in the great lakes, southeast, and northeast regions, versus 1.29 and 1.32 in the western and central states). We find less spatial variability in long-term averaged OM/OC ratios across the US (90% of our multiyear regressions estimate OM/OC ratios between 1.37 and 1.94) than previous studies (90% fell between 1.30 and 2.10). We attribute this difference largely to the inclusion of EC as a covariate in previous regression studies. Due to the colinearity of EC and OC, we find that up to one-quarter of the OM/OC estimates in a previous study are biased low. Assumptions about OC measurement artifacts add uncertainty to our estimates of OM/OC. In addition to estimating OM/OC ratios, our technique reveals trends that may be contrasted with conventional assumptions regarding nitrate, sulfate, and soil across the IMPROVE network. For example, our regressions show pronounced seasonal and spatial variability in both nitrate volatilization and sulfate neutralization and hydration.
The effect of H2SO4 – amine clustering on chemical ionization mass spectrometry (CIMS) measurements of gas-phase sulfuric acid

The state-of-the art method for measuring atmospheric gas-phase sulfuric acid is chemical ionization mass spectrometry (CIMS) based on nitrate reagent ions. We have assessed the possible effect of the sulfuric acid molecules clustering with base molecules on CIMS measurements using computational chemistry. From the computational data, three conclusions can be drawn. First, a significant fraction of the gas-phase sulfuric acid molecules are very likely clustered with amines if the amine concentration is around or above a few ppt. Second, some fraction of these acid-amine clusters may not be charged by the CIMS instrument, though the most reliable computational methods employed predict this fraction to be small; on the order of ten percent or less. Third, the amine molecules will evaporate practically immediately after charging, thus evading detection. These effects may need to be taken into account in the interpretation of atmospheric measurement data obtained using chemical ionization methods. The purpose of this study is not to criticize the CIMS method, but to help understand the implications of the measured results.
Photochemical processing of organic aerosol at nearby continental sites: contrast between urban plumes and regional aerosol

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.
SO2 and BrO observation in the plume of the Eyjafjallajökull volcano 2010: CARIBIC and GOME-2 retrievals

The ash cloud of the Eyjafjallajökull (also referred to as: Eyjafjalla (e.g. Schumann et al., 2011), Eyjafjöll or Eyjafjoll (e.g. Ansmann et al., 2010)) volcano on Iceland caused closure of large parts of European airspace in April and May 2010. For the validation and improvement of the European volcanic ash forecast models several research flights were performed. Also the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) flying laboratory, which routinely measures at cruise altitude (≈11 km) performed three dedicated measurements flights through sections of the ash plume. Although the focus of these flights was on the detection and quantification of the volcanic ash, we report here on sulphur dioxide (SO2) and bromine monoxide (BrO) measurements with the CARIBIC DOAS (Differential Optical Absorption Spectroscopy) instrument during the second of these special flights on 16 May 2010. As the BrO and the SO2 observations coincide, we assume the BrO to have been formed inside the volcanic plume. Average SO2 and BrO mixing ratios of ≈40 ppb and ≈5 ppt respectively are retrieved inside the plume. The BrO to SO2 ratio retrieved from the CARIBIC observation is ≈1.3×10−4. Both SO2 and BrO observations agree well with simultaneous satellite (GOME-2) observations. SO2 column densities retrieved from satellite observations are often used as an indicator for volcanic ash. As the CARIBIC O4 column densities changed rapidly during the plume observation, we conclude that the aerosol and the SO2 plume are collocated. For SO2 some additional information on the local distribution can be derived from a comparison of forward and back scan GOME-2 data. More details on the local plume size and position are retrieved by combining CARIBIC and GOME-2 data.
On the potential contribution of open lead particle emissions to the central Arctic aerosol concentration

We present direct eddy covariance measurements of aerosol number fluxes, dominated by sub-50 nm particles, at the edge of an ice floe drifting in the central Arctic Ocean. The measurements were made during the ice-breaker borne ASCOS (Arctic Summer Cloud Ocean Study) expedition in August 2008 between 2°–10° W longitude and 87°–87.5° N latitude. The median aerosol transfer velocities over different surface types (open water leads, ice ridges, snow and ice surfaces) ranged from 0.27 to 0.68 mm s−1 during deposition-dominated episodes. Emission periods were observed more frequently over the open lead, while the snow behaved primarily as a deposition surface. Directly measured aerosol fluxes were compared with particle deposition parameterizations in order to estimate the emission flux from the observed net aerosol flux. Finally, the contribution of the open lead particle source to atmospheric variations in particle number concentration was evaluated and compared with the observed temporal evolution of particle number. The direct emission of aerosol particles from the open lead can explain only 5–10% of the observed particle number variation in the mixing layer close to the surface.
Latitudinal distributions of organic nitrogen and organic carbon in marine aerosols over the western North Pacific

