Items

Advanced search

Effects of 20–100 nm particles on liquid clouds in the clean summertime Arctic

Observations addressing effects of aerosol particles on summertime Arctic clouds are limited. An airborne study, carried out during July 2014 from Resolute Bay, Nunavut, Canada, as part of the Canadian NETCARE project, provides a comprehensive in situ look into some effects of aerosol particles on liquid clouds in the clean environment of the Arctic summer. Median cloud droplet number concentrations (CDNC) from 62 cloud samples are 10 cm−3 for low-altitude cloud (clouds topped below 200 m) and 101 cm−3 for higher-altitude cloud (clouds based above 200 m). The lower activation size of aerosol particles is ≤  50 nm diameter in about 40 % of the cases. Particles as small as 20 nm activated in the higher-altitude clouds consistent with higher supersaturations (S) for those clouds inferred from comparison of the CDNC with cloud condensation nucleus (CCN) measurements. Over 60 % of the low-altitude cloud samples fall into the CCN-limited regime of Mauritsen et al. (2011), within which increases in CDNC may increase liquid water and warm the surface. These first observations of that CCN-limited regime indicate a positive association of the liquid water content (LWC) and CDNC, but no association of either the CDNC or LWC with aerosol variations. Above the Mauritsen limit, where aerosol indirect cooling may result, changes in particles with diameters from 20 to 100 nm exert a relatively strong influence on the CDNC. Within this exceedingly clean environment, as defined by low carbon monoxide and low concentrations of larger particles, the background CDNC are estimated to range between 16 and 160 cm−3, where higher values are due to activation of particles ≤  50 nm that likely derive from natural sources. These observations offer the first wide-ranging reference for the aerosol cloud albedo effect in the summertime Arctic.
Phase state of ambient aerosol linked with water uptake and chemical aging in the southeastern US

During the summer 2013 Southern Aerosol and Oxidant Study (SOAS) field campaign in a rural site in the southeastern United States, the effect of hygroscopicity and composition on the phase state of atmospheric aerosol particles dominated by the organic fraction was studied. The analysis is based on hygroscopicity measurements by a Hygroscopic Tandem Differential Mobility Analyzer (HTDMA), physical phase state investigations by an Aerosol Bounce Instrument (ABI) and composition measurements using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). To study the effect of atmospheric aging on these properties, an OH-radical oxidation flow reactor (OFR) was used to simulate longer atmospheric aging times of up to 3 weeks. Hygroscopicity and bounce behavior of the particles had a clear relationship showing higher bounce at elevated relative humidity (RH) values for less hygroscopic particles, which agrees well with earlier laboratory studies. Additional OH oxidation of the aerosol particles in the OFR increased the O : C and the hygroscopicity resulting in liquefying of the particles at lower RH values. At the highest OH exposures, the inorganic fraction starts to dominate the bounce process due to production of inorganics and concurrent loss of organics in the OFR. Our results indicate that at typical ambient RH and temperature, organic-dominated particles stay mostly liquid in the atmospheric conditions in the southeastern US, but they often turn semisolid when dried below ∼ 50 % RH in the sampling inlets. While the liquid phase state suggests solution behavior and equilibrium partitioning for the SOA particles in ambient air, the possible phase change in the drying process highlights the importance of thoroughly considered sampling techniques of SOA particles.
Ice nucleation efficiency of natural dust samples in the immersion mode

