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The terrestrial biosphere is an important source of natural aerosol. Natural aerosol sources alter climate, but are also strongly controlled by climate, leading to the potential for natural aerosol–climate feedbacks. Here we use a global aerosol model to make an assessment of terrestrial natural aerosol–climate feedbacks, constrained by observations of aerosol number. We find that warmer-than-average temperatures are associated with higher-than-average number concentrations of large (>100 nm diameter) particles, particularly during the summer. This relationship is well reproduced by the model and is driven by both meteorological variability and variability in natural aerosol from biogenic and landscape fire sources. We find that the calculated extratropical annual mean aerosol radiative effect (both direct and indirect) is negatively related to the observed global temperature anomaly, and is driven by a positive relationship between temperature and the emission of natural aerosol. The extratropical aerosol–climate feedback is estimated to be −0.14 W m−2 K−1 for landscape fire aerosol, greater than the −0.03 W m−2 K−1 estimated for biogenic secondary organic aerosol. These feedbacks are comparable in magnitude to other biogeochemical feedbacks, highlighting the need for natural aerosol feedbacks to be included in climate simulations.

The Atmospheric Cluster Dynamics Code (ACDC) is presented and explored. This program was created to study the first steps of atmospheric new particle formation by examining the formation of molecular clusters from atmospherically relevant molecules. The program models the cluster kinetics by explicit solution of the birth–death equations, using an efficient computer script for their generation and the MATLAB ode15s routine for their solution. Through the use of evaporation rate coefficients derived from formation free energies calculated by quantum chemical methods for clusters containing dimethylamine or ammonia and sulphuric acid, we have explored the effect of changing various parameters at atmospherically relevant monomer concentrations. We have included in our model clusters with 0–4 base molecules and 0–4 sulfuric acid molecules for which we have commensurable quantum chemical data. The tests demonstrate that large effects can be seen for even small changes in different parameters, due to the non-linearity of the system. In particular, changing the temperature had a significant impact on the steady-state concentrations of all clusters, while the boundary effects (allowing clusters to grow to sizes beyond the largest cluster that the code keeps track of, or forbidding such processes), coagulation sink terms, non-monomer collisions, sticking probabilities and monomer concentrations did not show as large effects under the conditions studied. Removal of coagulation sink terms prevented the system from reaching the steady state when all the initial cluster concentrations were set to the default value of 1 m−3, which is probably an effect caused by studying only relatively small cluster sizes.

Atmospheric observations from a boreal forest region, laboratory experiments and theoretical considerations are combined, and another compound is identified that has a significant capacity to oxidize sulphur dioxide and potentially other trace gases. Unknown 'extra' atmospheric oxidizing agent Ozone, the hydroxyl radical and nitrate are thought to be the main agents that act to remove trace gases, including pollutants, from the atmosphere. In this paper, the authors combine atmospheric observations from a forested region of Finland, laboratory experiments and theoretical considerations to identify another, previously unknown compound with significant capacity to oxidize sulphur dioxide and perhaps other trace gases. The compound seems to be a stabilized Criegee intermediate — a carbonyl oxide with two free-radical sites — or its derivative and could potentially enhance the reactivity of the atmosphere, contributing to the production of sulphuric acid and, consequently, atmospheric-aerosol formation. The chemistry investigated here is tightly connected with the presence of biogenic volatile organic compounds, and thereby with forest emissions. Atmospheric oxidation is a key phenomenon that connects atmospheric chemistry with globally challenging environmental issues, such as climate change 1 , stratospheric ozone loss 2 , acidification of soils and water 3 , and health effects of air quality 4 . Ozone, the hydroxyl radical and the nitrate radical are generally considered to be the dominant oxidants that initiate the removal of trace gases, including pollutants, from the atmosphere. Here we present atmospheric observations from a boreal forest region in Finland, supported by laboratory experiments and theoretical considerations, that allow us to identify another compound, probably a stabilized Criegee intermediate (a carbonyl oxide with two free-radical sites) or its derivative, which has a significant capacity to oxidize sulphur dioxide and potentially other trace gases. This compound probably enhances the reactivity of the atmosphere, particularly with regard to the production of sulphuric acid, and consequently atmospheric aerosol formation. Our findings suggest that this new atmospherically relevant oxidation route is important relative to oxidation by the hydroxyl radical, at least at moderate concentrations of that radical. We also find that the oxidation chemistry of this compound seems to be tightly linked to the presence of alkenes of biogenic origin.

Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of the reaction of stabilized Criegee intermediates (sCIs) with SO2, atmospheric oxidation processes were thought to be dominated by a few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes ( alpha -pinene and limonene), and subsequent reactions of the resulting sCIs with SO2 producing sulfuric acid (H2SO4). The measured total sCI yields were (0.15 plus or minus 0.07), (0.27 plus or minus 0.12) and (0.58 plus or minus 0.26) for alpha -pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO2, k(loss) /k(sCI + SO2), was determined at relative humidities of 10 and 50%. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene-derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO2) were in the range (2.0-2.4) 1012 molecules cm-3 and nearly independent of the relative humidity. This fact points to a minor importance of the sCI + H2O reaction in the case of the sCI arising from alpha -pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO2) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO2; k(sCI + acid) / k(sCI + SO2) = (2.8 plus or minus 0.3) for formic acid, and k(sCI + acid) / k(sCI + SO2) = (3.4 plus or minus 0.2) for acetic acid. This finding indicates that sCIs can play a role in the formation and loss of other atmospheric constituents besides SO2.

