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Effect of atmospheric aging on volatility and reactive oxygen species of biodiesel exhaust nano-particles

In the prospect of limited energy resources and climate change, effects of alternative biofuels on primary emissions are being extensively studied. Our two recent studies have shown that biodiesel fuel composition has a significant impact on primary particulate matter emissions. It was also shown that particulate matter caused by biodiesels was substantially different from the emissions due to petroleum diesel. Emissions appeared to have higher oxidative potential with the increase in oxygen content and decrease of carbon chain length and unsaturation levels of fuel molecules. Overall, both studies concluded that chemical composition of biodiesel is more important than its physical properties in controlling exhaust particle emissions. This suggests that the atmospheric aging processes, including secondary organic aerosol formation, of emissions from different fuels will be different as well. In this study, measurements were conducted on a modern common-rail diesel engine. To get more information on realistic properties of tested biodiesel particulate matter once they are released into the atmosphere, particulate matter was exposed to atmospheric oxidants, ozone and ultra-violet light; and the change in their properties was monitored for different biodiesel blends. Upon the exposure to oxidative agents, the chemical composition of the exhaust changes. It triggers the cascade of photochemical reactions resulting in the partitioning of semi-volatile compounds between the gas and particulate phase. In most of the cases, aging lead to the increase in volatility and oxidative potential, and the increment of change was mainly dependent on the chemical composition of fuels as the leading cause for the amount and the type of semi-volatile compounds present in the exhaust.
Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

Laboratory experiments of efficient oligomerization from methyl vinyl ketone (MVK) in the bulk aqueous phase were simulated in a box model. Kinetic data are applied (if known) or fitted to the observed MVK decay and oligomer mass increase. Upon model sensitivity studies, in which unconstrained rate constants were varied over several orders of magnitude, a set of reaction parameters was found that could reproduce laboratory data over a wide range of experimental conditions. This mechanism is the first that comprehensively describes such radical-initiated oligomer formation. This mechanism was implemented into a multiphase box model that simulates secondary organic aerosol (SOA) formation from isoprene, as a precursor of MVK and methacrolein (MACR) in the aqueous and gas phases. While in laboratory experiments oxygen limitation might occur and lead to accelerated oligomer formation, such conditions are likely not met in the atmosphere. The comparison of predicted oligomer formation shows that MVK and MACR likely do negligibly contribute to total SOA as their solubilities are low and even reduced in aerosol water due to ionic strength effects (Setchenov coefficients). Significant contribution by oligomers to total SOA might only occur if a substantial fraction of particulate carbon acts as oligomer precursors and/or if oxygen solubility in aerosol water is strongly reduced due to salting-out effects.
What is the limit of climate engineering by stratospheric injection of SO2?

The injection of sulfur dioxide (SO2) into the stratosphere to form an artificial stratospheric aerosol layer is discussed as an option for solar radiation management. The related reduction of radiative forcing depends upon the injected amount of sulfur dioxide, but aerosol model studies indicate a decrease in forcing efficiency with increasing injection rate. None of these studies, however, consider injection rates greater than 20 Tg(S) yr−1. But this would be necessary to counteract the strong anthropogenic forcing expected if "business as usual" emission conditions continue throughout this century. To understand the effects of the injection of larger amounts of SO2, we have calculated the effects of SO2 injections up to 100 Tg(S) yr−1. We estimate the reliability of our results through consideration of various injection strategies and from comparison with results obtained from other models. Our calculations show that the efficiency of such a geoengineering method, expressed as the ratio between sulfate aerosol forcing and injection rate, decays exponentially. This result implies that the sulfate solar radiation management strategy required to keep temperatures constant at that anticipated for 2020, while maintaining business as usual conditions, would require atmospheric injections of approximately 45 Tg(S) yr−1 (±15 % or 7 Tg(S) yr−1) at a height corresponding to 60 hPa. This emission is equivalent to 5 to 7 times the Mt. Pinatubo eruption each year.
Transport of Antarctic stratospheric strongly dehydrated air into the troposphere observed during the HALO-ESMVal campaign 2012

Dehydration in the Antarctic winter stratosphere is a well-known phenomenon that is annually observed by satellites and occasionally observed by balloon-borne measurements. However, in situ measurements of dehydrated air masses in the Antarctic vortex are very rare. Here, we present detailed observations with the in situ and GLORIA remote sensing instrument payload aboard the German aircraft HALO. Strongly dehydrated air masses down to 1.6 ppmv of water vapor were observed as far north as 47° S in an altitude between 12 and 13 km in the lowermost stratosphere. The dehydration can be traced back to individual ice formation events above the Antarctic Peninsula and Plateau, where ice crystals sedimented out and water vapor was irreversibly removed. Within these dehydrated stratospheric air masses, filaments of moister air reaching down to the tropopause are detected with the high-resolution limb sounder, GLORIA. Furthermore, dehydrated air masses are observed with GLORIA in the Antarctic lowermost stratosphere down to 7 km. With the help of a backward trajectory analysis, a midlatitude origin of the moist filaments in the vortex can be identified, while the dry air masses down to 7 km have stratospheric origins. Antarctic stratosphere–troposphere exchange (STE) and transport of dehydrated air masses into the troposphere are investigated. Further, it is shown that the exchange process can be attributed to several successive Rossby wave events in combination with an isentropic exchange of air masses across the thermal tropopause. The transport into the troposphere is caused by air masses that are detached from the potential vorticity (PV) structure by Rossby wave breaking events and subsequently transported diabatically across the dynamical tropopause. Once transported to the troposphere, air masses with stratospheric origin can reach near-surface levels within several days.
A better understanding of hydroxyl radical photochemical sources in cloud waters collected at the puy de Dôme station – experimental versus modelled formation rates

