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This study focuses on the analysis of the sub-micron aerosol characteristics at El Arenosillo Station, a rural and coastal environment in South-western Spain between 1 August 2004 and 31 July 2006 (594 days). The mean total concentration (<i>N</i><sub>T</sub>) was 8660 cm<sup>−3</sup> and the mean concentrations in the nucleation (<i>N</i><sub>NUC</sub>), Aitken (<i>N</i><sub>AIT</sub>) and accumulation (<i>N</i><sub>ACC</sub>) particle size ranges were 2830 cm<sup>−3</sup>, 4110 cm<sup>−3</sup> and 1720 cm<sup>−3</sup>, respectively. Median size distribution was characterised by a single-modal fit, with a geometric diameter, median number concentration and geometric standard deviation of 60 nm, 5390 cm<sup>−3</sup> and 2.31, respectively. Characterisation of primary emissions, secondary particle formation, changes to meteorology and long-term transport has been necessary to understand the seasonal and annual variability of the total and modal particle concentration. Number concentrations exhibited a diurnal pattern with maximum concentrations around noon. This was governed by the concentrations of the nucleation and Aitken modes during the warm seasons and only by the nucleation mode during the cold seasons. Similar monthly mean total concentrations were observed throughout the year due to a clear inverse variation between the monthly mean <i>N</i><sub>NUC</sub> and <i>N</i><sub>ACC</sub>. It was related to the impact of desert dust and continental air masses on the monthly mean particle levels. These air masses were associated with high values of <i>N</i><sub>ACC</sub> which suppressed the new particle formation (decreasing <i>N</i><sub>NUC</sub>). Each day was classified according to a land breeze flow or a synoptic pattern influence. The median size distribution for desert dust and continental aerosol was dominated by the Aitken and accumulation modes, and marine air masses were dominated by the nucleation and Aitken modes. Particles moved offshore due to the land breeze and had an impact on the particle burden at noon, especially when the wind was blowing from the NW sector in the morning during summer time. This increased <i>N</i><sub>NUC</sub> and <i>N</i><sub>AIT</sub> by factors of 3.1 and 2.4, respectively. Nucleation events with the typical "banana" shape were characterised by a mean particle nucleation rate of 0.74 cm<sup>−3</sup> s<sup>−1</sup>, a mean growth rate of 1.96 nm h<sup>−1</sup> and a mean total duration of 9.25 h (starting at 10:55 GMT and ending at 20:10 GMT). They were observed for 48 days. Other nucleation events were identified as those produced by the emissions from the industrial areas located at a distance of 35 km. They were observed for 42 days. Both nucleation events were strongly linked to the marine air mass origin.
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We present over one year (January 2010–February 2011) of continuous atmospheric methanol measurements from the University of Minnesota tall tower Trace Gas Observatory (KCMP tall tower; 244 m a.g.l.), and interpret the dataset in terms of constraints on regional methanol sources and seasonality. The seasonal cycle of methanol concentrations observed at the KCMP tall tower is generally similar to that simulated by a global 3-D chemical transport model (GEOS-Chem, driven with MEGANv2.0 biogenic emissions) except the seasonal peak occurs ~1 month earlier in the observations, apparently reflecting a model underestimate of emission rates for younger versus older leaves. Based on a source tracer approach, which we evaluate using GEOS-Chem and with multiple tracers, we estimate that anthropogenic emissions account for approximately 40% of ambient methanol abundance during winter and 10% during summer. During daytime in summer, methanol concentrations increase exponentially with temperature, reflecting the temperature sensitivity of the biogenic source, and the observed temperature dependence is statistically consistent with that in the model. Nevertheless, summertime concentrations are underestimated by on average 35% in the model for this region. The seasonal importance of methanol as a source of formaldehyde (HCHO) and carbon monoxide (CO) is highest in spring through early summer, when biogenic methanol emissions are high but isoprene emissions are still relatively low. During that time observed methanol concentrations account for on average 20% of the total CO and HCHO production rates as simulated by GEOS-Chem, compared to 12% later in the summer and 12% on an annual average basis. The biased seasonality in the model means that the photochemical role for methanol early in the growing season is presently underestimated.
