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We present an analysis of SO<sub>2</sub> column densities derived from GOME-2 satellite measurements for the Kīlauea volcano (Hawai`i) for 2007–2012. During a period of enhanced degassing activity in March–November 2008, monthly mean SO<sub>2</sub> emission rates and effective SO<sub>2</sub> lifetimes are determined simultaneously from the observed downwind plume evolution and meteorological wind fields, without further model input. Kīlauea is particularly suited for quantitative investigations from satellite observations owing to the absence of interfering sources, the clearly defined downwind plumes caused by steady trade winds, and generally low cloud fractions. For March–November 2008, the effective SO<sub>2</sub> lifetime is 1–2 days, and Kīlauea SO<sub>2</sub> emission rates are 9–21 kt day<sup>−1</sup>, which is about 3 times higher than initially reported from ground-based monitoring systems.
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The dominant component of atmospheric, organic aerosol is that derived from the oxidation of volatile organic compounds (VOCs), so-called secondary organic aerosol (SOA). SOA consists of a multitude of organic compounds, only a small fraction of which has historically been identified. Formation and evolution of SOA is a complex process involving coupled chemical reaction and mass transport in the gas and particle phases. Current SOA models do not embody the full spectrum of reaction and transport processes, nor do they identify the dominant rate-limiting steps in SOA formation. Based on molecular identification of SOA oxidation products, we show here that the chemical evolution of SOA from a variety of VOC precursors adheres to characteristic "molecular corridors" with a tight inverse correlation between volatility and molar mass. The slope of these corridors corresponds to the increase in molar mass required to decrease volatility by one order of magnitude (-d<i>M</i> / dlog<i>C</i><sub>0</sub>). It varies in the range of 10–30 g mol<sup>−1</sup>, depending on the molecular size of the SOA precursor and the O : C ratio of the reaction products. Sequential and parallel reaction pathways of oxidation and dimerization or oligomerization progressing along these corridors pass through characteristic regimes of reaction-, diffusion-, or accommodation-limited multiphase chemical kinetics that can be classified according to reaction location, degree of saturation, and extent of heterogeneity of gas and particle phases. The molecular corridors and kinetic regimes help to constrain and describe the properties of the products, pathways, and rates of SOA evolution, thereby facilitating the further development of aerosol models for air quality and climate.
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The feedback between soil moisture and precipitation has long been a topic of interest due to its potential for improving weather and seasonal forecasts. The generally proposed mechanism assumes a control of soil moisture on precipitation via the partitioning of the surface turbulent heat fluxes, as assessed via the evaporative fraction (EF), i.e., the ratio of latent heat to the sum of latent and sensible heat, in particular under convective conditions. Our study investigates the poorly understood link between EF and precipitation by relating the before-noon EF to the frequency of afternoon precipitation over the contiguous US, through statistical analyses of multiple EF and precipitation data sets. We analyze remote-sensing data products (Global Land Evaporation: the Amsterdam Methodology (GLEAM) for EF, and radar precipitation from the NEXt generation weather RADar system (NEXRAD)), FLUXNET station data, and the North American Regional Reanalysis (NARR). Data sets agree on a region of positive relationship between EF and precipitation occurrence in the southwestern US. However, a region of strong positive relationship over the eastern US in NARR cannot be confirmed with observation-derived estimates (GLEAM, NEXRAD and FLUXNET). The GLEAM–NEXRAD data set combination indicates a region of positive EF–precipitation relationship in the central US. These disagreements emphasize large uncertainties in the EF data. Further analyses highlight that much of these EF–precipitation relationships could be explained by precipitation persistence alone, and it is unclear whether EF has an additional role in triggering afternoon precipitation. This also highlights the difficulties in isolating a land impact on precipitation. Regional analyses point to contrasting mechanisms over different regions. Over the eastern US, our analyses suggest that the EF–precipitation relationship in NARR is either atmospherically controlled (from precipitation persistence and potential evaporation) or driven by vegetation interception rather than soil moisture. Although this aligns well with the high forest cover and the wet regime of that region, the role of interception evaporation is likely overestimated because of low nighttime evaporation in NARR. Over the central and southwestern US, the EF–precipitation relationship is additionally linked to soil moisture variations, owing to the soil-moisture-limited climate regime.