A total of 12 natural surface dust samples, which were surface-collected on four continents, most of them in dust source regions, were investigated with respect to their ice nucleation activity. Dust collection sites were distributed across Africa, South America, the Middle East, and Antarctica. Mineralogical composition has been determined by means of X-ray diffraction. All samples proved to be mixtures of minerals, with major contributions from quartz, calcite, clay minerals, K-feldspars, and (Na, Ca)-feldspars. Reference samples of these minerals were investigated with the same methods as the natural dust samples. Furthermore, Arizona test dust (ATD) was re-evaluated as a benchmark. Immersion freezing of emulsion and bulk samples was investigated by differential scanning calorimetry. For emulsion measurements, water droplets with a size distribution peaking at about 2 µm, containing different amounts of dust between 0.5 and 50 wt % were cooled until all droplets were frozen. These measurements characterize the average freezing behaviour of particles, as they are sensitive to the average active sites present in a dust sample. In addition, bulk measurements were conducted with one single 2 mg droplet consisting of a 5 wt % aqueous suspension of the dusts/minerals. These measurements allow the investigation of the best ice-nucleating particles/sites available in a dust sample. All natural dusts, except for the Antarctica and ATD samples, froze in a remarkably narrow temperature range with the heterogeneously frozen fraction reaching 10 % between 244 and 250 K, 25 % between 242 and 246 K, and 50 % between 239 and 244 K. Bulk freezing occurred between 255 and 265 K. In contrast to the natural dusts, the reference minerals revealed ice nucleation temperatures with 2–3 times larger scatter. Calcite, dolomite, dolostone, and muscovite can be considered ice nucleation inactive. For microcline samples, a 50 % heterogeneously frozen fraction occurred above 245 K for all tested suspension concentrations, and a microcline mineral showed bulk freezing temperatures even above 270 K. This makes microcline (KAlSi3O8) an exceptionally good ice-nucleating mineral, superior to all other analysed K-feldspars, (Na, Ca)-feldspars, and the clay minerals. In summary, the mineralogical composition can explain the observed freezing behaviour of 5 of the investigated 12 natural dust samples, and partly for 6 samples, leaving the freezing efficiency of only 1 sample not easily explained in terms of its mineral reference components. While this suggests that mineralogical composition is a major determinant of ice-nucleating ability, in practice, most natural samples consist of a mixture of minerals, and this mixture seems to lead to remarkably similar ice nucleation abilities, regardless of their exact composition, so that global models, in a first approximation, may represent mineral dust as a single species with respect to ice nucleation activity. However, more sophisticated representations of ice nucleation by mineral dusts should rely on the mineralogical composition based on a source scheme of dust emissions.
Synoptic perspectives on pollutant transport patterns observed by satellites over East Asia: Case studies with a conceptual model

We demonstrate that daily pollutant transport patterns in East Asia are visible from satellite images when inspected with corresponding synoptic weather analyses. Transport pathways of air pollutants in East Asia are investigated using satellite observations, surface weather charts, and chemical-transport model simulations. It is found that during cool season (fall to spring), pollutant transports in East Asia are largely determined by synoptic weather patterns associated with high pressure system over southern China, which is extended from the Siberia High, and low pressure system over Manchuria, which is initiated by Altai-Sayan cyclogenesis. Based on the relative location and strength of these weather systems, three types of synoptic weather patterns that may contribute to pollutants transport in East Asia, especially in China and Korea, are identified: i.e., (1) a strengthening of the Siberian High and its southeastward propagation; (2) a high-pressure system over southern China followed by a frontal passage associated with a northern low-pressure system; and (3) a stagnant high-pressure system over southern China. For all three patterns, the high-pressure system in southern China is essential for the development of regional air pollution, while frontal activities associated with low-pressure system provide a forcing mechanism to transport those pollutants eastward or southeastward. Observed and simulated surface PM distributions show good agreement in both aerosol optical depth and NO2 column density further implying that anthropogenic emissions also contribute to regional events of high surface PM concentrations. It is argued that the quasi-periodic migration of synoptic weather systems in East Asia works as an efficient pump of pollutants; i.e., regional air pollutions developed under high-pressure systems are transported downstream by low-pressure systems.
Impact of NOx and OH on secondary organic aerosol formation from β-pinene photooxidation

In this study, the NOx dependence of secondary organic aerosol (SOA) formation from photooxidation of the biogenic volatile organic compound (BVOC) β-pinene was comprehensively investigated in the Jülich Plant Atmosphere Chamber. Consistent with the results of previous NOx studies we found increases of SOA yields with increasing [NOx] at low-NOx conditions ([NOx]0  <  30 ppb, [BVOC]0 ∕ [NOx]0  >  10 ppbC ppb−1). Furthermore, increasing [NOx] at high-NOx conditions ([NOx]0  >  30 ppb, [BVOC]0 ∕ [NOx]0  ∼  10 to ∼  2.6 ppbC ppb−1) suppressed the SOA yield. The increase of SOA yield at low-NOx conditions was attributed to an increase of OH concentration, most probably by OH recycling in NO + HO2  →  NO2 + OH reaction. Separate measurements without NOx addition but with different OH primary production rates confirmed the OH dependence of SOA yields. After removing the effect of OH concentration on SOA mass growth by keeping the OH concentration constant, SOA yields only decreased with increasing [NOx]. Measuring the NOx dependence of SOA yields at lower [NO] ∕ [NO2] ratio showed less pronounced increase in both OH concentration and SOA yield. This result was consistent with our assumption of OH recycling by NO and to SOA yields being dependent on OH concentrations. Our results furthermore indicated that NOx dependencies vary for different NOx compositions. A substantial fraction of the NOx-induced decrease of SOA yields at high-NOx conditions was caused by NOx-induced suppression of new particle formation (NPF), which subsequently limits the particle surface where low volatiles condense. This was shown by probing the NOx dependence of SOA formation in the presence of seed particles. After eliminating the effect of NOx-induced suppression of NPF and NOx-induced changes of OH concentrations, the remaining effect of NOx on the SOA yield from β-pinene photooxidation was moderate. Compared to β-pinene, the SOA formation from α-pinene photooxidation was only suppressed by increasing NOx. However, basic mechanisms of the NOx impacts were the same as that of β-pinene.
Source apportionment of PM2.5 at a regional background site in North China using PMF linked with radiocarbon analysis: insight into the contribution of biomass burning