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The influence of the properties of fine particles on the formation of clouds and precipitation in the tropical atmosphere is of primary importance to their impacts on radiative forcing and the hydrological cycle. Measurements of aerosol number size distribution, hygroscopicity in both sub- and supersaturated regimes and composition were taken between March and July 2008 in the tropical rainforest in Borneo, Malaysia, marking the first study of this type in an Asian tropical rainforest. Hygroscopic growth factors (GF) at 90 % relative humidity (RH) for the dry diameter range <i>D</i><sub>0</sub> = 32–258 nm, supersaturated water uptake behaviour for the dry diameter range <i>D</i><sub>0</sub> = 45–300 nm and aerosol chemical composition were simultaneously measured using a Hygroscopicity Tandem Differential Mobility Analyser (HTDMA), a Droplet Measurement Technologies Cloud Condensation Nuclei counter (CCNc) and an Aerodyne Aerosol Mass Spectrometer (AMS) respectively. <br><br> The hygroscopicity parameter κ was derived from both CCNc and HTDMA measurements, with the resulting values of κ ranging from 0.05–0.37, and 0.17–0.37, respectively. Although the total range of κ values is in good agreement, there are inconsistencies between CCNc and HTDMA derived κ values at different dry diameters. Results from a study with similar methodology performed in the Amazon rainforest report values for κ within a similar range to those reported in this work, indicating that the aerosol as measured from both sites shows similar hygroscopic properties. However, the derived number of cloud condensation nuclei (<i>N</i><sub>CCN</sub>) were much higher in the present experiment than the Amazon, resulting in part from the increased total particle number concentrations observed in the Bornean rainforest. This contrast between the two environments may be of substantial importance in describing the impacts of particles in the tropical atmosphere.
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The degree of non-linearity in DMS-cloud-climate interactions is assessed using the ECHAM5-HAMMOZ model by taking into account end-to-end aerosol chemistry-cloud microphysics link. The evaluation is made over the Southern oceans in austral summer, a region of minimal anthropogenic influence. In this study, we compare the DMS-derived changes in the aerosol and cloud microphysical properties between a baseline simulation with the ocean DMS emissions from a prescribed climatology, and a scenario where the DMS emissions are doubled. Our results show that doubling the DMS emissions in the current climate results in a non-linear response in atmospheric DMS burden and subsequently, in SO<sub>2</sub> and H<sub>2</sub>SO<sub>4</sub> burdens due to inadequate OH oxidation. The aerosol optical depth increases by only ~20 % in the 30° S–75° S belt in the SH summer months. This increases the vertically integrated cloud droplet number concentrations (CDNC) by 25 %. Since the vertically integrated liquid water vapor is constant in our model simulations, an increase in CDNC leads to a reduction in cloud droplet radius of 3.4 % over the Southern oceans in summer. The equivalent increase in cloud liquid water path is 10.7 %. The above changes in cloud microphysical properties result in a change in global annual mean radiative forcing at the TOA of −1.4 W m<sup>−2</sup>. The results suggest that the DMS-cloud microphysics link is highly non-linear. This has implications for future studies investigating the DMS-cloud climate feedbacks in a warming world and for studies evaluating geoengineering options to counteract warming by modulating low level marine clouds.
