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Bioaerosols pose risks to human health and agriculture and may influence the evolution of mixed-phase clouds and the hydrological cycle on local and regional scales. The availability and reliability of methods and data on the abundance and properties of atmospheric bioaerosols, however, are rather limited. Here we analyze and compare data from different real-time ultraviolet laser/light-induced fluorescence (UV-LIF) instruments with results from a culture-based spore sampler and offline molecular tracers for airborne fungal spores in a semi-arid forest in the southern Rocky Mountains of Colorado. Commercial UV-APS (ultraviolet aerodynamic particle sizer) and WIBS-3 (wideband integrated bioaerosol sensor, version 3) instruments with different excitation and emission wavelengths were utilized to measure fluorescent aerosol particles (FAPs) during both dry weather conditions and periods heavily influenced by rain. Seven molecular tracers of bioaerosols were quantified by analysis of total suspended particle (TSP) high-volume filter samples using a high-performance anion-exchange chromatography system with pulsed amperometric detection (HPAEC-PAD). From the same measurement campaign, Huffman et al. (2013) previously reported dramatic increases in total and fluorescent particle concentrations during and immediately after rainfall and also showed a strong relationship between the concentrations of FAPs and ice nuclei (Huffman et al., 2013; Prenni et al., 2013). Here we investigate molecular tracers and show that during rainy periods the atmospheric concentrations of arabitol (35.2 ± 10.5 ng m<sup>−3</sup>) and mannitol (44.9 ± 13.8 ng m<sup>−3</sup>) were 3–4 times higher than during dry periods. During and after rain, the correlations between FAP and tracer mass concentrations were also significantly improved. Fungal spore number concentrations on the order of 10<sup>4</sup> m<sup>−3</sup>, accounting for 2–5 % of TSP mass during dry periods and 17–23 % during rainy periods, were obtained from scaling the tracer measurements and from multiple analysis methods applied to the UV-LIF data. Endotoxin concentrations were also enhanced during rainy periods, but showed no correlation with FAP concentrations. Average mass concentrations of erythritol, levoglucosan, glucose, and (1 → 3)-<i>β</i>-D-glucan in TSP samples are reported separately for dry and rainy weather conditions. Overall, the results indicate that UV-LIF measurements can be used to infer fungal spore concentrations, but substantial development of instrumental and data analysis methods appears to be required for improved quantification.
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There are two fundamental mechanisms through which cirrus clouds form; homo- and heterogeneous ice nucleation (henceforth hom and het). The relative contribution of each mechanism to ice crystal production often determines the microphysical and radiative properties of a cirrus cloud. A new satellite remote sensing method is described in this study to estimate cirrus cloud ice particle number concentration and the relative contribution of hom and het to cirrus cloud formation as a function of altitude, latitude, season and surface type (e.g. land vs. ocean). This method uses co-located observations from the Infrared Imaging Radiometer (IIR) and from the CALIOP (<i>Cloud and Aerosol Lidar with Orthogonal Polarization</i>) lidar aboard the CALIPSO (<i>Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation</i>) polar orbiting satellite, employing IIR channels at 10.6 μm and 12.05 μm. The method is applied here to single-layered clouds of visible optical depth between about 0.3 and 3. Two years of Version 3 data have been analyzed for the years 2008 and 2013, with each season characterized in terms of 532 nm cirrus cloud centroid altitude and temperature, the cirrus cloud ice particle number concentration, effective diameter, layer-average ice water content and visible optical depth. Using a conservative criterion for hom cirrus, on average, the sampled cirrus clouds formed through hom occur about 43 % of the time in the Arctic and 50 % of the time in the Antarctic, and during winter at mid-latitudes in the Northern Hemisphere, hom cirrus occur 37 % of the time. Elsewhere (and during other seasons in the Northern Hemisphere mid-latitudes), this hom cirrus fraction is lower. Processes that could potentially explain these observations are discussed, as well as the potential relevancy of these results to ice nucleation studies, climate modeling and jet-stream dynamics.