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We present measurements of a long-range smoke transport event recorded on 20–21 July 2011 over Halifax, Nova Scotia, Canada, during the Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites (BORTAS-B) campaign. Ground-based Fourier transform spectrometers and photometers detected air masses associated with large wildland fires burning in eastern Manitoba and western Ontario. <br><br> We investigate a plume with high trace gas amounts but low amounts of particles that preceded and overlapped at the Halifax site with a second plume with high trace gas loadings and significant amounts of particulate material. We show that the first plume experienced a meteorological scavenging event, but the second plume had not been similarly scavenged. This points to the necessity to account carefully for the plume history when considering long-range transport since simultaneous or near-simultaneous times of arrival are not necessarily indicative of either similar trajectories or meteorological history. We investigate the origin of the scavenged plume, and the possibility of an aerosol wet deposition event occurring in the plume ~ 24 h prior to the measurements over Halifax. The region of lofting and scavenging is only monitored on an intermittent basis by the present observing network, and thus we must consider many different pieces of evidence in an effort to understand the early dynamics of the plume. Through this discussion we also demonstrate the value of having many simultaneous remote-sensing measurements in order to understand the physical and chemical behaviour of biomass burning plumes.
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Surface concentrations of secondary inorganic particle components over the UK have been analysed for 2001–2010 using the EMEP4UK regional atmospheric chemistry transport model and evaluated against measurements. Gas/particle partitioning in the EMEP4UK model simulations used a bulk approach, which may lead to uncertainties in simulated secondary inorganic aerosol. However, model simulations were able to accurately represent both the long-term decadal surface concentrations of particle sulfate and nitrate and an episode in early 2003 of substantially elevated nitrate measured across the UK by the AGANet network. The latter was identified as consisting of three separate episodes, each of less than 1 month duration, in February, March and April. The primary cause of the elevated nitrate levels across the UK was meteorological: a persistent high-pressure system, whose varying location impacted the relative importance of transboundary versus domestic emissions. Whilst long-range transport dominated the elevated nitrate in February, in contrast it was domestic emissions that mainly contributed to the March episode, and for the April episode both domestic emissions and long-range transport contributed. A prolonged episode such as the one in early 2003 can have substantial impact on annual average concentrations. The episode led to annual concentration differences at the regional scale of similar magnitude to those driven by long-term changes in precursor emissions over the full decade investigated here. The results demonstrate that a substantial part of the UK, particularly the south and southeast, may be close to or exceeding annual mean limit values because of import of inorganic aerosol components from continental Europe under specific conditions. The results reinforce the importance of employing multiple year simulations in the assessment of emissions reduction scenarios on particulate matter concentrations and the need for international agreements to address the transboundary component of air pollution.
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The molecular characteristics of aerosol organic matter (OM) determines to a large extent its impacts on the atmospheric radiative budget and ecosystem function in terrestrial and aquatic environments, yet the OM molecular details of aerosols from different sources are not well established. Aerosol particulate samples with North American-influenced, North African-influenced, and marine (minimal recent continental influence) air mass back trajectories were collected as part of the 2011 trans-North Atlantic US GEOTRACES cruise and analyzed for their water soluble OM (WSOM) molecular characteristics using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Principal component analysis (PCA) separated the samples into five groups defined by distinct molecular formula characteristics. An abundance of nitrogen containing compounds with molecular formulas consistent with amino acid derivatives defined the two samples comprising the primary marine group (henceforth referred to as Primary Marine), which suggest a primary marine biological source to their WSOM in spite of their North American-influenced air mass trajectories. A second group of samples (aged marine, henceforth referred to as Aged Marine) with marine air mass trajectories was characterized by an abundance of low O / C (0.15–0.45) sulfur containing compounds consistent with organosulfate compounds formed via secondary aging reactions in the atmosphere. Several samples having North American-influenced air mass trajectories formed another group again characterized by organosulfate and nitrooxyorganosulfate type compounds with higher O / C ratios (0.5–1.0) than the Aged Marine samples reflecting the combustion influence from the North American continent. All the samples with North African-influenced air mass trajectories were grouped together in the PCA and were characterized by a lack of heteroatom (N, S, P) containing molecular formulas covering a wide O / C range (0.15–0.90) reflecting the desert source of this WSOM. The two marine groups showed molecular formulas that, on average, had higher H / C ratios and lower O / C ratios and modified aromaticity indices than the two continentally influenced groups, which suggests that these properties are characteristic of marine vs. continental aerosol WSOM. The final sample group, the mixed source samples (henceforth referred to as Mixed Source), showed intermediate molecular characteristics, which suggests no dominant continental or marine source. The source-specific OM details described here will aid efforts to link aerosol OM source with molecular characteristics and impacts in the environment.