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Forest fires are an important source to carbonaceous aerosols in the Western United States (WUS). We quantify the relative contribution of biomass burning to black carbon (BC) in the WUS mountain ranges by analyzing surface BC observations for 2006 from the Interagency Monitoring of PROtected Visual Environment (IMPROVE) network using the GEOS-Chem global chemical transport model. Observed surface BC concentrations show broad maxima during late June to early November. Enhanced potassium concentrations and potassium/sulfur ratios observed during the high-BC events indicate a dominant biomass burning influence during the peak fire season. Model surface BC reproduces the observed day-to day and synoptic variabilities in regions downwind of but near urban centers. Major discrepancies are found at elevated mountainous sites during the July-October fire season when simulated BC concentrations are biased low by a factor of two. We attribute these low biases largely to the underestimated (by more than a factor of two) and temporally misplaced biomass burning emissions of BC in the model. Additionally, we find that the biomass burning contribution to surface BC concentrations in the USA likely was underestimated in a previous study using GEOS-Chem (Park et al., 2003), because of the unusually low planetary boundary layer (PBL) heights in the GEOS-3 meteorological reanalysis data used to drive the model. PBL heights from GEOS-4 and GEOS-5 reanalysis data are comparable to those from the North American Regional Reanalysis (NARR). Model simulations show slightly improved agreements with the observations when driven by GEOS-5 reanalysis data, but model results are still biased low. The use of biomass burning emissions with diurnal cycle, synoptic variability, and plume injection has relatively small impact on the simulated surface BC concentrations in the WUS.
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In the North Pacific, transport and deposition of mineral dust from Asia appear to be one of major sources of iron which can regulate growth of phytoplankton in the ocean. In this process, it is essential to identify chemical species of iron contained in Asian dust, because bioavailability of iron in the ocean is strongly influenced by the solubility of iron, which in turn is dependent on iron species in the dust. Here, we report that clay minerals (illite and chlorite) in the dusts near the source collected at Aksu (western China) can be transformed into ferrihydrite by atmospheric chemical processes during their long-range transport to eastern China (Qingdao) and Japan (Tsukuba) based on the speciation by X-ray absorption fine structure (XAFS) and other methods such as X-ray diffraction and chemical extraction. As a result, Fe molar ratio in Aksu (illite : chlorite : ferrihydrite = 70 : 25 : 5) was changed to that in Tsukuba (illite : chlorite : ferrihydrite = 65 : 10 : 25). Moreover, leaching experiments were conducted to study the change of iron solubility. It was found that the iron solubility for the dust in Tsukuba (soluble iron fraction: 11.8 % and 1.10 % for synthetic rain water and seawater, respectively) was larger than that in Aksu (4.1 % and 0.28 %, respectively), showing that iron in the dust after the transport becomes more soluble possibly due to the formation of ferrihydrite in the atmosphere. Our findings suggested that secondary formation of ferrihydrite during the transport should be considered as one of important processes in evaluating the supply of soluble iron to seawater.
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A continuous tropospheric and stratospheric vertically resolved ozone time series, from 1850 to 2099, has been generated to be used as forcing in global climate models that do not include interactive chemistry. A multiple linear regression analysis of SAGE I+II satellite observations and polar ozonesonde measurements is used for the stratospheric zonal mean dataset during the well-observed period from 1979 to 2009. In addition to terms describing the mean annual cycle, the regression includes terms representing equivalent effective stratospheric chlorine (EESC) and the 11-yr solar cycle variability. The EESC regression fit coefficients, together with pre-1979 EESC values, are used to extrapolate the stratospheric ozone time series backward to 1850. While a similar procedure could be used to extrapolate into the future, coupled chemistry climate model (CCM) simulations indicate that future stratospheric ozone abundances are likely to be significantly affected by climate change, and capturing such effects