-
We present a climatology of monthly and 10° zonal mean profiles of sulfur dioxide (SO<sub>2</sub>) volume mixing ratios (vmr) derived from MIPAS/Envisat measurements in the altitude range 15–45 km from July 2002 until April 2012. The vertical resolution varies from 3.5–4 km in the lower stratosphere up to 6–10 km at the upper end of the profiles, with estimated total errors of 5–20 pptv for single profiles of SO<sub>2</sub>. Comparisons with the few available observations of SO<sub>2</sub> up to high altitudes from ATMOS for a volcanically perturbed situation from ACE-FTS and, at the lowest altitudes, with stratospheric in situ observations reveal general consistency of the datasets. The observations are the first empirical confirmation of features of the stratospheric SO<sub>2</sub> distribution, which have only been shown by models up to now: (1) the local maximum of SO<sub>2</sub> at around 25–30 km altitude, which is explained by the conversion of carbonyl sulfide (COS) as the precursor of the Junge layer; and (2) the downwelling of SO<sub>2</sub>-rich air to altitudes of 25–30 km at high latitudes during winter and its subsequent depletion on availability of sunlight. This has been proposed as the reason for the sudden appearance of enhanced concentrations of condensation nuclei during Arctic and Antarctic spring. Further, the strong increase of SO<sub>2</sub> to values of 80–100 pptv in the upper stratosphere through photolysis of H<sub>2</sub>SO<sub>4</sub> has been confirmed. Lower stratospheric variability of SO<sub>2</sub> could mainly be explained by volcanic activity, and no hints of a strong anthropogenic influence have been found. Regression analysis revealed a QBO (quasi-biennial oscillation) signal of the SO<sub>2</sub> time series in the tropics at about 30–35 km, an SAO (semi-annual oscillation) signal at tropical and subtropical latitudes above 32 km and annual periodics predominantly at high latitudes. Further, the analysis indicates a correlation with the solar cycle in the tropics and southern subtropics above 30 km. Significant negative linear trends are found in the tropical lower stratosphere, probably due to reduced tropical volcanic activity and at southern mid-latitudes above 35 km. A positive trend is visible in the lower and middle stratosphere at polar to subtropical southern latitudes.
-
An aerosol optical depth (AOD) three-dimensional variational data assimilation technique is developed for the Gridpoint Statistical Interpolation (GSI) system for which WRF-Chem forecasts are performed with a detailed sectional model, the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC). Within GSI, forward AOD and adjoint sensitivities are performed using Mie computations from the WRF-Chem optical properties module, providing consistency with the forecast. GSI tools such as recursive filters and weak constraints are used to provide correlation within aerosol size bins and upper and lower bounds for the optimization. The system is used to perform assimilation experiments with fine vertical structure and no data thinning or re-gridding on a 12 km horizontal grid over the region of California, USA, where improvements on analyses and forecasts is demonstrated. A first set of simulations was performed, comparing the assimilation impacts of using the operational MODIS (Moderate Resolution Imaging Spectroradiometer) dark target retrievals to those using observationally constrained ones, i.e., calibrated with AERONET (Aerosol RObotic NETwork) data. It was found that using the observationally constrained retrievals produced the best results when evaluated against ground based monitors, with the error in PM<sub>2.5</sub> predictions reduced at over 90% of the stations and AOD errors reduced at 100% of the monitors, along with larger overall error reductions when grouping all sites. A second set of experiments reveals that the use of fine mode fraction AOD and ocean multi-wavelength retrievals can improve the representation of the aerosol size distribution, while assimilating only 550 nm AOD retrievals produces no or at times degraded impact. While assimilation of multi-wavelength AOD shows positive impacts on all analyses performed, future work is needed to generate observationally constrained multi-wavelength retrievals, which when assimilated will generate size distributions more consistent with AERONET data and will provide better aerosol estimates.