The oxidative capacity of the cloud aqueous phase is investigated during three field campaigns from 2013 to 2014 at the top of the puy de Dôme station (PUY) in France. A total of 41 cloud samples are collected and the corresponding air masses are classified as highly marine, marine and continental. Hydroxyl radical (HO•) formation rates (RHO•f) are determined using a photochemical setup (xenon lamp that can reproduce the solar spectrum) and a chemical probe coupled with spectroscopic analysis that can trap all of the generated radicals for each sample. Using this method, the obtained values correspond to the total formation of HO• without its chemical sinks. These formation rates are correlated with the concentrations of the naturally occurring sources of HO•, including hydrogen peroxide, nitrite, nitrate and iron. The total hydroxyl radical formation rates are measured as ranging from approximately 2 × 10−11 to 4 × 10−10 M s−1, and the hydroxyl radical quantum yield formation (ΦHO•) is estimated between 10−4 and 10−2. Experimental values are compared with modelled formation rates calculated by the model of multiphase cloud chemistry (M2C2), considering only the chemical sources of the hydroxyl radicals. The comparison between the experimental and the modelled results suggests that the photoreactivity of the iron species as a source of HO• is overestimated by the model, and H2O2 photolysis represents the most important source of this radical (between 70 and 99 %) for the cloud water sampled at the PUY station (primarily marine and continental).
Dust–air pollution dynamics over the eastern Mediterranean

Interactions of desert dust and air pollution over the eastern Mediterranean (EM) have been studied, focusing on two distinct dust transport events on 22 and 28 September 2011. The atmospheric chemistry–climate model EMAC has been used at about 50 km grid spacing, applying an online dust emission scheme and calcium as a proxy for dust reactivity. EMAC includes a detailed tropospheric chemistry mechanism, aerosol microphysics and thermodynamics schemes to describe dust "aging". The model is evaluated using ground-based observations for aerosol concentrations and aerosol optical depth (AOD) as well as satellite observations. Simulation results and back trajectory analysis show that the development of synoptic disturbances over the EM can enhance dust transport from the Sahara and Arabian deserts in frontal systems that also carry air pollution to the EM. The frontal systems are associated with precipitation that controls the dust removal. Our results show the importance of chemical aging of dust, which increases particle size, dust deposition and scavenging efficiency during transport, overall reducing the lifetime relative to non-aged dust particles. The relatively long travel periods of Saharan dust result in more sustained aging compared to Arabian dust. Sensitivity simulations indicate 3 times more dust deposition of aged relative to pristine dust, which significantly decreases the dust lifetime and loading.
Laboratory studies of collection efficiency of sub-micrometer aerosol particles by cloud droplets on a single-droplet basis

An experimental setup has been constructed to measure the collection efficiency (CE) of sub-micrometer aerosol particles by cloud droplets. Droplets of a dilute aqueous ammonium sulfate solution with an average radius of 21.6 μm fall freely into a chamber and collide with sub-micrometer polystyrene latex (PSL) sphere particles of known sizes and concentrations. Two relative humidity (RH) conditions, 15 ± 3 % and 88 ± 3 %, hereafter termed "low" and "high", respectively, were varied with different particles sizes and concentrations. After passing through the chamber, the droplets and aerosol particles were sent to the Particle Analysis by Laser Mass Spectrometry (PALMS) instrument to determine chemical compositions on a single-droplet basis. "Coagulated droplets" (droplets that collected aerosols) had mass spectra that contained signatures from both an aerosol particle and a droplet residual. CE values range from 2.0 × 10−1 to 1.6 for the low-RH case and from 1.5 × 10−2 to 9.0 × 10−2 for the high-RH case. CE values were, within experimental uncertainty, independent of the aerosol concentrations. CE values in this study were found to be in agreement with previous experimental and theoretical studies. To our knowledge, this is the first collection experiment performed on a single-droplet basis with atmospherically relevant conditions such as droplet sizes, droplet charges and flow.
Organic photolysis reactions in tropospheric aerosols: effect on secondary organic aerosol formation and lifetime