through a regression model approach is not feasible. Therefore, the stratospheric ozone dataset is extended into the future (merged in 2009) with multi-model mean projections from 13 CCMs that performed a simulation until 2099 under the SRES (Special Report on Emission Scenarios) A1B greenhouse gas scenario and the A1 adjusted halogen scenario in the second round of the Chemistry-Climate Model Validation (CCMVal-2) Activity. The stratospheric zonal mean ozone time series is merged with a three-dimensional tropospheric data set extracted from simulations of the past by two CCMs (CAM3.5 and GISS-PUCCINI) and of the future by one CCM (CAM3.5). The future tropospheric ozone time series continues the historical CAM3.5 simulation until 2099 following the four different Representative Concentration Pathways (RCPs). Generally good agreement is found between the historical segment of the ozone database and satellite observations, although it should be noted that total column ozone is overestimated in the southern polar latitudes during spring and tropospheric column ozone is slightly underestimated. Vertical profiles of tropospheric ozone are broadly consistent with ozonesondes and in-situ measurements, with some deviations in regions of biomass burning. The tropospheric ozone radiative forcing (RF) from the 1850s to the 2000s is 0.23 W m<sup>−2</sup>, lower than previous results. The lower value is mainly due to (i) a smaller increase in biomass burning emissions; (ii) a larger influence of stratospheric ozone depletion on upper tropospheric ozone at high southern latitudes; and possibly (iii) a larger influence of clouds (which act to reduce the net forcing) compared to previous radiative forcing calculations. Over the same period, decreases in stratospheric ozone, mainly at high latitudes, produce a RF of −0.08 W m<sup>−2</sup>, which is more negative than the central Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4) value of −0.05 W m<sup>−2</sup>, but which is within the stated range of −0.15 to +0.05 W m<sup>−2</sup>. The more negative value is explained by the fact that the regression model simulates significant ozone depletion prior to 1979, in line with the increase in EESC and as confirmed by CCMs, while the AR4 assumed no change in stratospheric RF prior to 1979. A negative RF of similar magnitude persists into the future, although its location shifts from high latitudes to the tropics. This shift is due to increases in polar stratospheric ozone, but decreases in tropical lower stratospheric ozone, related to a strengthening of the Brewer-Dobson circulation, particularly through the latter half of the 21st century. Differences in trends in tropospheric ozone among the four RCPs are mainly driven by different methane concentrations, resulting in a range of tropospheric ozone RFs between 0.4 and 0.1 W m<sup>−2</sup> by 2100. The ozone dataset described here has been released for the Coupled Model Intercomparison Project (CMIP5) model simulations in netCDF Climate and Forecast (CF) Metadata Convention at the PCMDI website (<a href="http://cmip-pcmdi.llnl.gov/"target="_blank">http://cmip-pcmdi.llnl.gov/</a>).
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The impact of future emissions from aviation and shipping on the atmospheric chemical composition has been estimated using an ensemble of six different atmospheric chemistry models. This study considers an optimistic emission scenario (B1) taking into account e.g. rapid introduction of clean and resource-efficient technologies, and a mitigation option for the aircraft sector (B1 ACARE), assuming further technological improvements. Results from sensitivity simulations, where emissions from each of the transport sectors were reduced by 5%, show that emissions from both aircraft and shipping will have a larger impact on atmospheric ozone and OH in near future (2025; B1) and for longer time horizons (2050; B1) compared to recent time (2000). However, the ozone and OH impact from aircraft can be reduced substantially in 2050 if the technological improvements considered in the B1 ACARE will be achieved. <br><br> Shipping emissions have the largest impact in the marine boundary layer and their ozone contribution may exceed 4 ppbv (when scaling the response of the 5% emission perturbation to 100% by applying a factor 20) over the North Atlantic Ocean in the future (2050; B1) during northern summer (July). In the zonal mean, ship-induced ozone relative to the background levels may exceed 12% near the surface. Corresponding numbers for OH are 6.0 × 10<sup>5</sup> molecules cm<sup>−3</sup> and 30%, respectively. This large impact on OH from shipping