Source apportionment of fine particles (PM2.5) at a background site in North China in the winter of 2014 was done using statistical analysis, radiocarbon (14C) measurement and positive matrix factorization (PMF) modeling. Results showed that the concentration of PM2.5 was 77.6 ± 59.3 µg m−3, of which sulfate (SO42−) concentration was the highest, followed by nitrate (NO3−), organic carbon (OC), elemental carbon (EC) and ammonium (NH4+). As demonstrated by backward trajectory, more than half of the air masses during the sampling period were from the Beijing–Tianjin–Hebei (BTH) region, followed by Mongolia and the Shandong Peninsula. Cluster analysis of chemical species suggested an obvious signal of biomass burning in the PM2.5 from the Shandong Peninsula, while the PM2.5 from the BTH region showed a vehicle emission pattern. This finding was further confirmed by the 14C measurement of OC and EC in two merged samples. The 14C result indicated that biogenic and biomass burning emission contributed 59 ± 4 and 52 ± 2 % to OC and EC concentrations, respectively, when air masses originated from the Shandong Peninsula, while the contributions fell to 46 ± 4 and 38 ± 1 %, respectively, when the prevailing wind changed and came from the BTH region. The minimum deviation between source apportionment results from PMF and 14C measurement was adopted as the optimal choice of the model exercises. Here, two minor overestimates with the same range (3 %) implied that the PMF result provided a reasonable source apportionment of the regional PM2.5 in this study. Based on the PMF modeling, eight sources were identified; of these, coal combustion, biomass burning and vehicle emission were the main contributors of PM2.5, accounting for 29.6, 19.3 and 15.9 %, respectively. Compared with overall source apportionment, the contributions of vehicle emission, mineral dust, coal combustion and biomass burning increased when air masses came from the BTH region, Mongolia and the Shandong Peninsula, respectively. Since coal combustion and vehicle emission have been considered as the leading emission sources to be controlled for improving air quality, biomass burning was highlighted in the present study.
Long-term visibility variation in Athens (1931–2013): a proxy for local and regional atmospheric aerosol loads

This study explores the interdecadal variability and trends of surface horizontal visibility at the urban area of Athens from 1931 to 2013, using the historical archives of the National Observatory of Athens (NOA). A prominent deterioration of visibility in the city was detected, with the long-term linear trend amounting to −2.8 km decade−1 (p < 0.001), over the entire study period. This was not accompanied by any significant trend in relative humidity or precipitation over the same period. A slight recovery of visibility levels seems to be established in the recent decade (2004–2013). It was found that very good visibility (>  20 km) occurred at a frequency of 34 % before the 1950s, while this percentage drops to just 2 % during the decade 2004–2013. The rapid impairment of the visual air quality in Athens around the 1950s points to the increased levels of air pollution on a local and/or regional scale, related to high urbanization rates and/or increased anthropogenic emissions on a global scale at that period. Visibility was found to be negatively/positively correlated with relative humidity/wind speed, the correlation being statistically valid at certain periods. Wind regime and mainly wind direction and corresponding air mass origin were found to highly control visibility levels in Athens. The comparison of visibility variation in Athens and at a non-urban reference site on Crete island revealed similar negative trends over the common period of observations. This suggests that apart local sources, visibility in Athens is highly determined by aerosol load of regional origin. AVHRR and MODIS satellite-derived aerosol optical depth (AOD) retrievals over Athens and surface measurements of PM10 confirmed the relation of visibility to aerosol load.
Aerosol optical extinction during the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) 2014 summertime field campaign, Colorado, USA