-
This paper serves as an overview and discusses the main findings from the Border Air Quality and Meteorology Study (BAQS-Met) in southwestern Ontario in 2007. This region is dominated by the Great Lakes, shares borders with the United States and consistently experiences the highest ozone (O<sub>3</sub>) and fine particulate matter concentrations in Canada. The purpose of BAQS-Met was to improve our understanding of how lake-driven meteorology impacts air quality in the region, and to improve models used for forecasting and policy scenarios. Results show that lake breeze occurrence frequencies and inland penetration distances were significantly greater than realized in the past. Due to their effect on local meteorology, the lakes were found to enhance secondary O<sub>3</sub> and aerosol formation such that local anthropogenic emissions have their impact closer to the populated source areas than would otherwise occur in the absence of the lakes. Substantial spatial heterogeneity in O<sub>3</sub> was observed with local peaks typically 30 ppb above the regional values. Sulfate and secondary organic aerosol (SOA) enhancements were also linked to local emissions being transported in the lake breeze circulations. This study included the first detailed evaluation of regional applications of a high-resolution (2.5 km grid) air quality model in the Great Lakes region. The model showed that maxima in secondary pollutants occur in areas of convergence, in localized updrafts and in distinct pockets over the lake surfaces. These effects are caused by lake circulations interacting with the synoptic flow, with each other or with circulations induced by urban heat islands. Biogenic and anthropogenic emissions were both shown to play a role in the formation of SOA in the region. Detailed particle measurements and multivariate receptor models reveal that while individual particles are internally mixed, they often exist within more complex external mixtures. This makes it difficult to predict aerosol optical properties and further highlights the challenges facing aerosol modelling. The BAQS-Met study has led to a better understanding of the value of high-resolution (2.5 km) modelling for air quality and meteorological predictions and has led to several model improvements.
-
Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of the Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of a pollution accumulation event (27–29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer-controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near-edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm equivalent circular diameter) increased with plume age, as did the organic mass per particle. Comparison of the CARES spectro-microscopic dataset with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that fresh particles in Mexico City contained three times as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (ranging from 16.6 to 47.3%) was larger than at the CARES urban site (13.4–15.7%), and the most aged samples from CARES contained fewer carbon–carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements will allow for a comprehensive evaluation of aerosol process models used in climate research.
-
A new modal aerosol parameterization scheme, the statistical–numerical aerosol parameterization (SNAP), was developed for studying aerosol processes and aerosol–cloud interactions in regional or global models. SNAP applies statistical fitting on numerical results to generate accurate parameterization formulas without sacrificing details of the growth kernel. Processes considered in SNAP include fundamental aerosol processes as well as processes related to aerosol–cloud interactions. Comparison of SNAP with numerical solutions, analytical solutions, and binned aerosol model simulations showed that the new method performs well, with accuracy higher than that of the high-order numerical quadrature technique, and with much less computation time. The SNAP scheme has been implemented in regional air quality models, producing results very close to those using binned-size schemes or numerical quadrature schemes.
-
Continuous measurements of atmospheric mercury concentration and speciation play a key role in identifying mercury sources and its behavior in the atmosphere. In this study, speciated atmospheric mercury including gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and particle-bound mercury (PBM) were continuously measured at Miyun, a rural site in Beijing, China, from December 2008 to November 2009. The average GEM, RGM and PBM concentrations were found to be 3.22 ± 1.74, 10.1 ± 18.8 and 98.2 ± 112.7 pg m<sup>−3</sup>, respectively, about 2–20 times higher than the background concentration of the Northern Hemisphere. The results indicated that atmospheric mercury concentrations in northern China were highly affected by anthropogenic emissions. The atmospheric mercury showed obvious seasonal variations, with the highest seasonal average GEM concentration in summer (3.48 ng m<sup>−3</sup>) and the lowest value in winter (2.66 ng m<sup>−3</sup>). In autumn and winter a diurnal variation of GEM was observed, with peak levels in the late afternoon till midnight. Most of the high RGM concentration values occurred in the afternoon of all seasons due to the higher oxidation. The PBM concentration was higher in early morning of all seasons because of the the temperature inversion that increases in depth as the night proceeds. The ratio of GEM to CO indicates that residential boilers play an important role in the elevation of GEM in winter. The ratio of RGM to O<sub>3</sub> could be an indicator of the contribution of local primary sources. The ratio of PBM to PM<sub>2.5</sub> reveals that the air mass from the east and southwest of the site in spring and summer carries more atmospheric mercury. The HYSPLIT back-trajectory analysis indicated that the monitoring site is affected by local, regional and interregional sources simultaneously during heavy pollution episodes. The results from the potential source contribution function (PSCF) model indicate that the atmospheric transport predominantly from the northwest contributes to the elevated atmospheric mercury in winter and autumn, while the North China Plain (NCP) region and the northern part of the Yangtze River Delta (YRD) region are the major source areas for mercury pollution in spring and summer.
-
The absorption Ångström exponent (AAE) of externally mixed black carbon (BC<sub>Ext</sub>), or BC internally mixed with non-absorbing material (BC<sub>Int</sub>), is often used to determine the contribution of brown carbon (BrC) light absorption at short visible wavelengths. This attribution method contains assumptions with uncertainties that have not been formally assessed. We show that the potential range of AAE for BC<sub>Ext</sub> (or BC<sub>Int</sub>) in the atmosphere can reasonably lead to +7% to −22% uncertainty in BC<sub>Ext</sub> (or BC<sub>Int</sub>) absorption at short wavelengths derived from measurements made at longer wavelengths, where BrC is assumed not to absorb light. These uncertainties propagate to errors in the attributed absorption of BrC. For uncertainty in attributed BrC absorption to be ≤ ± 33%, 23% to 41% of total absorption must be sourced from BrC. These uncertainties would be larger if absorption by dust were also to be considered due to additional AAE assumptions. For data collected during a biomass-burning event, the mean difference between measured and AAE attributed BrC absorption was found to be 34% – an additional uncertainty in addition to the theoretical uncertainties presented. In light of the potential for introducing significant and poorly constrained errors, we caution against the universal application of the AAE method for attributing BrC absorption.