Marine aerosol samples were collected over the western North Pacific along the latitudinal transect from 44° N to 10° N in late summer 2008 for measurements of organic nitrogen (ON) and organic carbon (OC) as well as isotopic ratios of total nitrogen (TN) and total carbon (TC). Increased concentrations of methanesulfonic acid (MSA) and diethylammonium (DEA+) at 40–44° N and subtropical regions (10–20° N) together with averaged satellite chlorophyll-a data and 5-day back trajectories suggest a significant influence of marine biological activities on aerosols in these regions. ON exhibited increased concentrations up to 260 ngN m−3 in these marine biologically influenced aerosols. Water-insoluble organic nitrogen (WION) was found to be the most abundant nitrogen in the aerosols, accounting for 55 ± 16% of total aerosol nitrogen. In particular, the average WION/ON ratio was as high as 0.93 ± 0.07 at 40–44° N. These results suggest that marine biological sources significantly contributed to ON, a majority of which is composed of water-insoluble fractions in the study region. Analysis of the stable carbon isotopic ratios (δ13C) indicated that, on average, marine-derived carbon accounted for ~88 ± 12% of total carbon in the aerosols. In addition, the δ13C showed higher values (from −22 to −20&permil;) when ON/OC ratios increased from 0.15 to 0.35 in marine biologically influenced aerosols. These results clearly show that organic nitrogen is enriched in organic aerosols originated from an oceanic region with high biological productivity, indicating a preferential transfer of nitrogen-containing organic compounds from the sea surface to the marine atmosphere. Both WION concentrations and WION/water-insoluble organic carbon (WIOC) ratios tended to increase with increasing local wind speeds, indicating that sea-to-air emissions of ON via sea spray contribute significantly to the marine organic aerosols over the study region.
Evaluation of the accuracy of analysis tools for atmospheric new particle formation

Several mathematical tools have been developed in recent years to analyze new particle formation rates and to estimate nucleation rates and mechanisms at sub-3 nm sizes from atmospheric aerosol data. Here we evaluate these analysis tools using 1239 numerical nucleation events for which the nucleation mechanism and formation rates were known exactly. The accuracy of the estimates of particle formation rate at 3 nm (J3) showed significant sensitivity to the details of the analysis, i.e. form of equations used and assumptions made about the initial size of nucleating clusters, with the fraction of events within a factor-of-two accuracy ranging from 43–97%. In general, the estimates of the actual nucleation rate at 1.5 nm (J1.5) were less accurate, and even the most accurate analysis set-up estimated only 59% of the events within a factor of two of the simulated mean nucleation rate. The J1.5 estimates were deteriorated mainly by the size dependence of the cluster growth rate below 3 nm, which the analysis tools do not take into account, but also by possible erroneous assumptions about the initial cluster size. The poor estimates of J1.5 can lead to large uncertainties in the nucleation prefactors (i.e. constant P in nucleation equation J1.5 = P × [H2SO4]k). Large uncertainties were found also in the procedures that are used to determine the nucleation mechanism. When applied to individual events, the analysis tools clearly overestimated the number of H2SO4 molecules in a critical cluster for most events, and thus associated them with a wrong nucleation mechanism. However, in some conditions the number of H2SO4 molecules in a critical cluster was underestimated. This indicates that analysis of field data that implies a maximum of 2 H2SO4 molecules in a cluster does not automatically rule out a higher number of molecules in the actual nucleating cluster. Our analysis also suggests that combining data from several new particle formation events to scatter plots of H2SO4 vs formation rates (J1.5 or J3) and determining the slope of the regression line may not give reliable information about the nucleation mechanism. Overall, while the analysis tools for new particle formation are useful for getting order-of-magnitude estimates of parameters related to atmospheric nucleation, one should be very cautious in interpreting the results. It is, for example, possible that the tools may have misdirected our theoretical understanding of the nucleation mechanism.
Microphysical and radiative effects of aerosols on warm clouds during the Amazon biomass burning season as observed by MODIS: impacts of water vapor and land cover

Aerosol, cloud, water vapor, and temperature profile data from the Moderate Resolution Imaging Spectroradiometer (MODIS) are utilized to examine the impact of aerosols on clouds during the Amazonian biomass burning season in Rondônia, Brazil. It is found that increasing background column water vapor (CWV) throughout this transition season between the Amazon dry and wet seasons likely exerts a strong effect on cloud properties. As a result, proper analysis of aerosol-cloud relationships requires that data be stratified by CWV to account better for the influence of background meteorological variation. Many previous studies of aerosol-cloud interactions over Amazonia have ignored the systematic changes to meteorological factors during the transition season, leading to possible misinterpretation of their results. Cloud fraction (CF) is shown to increase or remain constant with aerosol optical depth (AOD), depending on the value of CWV, whereas the relationship between cloud optical depth (COD) and AOD is quite different. COD increases with AOD until AOD ~ 0.3, which is assumed to be due to the first indirect (microphysical) effect. At higher values of AOD, COD is found to decrease with increasing AOD, which may be due to: (1) the inhibition of cloud development by absorbing aerosols (radiative effect/semi-direct effect) and/or (2) a possible retrieval artifact in which the measured reflectance in the visible is less than expected from a cloud top either from the darkening of clouds through the addition of carbonaceous biomass burning aerosols within or above clouds or subpixel dark surface contamination in the measured cloud reflectance. If (1) is a contributing mechanism, as we suspect, then an empirically-derived increasing function between cloud drop number and aerosol concentration, assumed in a majority of global climate models, is inaccurate since these models do not include treatment of aerosol absorption in and around clouds. The relationship between aerosols and both CWV and clouds over varying land surface types is also analyzed. The study finds that the difference in CWV between forested and deforested land is not correlated with aerosol loading, supporting the assumption that temporal variation of CWV is primarily a function of the larger-scale meteorology. However, a difference in the response of CF to increasing AOD is observed between forested and deforested land. This suggests that dissimilarities between other meteorological factors, such as atmospheric stability, may have an impact on aerosol-cloud correlations between different land cover types.
Synergetic monitoring of Saharan dust plumes and potential impact on surface: a case study of dust transport from Canary Islands to Iberian Peninsula