Sulphuric acid and organic vapours have been identified as the key components in the ubiquitous secondary new particle formation in the atmosphere. In order to assess their relative contribution and spatial variability, we analysed altogether 36 new particle formation events observed at four European measurement sites during EUCAARI campaigns in 2007-2009. We tested models of several different nucleation mechanisms coupling the formation rate of neutral particles (J) with the concentration of sulphuric acid ([H2 SO4 ]) or low-volatility organic vapours ([org]) condensing on sub-4 nm particles, or with a combination of both concentrations. Furthermore, we determined the related nucleation coefficients connecting the neutral nucleation rate J with the vapour concentrations in each mechanism. The main goal of the study was to identify the mechanism of new particle formation and subsequent growth that minimizes the difference between the modelled and measured nucleation rates. At three out of four measurement sites - Hyytiälä (Finland), Melpitz (Germany) and San Pietro Capofiume (Italy) - the nucleation rate was closely connected to squared sulphuric acid concentration, whereas in Hohenpeissenberg (Germany) the low-volatility organic vapours were observed to be dominant. However, the nucleation rate at the sulphuric acid dominant sites could not be described with sulphuric acid concentration and a single value of the nucleation coefficient, as K in J=K [H2 SO4 ]2 , but the median coefficients for different sites varied over an order of magnitude. This inter-site variation was substantially smaller when the heteromolecular homogenous nucleation between H2 SO4 and organic vapours was assumed to take place in addition to homogenous nucleation of H2 SO4 alone, i.e., J=KSA1 [H2 SO4 ]2 +KSA2 [H2 SO4 ][org]. By adding in this equation a term describing homomolecular organic vapour nucleation, Ks3 [org]2 , equally good results were achieved. In general, our results suggest that organic vapours do play a role, not only in the condensational growth of the particles, but also in the nucleation process, with a site-specific degree.

Sulphuric acid is a key component in atmospheric new particle formation. However, sulphuric acid alone does not form stable enough clusters to initiate particle formation in atmospheric conditions. Strong bases, such as amines, have been suggested to stabilize sulphuric acid clusters and thus participate in particle formation. We modelled the formation rate of clusters with two sulphuric acid and two amine molecules (JA2B2) at varying atmospherically relevant conditions with respect to concentrations of sulphuric acid ([H2SO4]), dimethylamine ([DMA]) and trimethylamine ([TMA]), temperature and relative humidity (RH). We also tested how the model results change if we assume that the clusters with two sulphuric acid and two amine molecules would act as seeds for heterogeneous nucleation of organic vapours (other than amines) with higher atmospheric concentrations than sulphuric acid. The modelled formation rates JA2B2 were functions of sulphuric acid concentration with close to quadratic dependence, which is in good agreement with atmospheric observations of the connection between the particle formation rate and sulphuric acid concentration. The coefficients KA2B2 connecting the cluster formation rate and sulphuric acid concentrations as JA2B2=KA2B2[H2SO4]2 turned out to depend also on amine concentrations, temperature and relative humidity. We compared the modelled coefficients KA2B2 with the corresponding coefficients calculated from the atmospheric observations (Kobs) from environments with varying temperatures and levels of anthropogenic influence. By taking into account the modelled behaviour of JA2B2 as a function of [H2SO4], temperature and RH, the atmospheric particle formation rate was reproduced more closely than with the traditional semi-empirical formulae based on sulphuric acid concentration only. The formation rates of clusters with two sulphuric acid and two amine molecules with different amine compositions (DMA or TMA or one of both) had different responses to varying meteorological conditions and concentrations of vapours participating in particle formation. The observed inverse proportionality of the coefficient Kobs with RH and temperature agreed best with the modelled coefficient KA2B2 related to formation of a cluster with two H2SO4 and one or two TMA molecules, assuming that these clusters can grow in collisions with abundant organic vapour molecules. In case this assumption is valid, our results suggest that the formation rate of clusters with at least two of both sulphuric acid and amine molecules might be the rate-limiting step for atmospheric particle formation. More generally, our analysis elucidates the sensitivity of the atmospheric particle formation rate to meteorological variables and concentrations of vapours participating in particle formation (also other than H2SO4).

The effect of increased reaction rates of stabilized Criegee intermediates (sCIs) with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012) increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO) with SO2 according to the values recommended by Welz et al. (2012) increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.

Atmospheric concentrations of nitrous acid (HONO), one of the major precursors of the hydroxyl radical (OH) in the troposphere, significantly exceed the values predicted by the assumption of a photostationary state (PSS) during daytime. Therefore, additional sources of HONO were intensively investigated in the last decades. This study presents budget calculations of HONO based on simultaneous measurements of all relevant species, including HONO and OH at two different measurement heights, i.e. 1 m above the ground and about 2 to 3 m above the canopy (24 m above the ground), conducted in a boreal forest environment. We observed mean HONO concentrations of about 6.5 × 108 molecules cm−3 (26 ppt) during daytime, more than 20 times higher than expected from the PSS of 0.2 × 108 molecules cm−3 (1 ppt). To close the budgets at both heights, a strong additional source term during daytime is required. This unidentified source is at its maximum at noon (up to 1.1 × 106 molecules cm−3 s−1, 160 ppt h−1) and in general up to 2.3 times stronger above the canopy than close to the ground. The insignificance of known gas phase reactions and other processes like dry deposition or advection compared to the photolytic decomposition of HONO at this measurement site was an ideal prerequisite to study possible correlations of this unknown term to proposed HONO sources. But neither the proposed emissions from soils nor the proposed photolysis of adsorbed HNO3 contributed substantially to the unknown source. However, the unknown source was found to be perfectly correlated to the unbalanced photolytic loss of HONO.

Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene) showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene. New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ), defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.