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Retrievals of tropospheric NO<sub>2</sub> columns from UV–visible observations of reflected sunlight require a priori vertical profiles to account for the variation in sensitivity of the observations to NO<sub>2</sub> at different altitudes. These profiles vary in space and time but are usually approximated using models that do not resolve the full details of this variation. Currently, no operational retrieval simulates these a priori profiles at both high spatial and high temporal resolution. Here we examine the additional benefits of daily variations in a priori profiles for retrievals already simulating a priori NO<sub>2</sub> profiles at sufficiently high spatial resolution to identify variations of NO<sub>2</sub> within urban plumes. We show the effects of introducing daily variation into a priori profiles can be as large as 40 % and 3 × 10<sup>15</sup> molec. cm<sup>−2</sup> for an individual day and lead to corrections as large as −13 % for a monthly average in a case study of Atlanta, GA, USA. Additionally, we show that NO<sub><i>x</i></sub> emissions estimated from space-based remote sensing using daily, high-spatial-resolution a priori profiles are ∼ 100 % greater than those of a retrieval using spatially coarse a priori profiles, and 26–40 % less than those of a retrieval using monthly averaged high-spatial-resolution profiles.
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Global simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) using artificial tracers of air mass origin are used to analyze transport mechanisms from the Asian monsoon region into the lower stratosphere. In a case study, the transport of air masses from the Asian monsoon anticyclone originating in India/China by an eastward-migrating anticyclone which broke off from the main anticyclone on 20 September 2012 and filaments separated at the northeastern flank of the anticyclone are analyzed. Enhanced contributions of young air masses (younger than 5 months) are found within the separated anticyclone confined at the top by the thermal tropopause. Further, these air masses are confined by the anticyclonic circulation and, on the polar side, by the subtropical jet such that the vertical structure resembles a bubble within the upper troposphere. Subsequently, these air masses are transported eastwards along the subtropical jet and enter the lower stratosphere by quasi-horizontal transport in a region of double tropopauses most likely associated with Rossby wave breaking events. As a result, thin filaments with enhanced signatures of tropospheric trace gases were measured in the lower stratosphere over Europe during the TACTS/ESMVal campaign in September 2012 in very good agreement with CLaMS simulations. Our simulations demonstrate that source regions in Asia and in the Pacific Ocean have a significant impact on the chemical composition of the lower stratosphere of the Northern Hemisphere. Young, moist air masses, in particular at the end of the monsoon season in September/October 2012, flooded the extratropical lower stratosphere in the Northern Hemisphere with contributions of up to ≈ 30 % at 380 K (with the remaining fraction being aged air). In contrast, the contribution of young air masses to the Southern Hemisphere is much lower. At the end of October 2012, approximately 1.5 ppmv H<sub>2</sub>O is found in the lower Northern Hemisphere stratosphere (at 380 K) from source regions both in Asia and in the tropical Pacific compared to a mean water vapor content of ≈ 5 ppmv. In addition to this main transport pathway from the Asian monsoon anticyclone to the east along the subtropical jet and subsequent transport into the northern lower stratosphere, a second horizontal transport pathway out of the anticyclone to the west into the tropics (TTL) is found in agreement with MIPAS HCFC-22 measurements.