The synergetic use of meteorological information, remote sensing both ground-based active (lidar) and passive (sun-photometry) techniques together with backtrajectory analysis and in-situ measurements is devoted to the characterization of dust intrusions. A case study of air masses advected from the Saharan region to the Canary Islands and the Iberian Peninsula, located relatively close and far away from the dust sources, respectively, was considered for this purpose. The observations were performed over three Spanish geographically strategic stations within the dust-influenced area along a common dust plume pathway monitored from 11 to 19 of March 2008. A 4-day long dust event (13–16 March) over the Santa Cruz de Tenerife Observatory (SCO), and a linked short 1-day dust episode (14 March) in the Southern Iberian Peninsula over the Atmospheric Sounding Station "El Arenosillo" (ARN) and the Granada station (GRA) were detected. Meteorological conditions favoured the dust plume transport over the area under study. Backtrajectory analysis clearly revealed the Saharan region as the source of the dust intrusion. Under the Saharan air masses influence, AERONET Aerosol Optical Depth at 500 nm (AOD500) ranged from 0.3 to 0.6 and Ångström Exponent at 440/675 nm wavelength pair (AE440/675) was lower than 0.5, indicating a high loading and predominance of coarse particles during those dusty events. Lidar observations characterized their vertical layering structure, identifying different aerosol contributions depending on altitude. In particular, the 3-km height dust layer transported from the Saharan region and observed over SCO site was later on detected at ARN and GRA stations. No significant differences were found in the lidar (extinction-to-backscatter) ratio (LR) estimation for that dust plume over all stations when a suitable aerosol scenario for lidar data retrieval is selected. Lidar-retrieved LR values of 60–70 sr were obtained during the main dust episodes. These similar LR values found in all the stations suggest that dust properties were kept nearly unchanged in the course of its medium-range transport. In addition, the potential impact on surface of that Saharan dust intrusion over the Iberian Peninsula was evaluated by means of ground-level in-situ measurements for particle deposition assessment together with backtrajectory analysis. However, no connection between those dust plumes and the particle sedimentation registered at ground level is found. Differences on particle deposition processes observed in both Southern Iberian Peninsula sites are due to the particular dust transport pattern occurred over each station. Discrepancies between columnar-integrated and ground-level in-situ measurements show a clear dependence on height of the dust particle size distribution. Then, further vertical size-resolved observations are needed for evaluation of the impact on surface of the Saharan dust arrival to the Iberian Peninsula.
Study on long-term aerosol distribution over the land of East China using MODIS data

East China is among the fastest developing and most populous area in Asia, where atmospheric aerosol loading is high due to heavy urban and industrial emission. These aerosols may have significant impact on regional climate and environment. In this report, MODIS level 2 aerosol products (2000–2007) were used to study aerosol spatial and temporal distributions, as well as their variations with local meteorological conditions over East China. By combining Aerosol Optical Depth (AOD) and aerosol Fine Mode Fraction (FMF), we found that the urban/industrial aerosol and dust are two dominant species over northern part, whereas continental, marine and mixed aerosols dominate the southern part of East China, except for Poyang Lake Plain. Both annual mean AOD and area with high AOD increased from 2000 to 2007, with the largest increase seen in Yangtze River Delta region (YRD). In summer, AOD in East China reached the maximum of about 0.8 in YRD, dominated by fine mode particles. The minimum AOD occurred in winter with mostly coarse mode particles. The higher AOD in spring is attributed to coarse particles. Local aerosol properties were analyzed in three typical zones: the northern dry zone (I), the central urban/industrial zone (II) and the southern natural background zone (III). Monthly mean AODs in zone I and II were above 0.5 throughout the entire year, with the maximum AOD in June. High FMFs in this period indicated heavy urban and industrial pollutions. Monthly mean AODs and FMFs in zone III reached maximum of 0.51 in April and September (up to 90.7%) respectively. High AOD in spring in zone III appears mostly due to the long-range dust transport from the North. In fact, dust particles contributed 50–80% to aerosol loading in zone I and II, but only 20% in zone III. The effect of meteorological conditions such as temperature, relative humidity (RH) and wind on aerosol loadings over East China were also investigated.