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Iron and phosphorous are essential to marine microorganisms in vast regions in oceans worldwide. Atmospheric inputs are important allochthonous sources of Fe and P. The variability in airborne Fe deposition is hypothesized to serve an important function in previous glacial–interglacial cycles, contributing to the variability in atmospheric CO<sub>2</sub> and ultimately the climate. Understanding the mechanisms underlying the mobilization of airborne Fe and P from insoluble to soluble forms is critical to evaluate the biogeochemical effects of these elements. In this study, we present a robust power-law correlation between fractional Fe solubility and non-sea-salt-sulfate / Total-Fe (nss-sulfate / Fe<sub>T</sub>) molar ratio independent of distinct sources of airborne Fe of natural and/or anthropogenic origins over the South China Sea. This area receives Asian dust and pollution outflows and Southeast Asian biomass burning. This correlation is also valid for nitrate and total acids, demonstrating the significance of acid processing in enhancing Fe mobilization. Such correlations are also found for P, yet source dependent. These relationships serve as straightforward parameters that can be directly incorporated into available atmosphere–ocean coupling models that facilitate the assessment of Fe and P fertilization effects. Although biomass burning activity may supply Fe to the bioavailable Fe pool, pyrogenic soils are possibly the main contributors, not the burned plants. This finding warrants a multidisciplinary investigation that integrates atmospheric observations with the resulting biogeochemistry in the South China Sea, which is influenced by atmospheric forcings and nutrient dynamics with monsoons.
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The air quality of megacities can be influenced by external emission sources on both global and regional scales. At the same time their outflow emissions can exert an impact to the surrounding environment. The present study evaluates an SO<sub>2</sub> peak observed on 24 March 2006 at the suburban supersite T1 and at ambient air quality monitoring stations located in the northern region of the Mexico City Metropolitan Area (MCMA) during the Megacity Initiative: Local and Global Research Observations (MILAGRO) field campaign. We found that this peak could be related to an important episodic emission event coming from Tizayuca region, northeast of the MCMA. Back-trajectory analyses suggest that the emission event started in the early morning at 04:00 LST and lasted for about 9 h. The estimated emission rate is about 2 kg s<sup>−1</sup>. To the best of our knowledge, sulfur dioxide emissions from the Tizayuca region have not been considered in previous studies. This finding suggests the possibility of "overlooked" emission sources in this region that could influence the air quality of the MCMA. This further motivated us to study the cement plants, including those in the state of Hidalgo and in the State of Mexico. It was found that they can contribute to the SO<sub>2</sub> levels in the northeast (NE) region of the basin (about 42%), at the suburban supersite T1 (41%) and that at some monitoring stations their contribution can be even higher than the contribution from the Tula Industrial Complex (TIC). <br><br> The contribution of the Tula Industrial Complex to regional ozone levels is estimated. The model suggests low contribution to the MCMA (1 to 4 ppb) and slightly higher contribution at the suburban T1 (6 ppb) and rural T2 (5 ppb) supersites. However, the contribution could be as high as 10 ppb in the upper northwest region of the basin and in the southwest and south-southeast regions of the state of Hidalgo. In addition, the results indicated that the ozone plume could also be transported to northwest Tlaxcala, eastern Hidalgo, and farther northeast of the State of Mexico, but with rather low values. A first estimate of the potential contribution from flaring activities to regional ozone levels is presented. Results suggest that up to 30% of the total regional ozone from TIC could be related to flaring activities. <br><br> Finally, the influence on SO<sub>2</sub> levels from technological changes in the existing refinery is briefly discussed. These changes are due to the upcoming construction of a new refinery in Tula. The combination of emission reductions in the power plant, the refinery and in local sources in the MCMA could result in higher reductions on the average SO<sub>2</sub> concentration. Reductions in external sources tend to affect more the northern part of the basin (−16 to −46%), while reductions of urban sources in the megacity tend to diminish SO<sub>2</sub> levels substantially in the central, southwest, and southeast regions (−31 to −50%).