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The Bermuda High (BH) quasi-permanent pressure system is the key large-scale circulation pattern influencing summertime weather over the eastern and southern US. Here we developed a multiple linear regression (MLR) model to characterize the effect of the BH on year-to-year changes in monthly-mean maximum daily 8 h average (MDA8) ozone in the Houston–Galveston–Brazoria (HGB) metropolitan region during June, July, and August (JJA). The BH indicators include the longitude of the BH western edge (BH-Lon) and the BH intensity index (BHI) defined as the pressure gradient along its western edge. Both BH-Lon and BHI are selected by MLR as significant predictors (<i>p</i> < 0.05) of the interannual (1990–2015) variability of the HGB-mean ozone throughout JJA, while local-scale meridional wind speed is selected as an additional predictor for August only. Local-scale temperature and zonal wind speed are not identified as important factors for any summer month. The best-fit MLR model can explain 61–72 % of the interannual variability of the HGB-mean summertime ozone over 1990–2015 and shows good performance in cross-validation (<i>R</i><sup>2</sup> higher than 0.48). The BH-Lon is the most important factor, which alone explains 38–48 % of such variability. The location and strength of the Bermuda High appears to control whether or not low-ozone maritime air from the Gulf of Mexico can enter southeastern Texas and affect air quality. This mechanism also applies to other coastal urban regions along the Gulf Coast (e.g., New Orleans, LA, Mobile, AL, and Pensacola, FL), suggesting that the BH circulation pattern can affect surface ozone variability through a large portion of the Gulf Coast.
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Chlorofluorocarbons (CFCs) are ozone-depleting substances as well as strong greenhouse gases, and the control of their production and use under the Montreal Protocol has had demonstrable benefits to both mitigation of increasing surface UV radiation and climate forcing. A global ban on consumption came into force in 2010, but there is evidence of continuing emissions of certain CFCs from a range of sources. One compound has received little attention in the literature, namely CFC-114 (C<sub>2</sub>Cl<sub>2</sub>F<sub>4</sub>). Of particular interest here is the differentiation between CFC-114 (CClF<sub>2</sub>CClF<sub>2</sub>) and its asymmetric isomeric form CFC-114a (CF<sub>3</sub>CCl<sub>2</sub>F) as atmospheric long-term measurements in the peer-reviewed literature to date have been assumed to represent the sum of both isomers with a time-invariant isomeric speciation. Here we report the first long-term measurements of the two isomeric forms separately, and find that they have different origins and trends in the atmosphere. <br><br> Air samples collected at Cape Grim (41° S), Australia, during atmospheric background conditions since 1978, combined with samples collected from deep polar snow (firn) enable us to obtain a near-complete record of both gases since their initial production and release in the 1940s. Both isomers were present in the unpolluted atmosphere in comparably small amounts before 1960. The mixing ratio of CFC-114 doubled from 7.9 to 14.8 parts per trillion (ppt) between the start of the Cape Grim record in 1978 and the end of our record in 2014, while over the same time CFC-114a trebled from 0.35 to 1.03 ppt. Mixing ratios of both isomers are slowly decreasing by the end of this period. This is consistent with measurements of recent aircraft-based samples showing no significant interhemispheric mixing ratio gradient. <br><br> We also find that the fraction of CFC-114a mixing ratio relative to that of CFC-114 increased from 4.2 to 6.9 % over the 37-year period. This contradicts the current tacit assumption used in international climate change and ozone depletion assessments that both isomers have been largely co-emitted and that their atmospheric concentration ratio has remained approximately constant in time. Complementary observations of air collected in Taiwan indicate a persisting source of CFC-114a in South East Asia which may have been contributing to the changing balance between the two isomers. <br><br> In addition we present top-down global annual emission estimates of CFC-114 and CFC-114a derived from these measurements using a two-dimensional atmospheric chemistry-transport model. In general, the emissions for both compounds grew steadily during the 1980s, followed by a substantial reduction from the late 1980s onwards, which is consistent with the reduction of emission in response to the Montreal Protocol, and broadly consistent with bottom-up estimates derived by industry. However, we find that small but significant emissions of both isomers remain in 2014. Moreover the inferred changes to the ratio of emissions of the two isomers since the 1990s also indicate that the sources of the two gases are, in part, independent.