-
The influence of air pollutants, especially aerosols, on regional and global climate has been widely investigated, but only a very limited number of studies report their impacts on everyday weather. In this work, we present for the first time direct (observational) evidence of a clear effect of how a mixed atmospheric pollution changes the weather with a substantial modification in the air temperature and rainfall. By using comprehensive measurements in Nanjing, China, we found that mixed agricultural burning plumes with fossil fuel combustion pollution resulted in a decrease in the solar radiation intensity by more than 70%, a decrease in the sensible heat by more than 85%, a temperature drop by almost 10 K, and a change in rainfall during both daytime and nighttime. Our results show clear air pollution–weather interactions, and quantify how air pollution affects weather via air pollution–boundary layer dynamics and aerosol–radiation–cloud feedbacks. This study highlights cross-disciplinary needs to investigate the environmental, weather and climate impacts of the mixed biomass burning and fossil fuel combustion sources in East China.
-
This paper presents a set of observations and analyses of trace gas cross sections in the extratropical upper troposphere/lower stratosphere (UTLS). The spatially highly resolved (≈0.5 km vertically and 12.5 km horizontally) cross sections of ozone (O<sub>3</sub>), nitric acid (HNO<sub>3</sub>), and peroxyacetyl nitrate (PAN), retrieved from the measurements of the CRISTA-NF infrared limb sounder flown on the Russian M55-Geophysica, revealed intricate layer structures in the region of the subtropical tropopause break. The chemical structure in this region shows an intertwined stratosphere and troposphere. The observed filaments in all discussed trace gases are of a spatial scale of less than 0.8 km vertically and about 200 km horizontally across the jet stream. Backward trajectory calculations confirm that the observed filaments are the result of a breaking Rossby wave in the preceding days. An analysis of the trace gas relationships between PAN and O<sub>3</sub> identifies four distinct groups of air mass: polluted subtropical tropospheric air, clean tropical upper-tropospheric air, the lowermost stratospheric air, and air from the deep stratosphere. The tracer relationships further allow the identification of tropospheric, stratospheric, and the transitional air mass made of a mixture of UT and LS air. Mapping of these air mass types onto the geo-spatial location in the cross sections reveals a highly structured extratropical transition layer (ExTL). Finally, the ratio between the measured reactive nitrogen species (HNO<sub>3</sub> + PAN + ClONO<sub>2</sub>) and O<sub>3</sub> is analysed to estimate the influence of tropospheric pollution on the extratropical UTLS. <br><br> In combination, these diagnostics provide the first example of a multi-species two-dimensional picture of the inhomogeneous distribution of chemical species within the UTLS region. Since Rossby wave breaking occurs frequently in the region of the tropopause break, these observed fine-scale filaments are likely ubiquitous in the region. The implications of the layered structure for chemistry and radiation need to be examined, and the representation of this structure in chemistry-climate models is discussed.
-
The sensitivity of the process parameters of the Biosphere Energy Transfer HYdrology (BETHY) model to choices of atmospheric concentration network, high frequency terrestrial fluxes, and the choice of flux measurement network is investigated by using a carbon cycle data assimilation system. We use BETHY-generated fluxes as a proxy of flux measurements. Results show that monthly mean or low-frequency observations of CO<sub>2</sub> concentration provide strong constraints on parameters relevant for net flux (NEP) but only weak constraints for parameters controlling gross fluxes. The use of high-frequency CO<sub>2</sub> concentration observations, which has led to great refinement of spatial scales in inversions of net flux, adds little to the observing system in the Carbon Cycle Data Assimilation System (CCDAS) case. This unexpected result is explained by the fact that the stations of the CO<sub>2</sub> concentration network we use are not well placed to measure such high frequency signals. Indeed, CO<sub>2</sub> concentration sensitivities relevant for such high frequency fluxes are found to be largely confined in the vicinity of the corresponding fluxes, and are therefore not well observed by background monitoring stations. In contrast, our results clearly show the potential of flux measurements to better constrain the model parameters relevant for gross primary productivity (GPP) and net primary productivity (NPP). Given uncertainties in the spatial description of ecosystem functions, we recommend a combined observing strategy.