Summertime aerosol optical extinction (βext) was measured in the Colorado Front Range and Denver metropolitan area as part of the Front Range Air Pollution and Photochemistry Éxperiment (FRAPPÉ) campaign during July–August 2014. An Aerodyne cavity attenuated phase shift particle light extinction monitor (CAPS-PMex) was deployed to measure βext (at average relative humidity of 20 ± 7 %) of submicron aerosols at λ = 632 nm at 1 Hz. Data from a suite of gas-phase instrumentation were used to interpret βext behavior in various categories of air masses and sources. Extinction enhancement ratios relative to CO (Δβext ∕ ΔCO) were higher in aged urban air masses compared to fresh air masses by ∼  50 %. The resulting increase in Δβext ∕ ΔCO for highly aged air masses was accompanied by formation of secondary organic aerosols (SOAs). In addition, the impacts of aerosol composition on βext in air masses under the influence of urban, natural oil and gas operations (O&G), and agriculture and livestock operations were evaluated. Estimated non-refractory mass extinction efficiency (MEE) values for different air mass types ranged from 1.51 to 2.27 m2 g−1, with the minimum and maximum values observed in urban and agriculture-influenced air masses, respectively. The mass distribution for organic, nitrate, and sulfate aerosols presented distinct profiles in different air mass types. During 11–12 August, regional influence of a biomass burning event was observed, increasing the background βext and estimated MEE values in the Front Range.
Surface–atmosphere exchange of ammonia over peatland using QCL-based eddy-covariance measurements and inferential modeling

Recent advances in laser spectrometry offer new opportunities to investigate ecosystem–atmosphere exchange of environmentally relevant trace gases. In this study, we demonstrate the applicability of a quantum cascade laser (QCL) absorption spectrometer to continuously measure ammonia concentrations at high time resolution and thus to quantify the net exchange between a seminatural peatland ecosystem and the atmosphere based on the eddy-covariance approach. Changing diurnal patterns of both ammonia concentration and fluxes were found during different periods of the campaign. We observed a clear tipping point in early spring with decreasing ammonia deposition velocities and increasingly bidirectional fluxes that occurred after the switch from dormant vegetation to CO2 uptake but was triggered by a significant weather change. While several biophysical parameters such as temperature, radiation, and surface wetness were identified to partially regulate ammonia exchange at the site, the seasonal concentration pattern was clearly dominated by agricultural practices in the surrounding area. Comparing the results of a compensation point model with our measurement-based flux estimates showed considerable differences in some periods of the campaign due to overestimation of non-stomatal resistances caused by low acid ratios. The total cumulative campaign exchange of ammonia after 9 weeks, however, differed only in a 6 % deviation with 911 and 857 g NH3-N ha−1 deposition being found by measurements and modeling, respectively. Extrapolating our findings to an entire year, ammonia deposition was lower than reported by Hurkuck et al. (2014) for the same site in previous years using denuder systems. This was likely due to a better representation of the emission component in the net signal of eddy-covariance fluxes as well as better adapted site-specific parameters in the model. Our study not only stresses the importance of high-quality measurements for studying and assessing land surface–atmosphere interactions but also demonstrates the potential of QCL spectrometers for continuous observation of reactive nitrogen species as important additional instruments within long-term monitoring research infrastructures such as ICOS or NEON at sites with strong nearby ammonia sources leading to relatively high mean background concentrations and fluxes.
A long-term study of aerosol–cloud interactions and their radiative effect at the Southern Great Plains using ground-based measurements

Empirical estimates of the microphysical response of cloud droplet size distribution to aerosol perturbations are commonly used to constrain aerosol–cloud interactions in climate models. Instead of empirical microphysical estimates, here macroscopic variables are analyzed to address the influence of aerosol particles and meteorological descriptors on instantaneous cloud albedo and the radiative effect of shallow liquid water clouds. Long-term ground-based measurements from the Atmospheric Radiation Measurement (ARM) program over the Southern Great Plains are used. A broad statistical analysis was performed on 14 years of coincident measurements of low clouds, aerosol, and meteorological properties. Two cases representing conflicting results regarding the relationship between the aerosol and the cloud radiative effect were selected and studied in greater detail. Microphysical estimates are shown to be very uncertain and to depend strongly on the methodology, retrieval technique and averaging scale. For this continental site, the results indicate that the influence of the aerosol on the shallow cloud radiative effect and albedo is weak and that macroscopic cloud properties and dynamics play a much larger role in determining the instantaneous cloud radiative effect compared to microphysical effects. On a daily basis, aerosol shows no correlation with cloud radiative properties (correlation = −0.01 ± 0.03), whereas the liquid water path shows a clear signal (correlation = 0.56 ± 0.02).