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Persistent organic pollutants (POPs) are of considerable concern due to their well-recognized toxicity and their potential to bioaccumulate and engage in long-range transport. These compounds are semi-volatile and, therefore, create a partition between vapour and condensed phases in the atmosphere, while both phases can undergo chemical reactions. This work describes the extension of the Community Multiscale Air Quality (CMAQ) modelling system to POPs with a focus on establishing an adaptable framework that accounts for gaseous chemistry, heterogeneous reactions, and gas-particle partitioning (GPP). The effect of GPP is assessed by implementing a set of independent parameterizations within the CMAQ aerosol module, including the Junge–Pankow (JP) adsorption model, the Harner–Bidleman (HB) organic matter (OM) absorption model, and the dual Dachs–Eisenreich (DE) black carbon (BC) adsorption and OM absorption model. Use of these descriptors in a modified version of CMAQ for benzo[a]pyrene (BaP) results in different fate and transport patterns as demonstrated by regional-scale simulations performed for a European domain during 2006. The dual DE model predicted 24.1 % higher average domain concentrations compared to the HB model, which was in turn predicting 119.2 % higher levels compared to the baseline JP model. Evaluation with measurements from the European Monitoring and Evaluation Programme (EMEP) reveals the capability of the more extensive DE model to better capture the ambient levels and seasonal behaviour of BaP. It is found that the heterogeneous reaction of BaP with O<sub>3</sub> may decrease its atmospheric lifetime by 25.2 % (domain and annual average) and near-ground concentrations by 18.8 %. Marginally better model performance was found for one of the six EMEP stations (Košetice) when heterogeneous BaP reactivity was included. Further analysis shows that, for the rest of the EMEP locations, the model continues to underestimate BaP levels, an observation that can be attributed to low emission estimates for such remote areas. These findings suggest that, when modelling the fate and transport of organic pollutants on large spatio-temporal scales, the selection and parameterization of GPP can be as important as degradation (reactivity).
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The 2015/16 Northern Hemisphere winter stratosphere appeared to have the greatest potential yet seen for record Arctic ozone loss. Temperatures in the Arctic lower stratosphere were at record lows from December 2015 through early February 2016, with an unprecedented period of temperatures below ice polar stratospheric cloud thresholds. Trace gas measurements from the Aura Microwave Limb Sounder (MLS) show that exceptional denitrification and dehydration, as well as extensive chlorine activation, occurred throughout the polar vortex. Ozone decreases in 2015/16 began earlier and proceeded more rapidly than those in 2010/11, a winter that saw unprecedented Arctic ozone loss. However, on 5–6 March 2016 a major final sudden stratospheric warming ("major final warming", MFW) began. By mid-March, the mid-stratospheric vortex split after being displaced far off the pole. The resulting offspring vortices decayed rapidly preceding the full breakdown of the vortex by early April. In the lower stratosphere, the period of temperatures low enough for chlorine activation ended nearly a month earlier than that in 2011 because of the MFW. Ozone loss rates were thus kept in check because there was less sunlight during the cold period. Although the winter mean volume of air in which chemical ozone loss could occur was as large as that in 2010/11, observed ozone values did not drop to the persistently low values reached in 2011.<br><br>We use MLS trace gas measurements, as well as mixing and polar vortex diagnostics based on meteorological fields, to show how the timing and intensity of the MFW and its impact on transport and mixing halted chemical ozone loss. Our detailed characterization of the polar vortex breakdown includes investigations of individual offspring vortices and the origins and fate of air within them. Comparisons of mixing diagnostics with lower-stratospheric N<sub>2</sub>O and middle-stratospheric CO from MLS (long-lived tracers) show rapid vortex erosion and extensive mixing during and immediately after the split in mid-March; however, air in the resulting offspring vortices remained isolated until they disappeared. Although the offspring vortices in the lower stratosphere survived longer than those in the middle stratosphere, the rapid temperature increase and dispersal of chemically processed air caused active chlorine to quickly disappear. Furthermore, ozone-depleted air from the lower-stratospheric vortex core was rapidly mixed with ozone rich air from the vortex edge and midlatitudes during the split. The impact of the 2016 MFW on polar processing was the latest in a series of unexpected events that highlight the diversity of potential consequences of sudden warming events for Arctic ozone loss.