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Multiple-regression analyses have been performed on 32 years of total ozone column data that was spatially gridded with a 1 × 1.5° resolution. The total ozone data consist of the MSR (Multi Sensor Reanalysis; 1979–2008) and 2 years of assimilated SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY) ozone data (2009–2010). The two-dimensionality in this data set allows us to perform the regressions locally and investigate spatial patterns of regression coefficients and their explanatory power. Seasonal dependencies of ozone on regressors are included in the analysis. <br><br> A new physically oriented model is developed to parameterize stratospheric ozone. Ozone variations on nonseasonal timescales are parameterized by explanatory variables describing the solar cycle, stratospheric aerosols, the quasi-biennial oscillation (QBO), El Niño–Southern Oscillation (ENSO) and stratospheric alternative halogens which are parameterized by the effective equivalent stratospheric chlorine (EESC). For several explanatory variables, seasonally adjusted versions of these explanatory variables are constructed to account for the difference in their effect on ozone throughout the year. To account for seasonal variation in ozone, explanatory variables describing the polar vortex, geopotential height, potential vorticity and average day length are included. Results of this regression model are compared to that of a similar analysis based on a more commonly applied statistically oriented model. <br><br> The physically oriented model provides spatial patterns in the regression results for each explanatory variable. The EESC has a significant depleting effect on ozone at mid- and high latitudes, the solar cycle affects ozone positively mostly in the Southern Hemisphere, stratospheric aerosols affect ozone negatively at high northern latitudes, the effect of QBO is positive and negative in the tropics and mid- to high latitudes, respectively, and ENSO affects ozone negatively between 30° N and 30° S, particularly over the Pacific. The contribution of explanatory variables describing seasonal ozone variation is generally large at mid- to high latitudes. We observe ozone increases with potential vorticity and day length and ozone decreases with geopotential height and variable ozone effects due to the polar vortex in regions to the north and south of the polar vortices. <br><br> Recovery of ozone is identified globally. However, recovery rates and uncertainties strongly depend on choices that can be made in defining the explanatory variables. The application of several trend models, each with their own pros and cons, yields a large range of recovery rate estimates. Overall these results suggest that care has to be taken in determining ozone recovery rates, in particular for the Antarctic ozone hole.
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In order to understand the impact of ice formation in clouds, a quantitative understanding of ice nucleation is required, along with an accurate and efficient representation for use in cloud resolving models. Ice nucleation by atmospherically relevant particle types is complicated by interparticle variability in nucleating ability, as well as a stochastic, time-dependent, nature inherent to nucleation. Here we present a new and computationally efficient Framework for Reconciling Observable Stochastic Time-dependence (FROST) in immersion mode ice nucleation. This framework is underpinned by the finding that the temperature dependence of the nucleation-rate coefficient controls the residence-time and cooling-rate dependence of freezing. It is shown that this framework can be used to reconcile experimental data obtained on different timescales with different experimental systems, and it also provides a simple way of representing the complexities of ice nucleation in cloud resolving models. The routine testing and reporting of time-dependent behaviour in future experimental studies is recommended, along with the practice of presenting normalised data sets following the methods outlined here.