This study presents the first modeling estimates of the potential effect of gas- and particle-phase organic photolysis reactions on the formation and lifetime of secondary organic aerosols (SOAs). Typically only photolysis of smaller organic molecules (e.g., formaldehyde) for which explicit data exist is included in chemistry–climate models. Here, we specifically examine the photolysis of larger molecules that actively partition between the gas and particle phases. The chemical mechanism generator GECKO-A is used to explicitly model SOA formation from α-pinene, toluene, and C12 and C16 n-alkane reactions with OH at low and high NOx. Simulations are conducted for typical mid-latitude conditions and a solar zenith angle of 45° (permanent daylight). The results show that after 4 days of chemical aging under those conditions (equivalent to 8 days in the summer mid-latitudes), gas-phase photolysis leads to a moderate decrease in SOA yields, i.e., ~15 % (low NOx) to ~45 % (high NOx) for α-pinene, ~15 % for toluene, ~25 % for C12 n-alkane, and ~10 % for C16 n-alkane. The small effect of gas-phase photolysis on low-volatility n-alkanes such as C16 n-alkane is due to the rapid partitioning of early-generation products to the particle phase, where they are protected from gas-phase photolysis. Minor changes are found in the volatility distribution of organic products and in oxygen to carbon ratios. The decrease in SOA mass is increasingly more important after a day of chemical processing, suggesting that most laboratory experiments are likely too short to quantify the effect of gas-phase photolysis on SOA yields. Our results also suggest that many molecules containing chromophores are preferentially partitioned into the particle phase before they can be photolyzed in the gas phase. Given the growing experimental evidence that these molecules can undergo in-particle photolysis, we performed sensitivity simulations using an empirically estimated SOA photolysis rate of JSOA = 4 × 10−4 JNO2. Modeling results indicate that this photolytic loss rate would decrease SOA mass by 40–60 % for most species after 10 days of equivalent atmospheric aging at mid-latitudes in the summer. It should be noted that in our simulations we do not consider in-particle or aqueous-phase reactions which could modify the chemical composition of the particle and thus the quantity of photolabile species. The atmospheric implications of our results are significant for both the SOA global distribution and lifetime. GEOS-Chem global model results suggest that particle-phase photolytic reactions could be an important loss process for SOA in the atmosphere, removing aerosols from the troposphere on timescales of less than 7 days that are comparable to wet deposition.
A method for merging nadir-sounding climate records, with an application to the global-mean stratospheric temperature data sets from SSU and AMSU

A method is proposed for merging different nadir-sounding climate data records using measurements from high-resolution limb sounders to provide a transfer function between the different nadir measurements. The two nadir-sounding records need not be overlapping so long as the limb-sounding record bridges between them. The method is applied to global-mean stratospheric temperatures from the NOAA Climate Data Records based on the Stratospheric Sounding Unit (SSU) and the Advanced Microwave Sounding Unit-A (AMSU), extending the SSU record forward in time to yield a continuous data set from 1979 to present, and providing a simple framework for extending the SSU record into the future using AMSU. SSU and AMSU are bridged using temperature measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), which is of high enough vertical resolution to accurately represent the weighting functions of both SSU and AMSU. For this application, a purely statistical approach is not viable since the different nadir channels are not sufficiently linearly independent, statistically speaking. The near-global-mean linear temperature trends for extended SSU for 1980–2012 are −0.63 ± 0.13, −0.71 ± 0.15 and −0.80 ± 0.17 K decade−1 (95 % confidence) for channels 1, 2 and 3, respectively. The extended SSU temperature changes are in good agreement with those from the Microwave Limb Sounder (MLS) on the Aura satellite, with both exhibiting a cooling trend of ~ 0.6 ± 0.3 K decade−1 in the upper stratosphere from 2004 to 2012. The extended SSU record is found to be in agreement with high-top coupled atmosphere–ocean models over the 1980–2012 period, including the continued cooling over the first decade of the 21st century.
Atmospheric new particle formation as a source of CCN in the eastern Mediterranean marine boundary layer

While cloud condensation nuclei (CCN) production associated with atmospheric new particle formation (NPF) is thought to be frequent throughout the continental boundary layers, few studies on this phenomenon in marine air exist. Here, based on simultaneous measurement of particle number size distributions, CCN properties and aerosol chemical composition, we present the first direct evidence on CCN production resulting from NPF in the eastern Mediterranean atmosphere. We show that condensation of both gaseous sulfuric acid and organic compounds from multiple sources leads to the rapid growth of nucleated particles to CCN sizes in this environment during the summertime. Sub-100 nm particles were found to be substantially less hygroscopic than larger particles during the period with active NPF and growth (the value of κ was lower by 0.2–0.4 for 60 nm particles compared with 120 nm particles), probably due to enrichment of organic material in the sub-100 nm size range. The aerosol hygroscopicity tended to be at minimum just before the noon and at maximum in the afternoon, which was very likely due to the higher sulfate-to-organic ratios and higher degree of oxidation of the organic material during the afternoon. Simultaneous with the formation of new particles during daytime, particles formed during the previous day or even earlier were growing into the size range relevant to cloud droplet activation, and the particles formed in the atmosphere were possibly mixed with long-range-transported particles.