leads to a relative methane lifetime reduction of 3.92 (±0.48) on the global average in 2050 B1 (ensemble mean CH<sub>4</sub> lifetime is 8.0 (±1.0) yr), compared to 3.68 (±0.47)% in 2000. <br><br> Aircraft emissions have about 4 times higher ozone enhancement efficiency (ozone molecules enhanced relative to NO<sub>x</sub> molecules emitted) than shipping emissions, and the maximum impact is found in the UTLS region. Zonal mean aircraft-induced ozone could reach up to 5 ppbv at northern mid- and high latitudes during future summer (July 2050; B1), while the relative impact peaks during northern winter (January) with a contribution of 4.2%. Although the aviation-induced impact on OH is lower than for shipping, it still causes a reduction in the relative methane lifetime of 1.68 (±0.38)% in 2050 B1. However, for B1 ACARE the perturbation is reduced to 1.17 (±0.28)%, which is lower than the year 2000 estimate of 1.30 (±0.30)%. <br><br> Based on the fully scaled perturbations we calculate net radiative forcings from the six models taking into account ozone, methane (including stratospheric water vapour), and methane-induced ozone changes. For the B1 scenario, shipping leads to a net cooling with radiative forcings of −28.0 (±5.1) and −30.8 (±4.8) mW m<sup>−2</sup> in 2025 and 2050, respectively, due to the large impact on OH and, thereby, methane lifetime reductions. Corresponding values for the aviation sector shows a net warming effect with 3.8 (±6.1) and 1.9 (±6.3) mW m<sup>−2</sup>, respectively, but with a small net cooling of -0.6 (±4.6) mW m<sup>−2</sup> for B1 ACARE in 2050.
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Gaseous sulphuric acid is a key precursor for new particle formation in the atmosphere. Previous experimental studies have confirmed a strong correlation between the number concentrations of freshly formed particles and the ambient concentrations of sulphuric acid. This study evaluates a body of experimental gas phase sulphuric acid concentrations, as measured by Chemical Ionization Mass Spectrometry (CIMS) during six intensive measurement campaigns and one long-term observational period. The campaign datasets were measured in Hyytiälä, Finland, in 2003 and 2007, in San Pietro Capofiume, Italy, in 2009, in Melpitz, Germany, in 2008, in Atlanta, Georgia, USA, in 2002, and in Niwot Ridge, Colorado, USA, in 2007. The long term data were obtained in Hohenpeissenberg, Germany, during 1998 to 2000. The measured time series were used to construct proximity measures ("proxies") for sulphuric acid concentration by using statistical analysis methods. The objective of this study is to find a proxy for sulfuric acid that is valid in as many different atmospheric environments as possible. Our most accurate and universal formulation of the sulphuric acid concentration proxy uses global solar radiation, SO<sub>2</sub> concentration, condensation sink and relative humidity as predictor variables, yielding a correlation measure (<i>R</i>) of 0.87 between observed concentration and the proxy predictions. Interestingly, the role of the condensation sink in the proxy was only minor, since similarly accurate proxies could be constructed with global solar radiation and SO<sub>2</sub> concentration alone. This could be attributed to SO<sub>2</sub> being an indicator for anthropogenic pollution, including particulate and gaseous emissions which represent sinks for the OH radical that, in turn, is needed for the formation of sulphuric acid.
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The currently used "kinetic-fractionation" (KF) model of the differential incorporation of water-molecule isotopologues into vapor-grown ice omits surface processes on crystal facets that may be important in temperature reconstructions. This article introduces the "surface-kinetic" fractionation model, a model that includes such surface processes, and shows that differences in deposition coefficients for water isotopologues can produce isotopic fractionation coefficients that significantly differ from those of KF theory. For example, if the deposition coefficient of H<sub>2</sub><sup>18</sup>O differs by just 5% from that of ordinary water (H<sub>2</sub><sup>16</sup>O), the resulting fractionation coefficient at 20% supersaturation may deviate from the KF value by up to about ±17‰, and even more at greater supersaturation. As a result, the surface-kinetic theory may significantly change how fractionation depends on supersaturation. Moreover, the model introduces possible new temperature dependencies from the deposition coefficients. These parameters need to be constrained by new laboratory measurements.