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Despite a general decline in ozone depleting substances in the stratosphere due to the multi-national commitment to substantially reduce the emissions of their precursors, the magnitude of Arctic polar ozone loss has not decreased in recent years. Thus new observations at cold conditions can help to enhance our knowledge of polar stratospheric cloud (PSC) formation and life cycle which is of relevance for Arctic ozone loss. In the unique winter 2015/16, cold and persistent areas with temperatures below the ice frost point T<sub>ice</sub> developed in the Arctic stratosphere, caused by reduced perturbations of the polar vortex through planetary waves. Due to these extreme conditions, unprecedented and widespread ice PSCs formed and persisted for more than a month in the Arctic. These ice PSCs were repeatedly detected by lidars on the CALIPSO satellite and on the high altitude long range research aircraft HALO. A new lower threshold of the backscatter ratio<sup>−1</sup> of 0.3 for ice PSCs derived from high-resolution lidar measurements at 532 nm wavelength leads to enhanced ice PSC coverage compared to previous analysis. The ice PSCs were generally surrounded by nitric acid trihydrate (NAT) and supercooled ternary solution (STS) clouds. By combining optical PSC data and trajectory analysis, we investigate ice formation pathways. In addition to ice nucleation in STSm with meteoric dust, we find that ice nucleation on pre-existing NAT may play an important role in polar winter. Persistent synoptic-scale Arctic ice PSCs have not been observed so far. Hence, ice PSCs are a sensitive marker for cold stratospheric winter temperatures modulated by natural variability and climate change.
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Surface ozone concentrations in Mexico City frequently exceed the Mexican standard and have proven difficult to forecast due to changes in meteorological conditions at its tropical location. The Madden–Julian Oscillation (MJO) is largely responsible for intraseasonal variability in the tropics. Circulation patterns in the lower and upper troposphere and precipitation are associated with the oscillation as it progresses eastward around the planet. It is typically described by phases (labeled 1 through 8), which correspond to the broad longitudinal location of the active component of the oscillation with enhanced precipitation. In this study we evaluate the intraseasonal variability of winter and summer surface ozone concentrations in Mexico City, which was investigated over the period 1986–2014 to determine if there is a modulation by the MJO that would aid in the forecast of high-pollution episodes. <br><br> Over 1 000 000 hourly observations of surface ozone from five stations around the metropolitan area were standardized and then binned by active phase of the MJO, with phase determined using the real-time multivariate MJO index. Highest winter ozone concentrations were found in Mexico City on days when the MJO was active and in phase 2 (over the Indian Ocean), and highest summer ozone concentrations were found on days when the MJO was active and in phase 6 (over the western Pacific Ocean). Lowest winter ozone concentrations were found during active MJO phase 8 (over the eastern Pacific Ocean), and lowest summer ozone concentrations were found during active MJO phase 1 (over the Atlantic Ocean). Anomalies of reanalysis-based cloud cover and UV-B radiation supported the observed variability in surface ozone in both summer and winter: MJO phases with highest ozone concentration had largest positive UV-B radiation anomalies and lowest cloud-cover fraction, while phases with lowest ozone concentration had largest negative UV-B radiation anomalies and highest cloud-cover fraction. Furthermore, geopotential height anomalies at 250 hPa favoring reduced cloudiness, and thus elevated surface ozone, were found in both seasons during MJO phases with above-normal ozone concentrations. Similar height anomalies at 250 hPa favoring enhanced cloudiness, and thus reduced surface ozone, were found in both seasons during MJO phases with below-normal ozone concentrations. These anomalies confirm a physical pathway for MJO modulation of surface ozone via modulation of the upper troposphere.
