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PM<sub>2.5</sub> was collected during a winter campaign at two southern England sites, urban background North Kensington (NK) and rural Harwell (HAR), in January–February 2012. Multiple organic and inorganic source tracers were analysed and used in a Chemical Mass Balance (CMB) model, which apportioned seven separate primary sources, that explained on average 53% (NK) and 56% (HAR) of the organic carbon (OC), including traffic, woodsmoke, food cooking, coal combustion, vegetative detritus, natural gas and dust/soil. With the addition of source tracers for secondary biogenic aerosol at the NK site, 79% of organic carbon was accounted for. Secondary biogenic sources were represented by oxidation products of α-pinene and isoprene, but only the former made a substantial contribution to OC. Particle source contribution estimates for PM<sub>2.5</sub> mass were obtained by the conversion of the OC estimates and combining with inorganic components ammonium nitrate, ammonium sulfate and sea salt. Good mass closure was achieved with 81% (92% with the addition of the secondary biogenic source) and 83% of the PM<sub>2.5</sub> mass explained at NK and HAR respectively, with the remainder being secondary organic matter. While the most important sources of OC are vehicle exhaust (21 and 16%) and woodsmoke (15 and 28%) at NK and HAR respectively, food cooking emissions are also significant, particularly at the urban NK site (11% of OC), in addition to the secondary biogenic source, only measured at NK, which represented about 26%. In comparison, the major source components for PM<sub>2.5</sub> at NK and HAR are inorganic ammonium salts (51 and 56%), vehicle exhaust emissions (8 and 6%), secondary biogenic (10% measured at NK only), woodsmoke (4 and 7%) and sea salt (7 and 8%), whereas food cooking (4 and 1%) showed relatively smaller contributions to PM<sub>2.5</sub>. Results from the CMB model were compared with source contribution estimates derived from the AMS-PMF method. The overall mass of organic matter accounted for is rather similar for the two methods. However, appreciably different concentrations were calculated for the individual primary organic matter contributions, although for most source categories the CMB and AMS-PMF results were highly correlated (<i>r</i><sup>2</sup> = 0.69–0.91). In comparison with the CMB model, the AMS appears to overestimate the biomass burning/coal and food cooking sources by a factor of around 1.5 to 2 while estimates of the traffic source are rather similar for each model. The largest divergence is in the primary/secondary organic matter split, with the AMS estimating an appreciably smaller secondary component. Possible reasons for these discrepancies are discussed, but despite these substantial divergences, the strong correlation of the two methods gives some confidence in their application.
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Multiple axis differential absorption spectroscopy (MAX-DOAS) measurements of bromine monoxide (BrO) probed the vertical structure of halogen activation events during March–May 2012 at Barrow, Alaska. An analysis of the BrO averaging kernels and degrees of freedom obtained by optimal-estimation-based inversions from raw MAX-DOAS measurements reveals the information is best represented by reducing the retrieved BrO profile to two quantities: the integrated column from the surface through 200 m (VCD<sub>200 m</sub>), and the lower tropospheric vertical column density (LT-VCD), which represents the integrated column of BrO from the surface through 2 km. The percentage of lower tropospheric BrO in the lowest 200 m was found to be highly variable ranging from shallow layer events, where BrO is present primarily in the lowest 200 m, to distributed column events where BrO is observed at higher altitudes. The highest observed LT-VCD events occurred when BrO was distributed throughout the lower troposphere, rather than concentrated near the surface. Atmospheric stability in the lowest 200 m influenced the percentage of LT-VCD that is in the lowest 200 m, with inverted temperature structures having a first-to-third quartile range (Q1–Q3) of VCD<sub>200 m</sub>/LT-VCD from 15–39%, while near-neutral-temperature structures had a Q1–Q3 range of 7–13%. Data from this campaign show no clear influence of wind speed on either lower tropospheric bromine activation (LT-VCD) or the vertical distribution of BrO, while examination of seasonal trends and the temperature dependence of the vertical distribution supported the conclusion that the atmospheric stability affects the vertical distribution of BrO.
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Naturally emitted from the oceans, iodine compounds efficiently destroy atmospheric ozone and reduce its positive radiative forcing effects in the troposphere. Emissions of inorganic iodine have been experimentally shown to depend on the deposition to the oceans of tropospheric ozone, whose concentrations have significantly increased since 1850 as a result of human activities. A chemistry–climate model is used herein to quantify the current ocean emissions of inorganic iodine and assess the impact that the anthropogenic increase in tropospheric ozone has had on the natural cycle of iodine in the marine environment since pre-industrial times. Our results indicate that the human-driven enhancement of tropospheric ozone has doubled the oceanic inorganic iodine emissions following the reaction of ozone with iodide at the sea surface. The consequent build-up of atmospheric iodine, with maximum enhancements of up to 70% with respect to pre-industrial times in continental pollution outflow regions, has in turn accelerated the ozone chemical loss over the oceans with strong spatial patterns. We suggest that this ocean–atmosphere interaction represents a negative geochemical feedback loop by which current ocean emissions of iodine act as a natural buffer for ozone pollution and its radiative forcing in the global marine environment.
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The Brewer–Dobson circulation (mainly meridional circulation) is very important for stratospheric ozone dynamics and thus for the overall state of the stratosphere. There are some indications that the meridional circulation in the stratosphere could be longitudinally dependent, which would have an impact on the ozone distribution. Therefore, we analyse here the meridional component of the stratospheric wind at northern middle latitudes to study its longitudinal dependence. The analysis is based on the NCEP/NCAR-1 (National Centers for Environmental Prediction and the National Center for Atmospheric Research), MERRA (Modern Era-Retrospective Analysis) and ERA-Interim (European Centre for Medium-Range Weather Forecasts (ECMWF) Re-Analysis Interim) reanalysis data. The well-developed two-core structure of strong but opposite meridional winds, one in each hemisphere at 10 hPa at higher northern middle latitudes, and a less pronounced five-core structure at 100 hPa are identified. In the central areas of the two-core structure the meridional and zonal wind magnitudes are comparable. The two-core structure at 10 hPa is almost identical for all three different reanalysis data sets in spite of the different time periods covered. The two-core structure is not associated with tides. However, the two-core structure at the 10 hPa level is related to the Aleutian pressure high at 10 hPa. Zonal wind, temperature and the ozone mixing ratio at 10 hPa also exhibit the effect of the Aleutian high, which thus affects all parameters of the Northern Hemisphere middle stratosphere. Long-term trends in the meridional wind in the "core" areas are significant at the 99% level. Trends of meridional winds are negative during the period of ozone depletion development (1970–1995), while they are positive after the ozone trend turnaround (1996–2012). Meridional wind trends are independent of the sudden stratospheric warming (SSW) occurrence and the quasi-biennial oscillation (QBO) phase. The influence of the 11-year solar cycle on stratospheric winds has been identified only during the west phase of QBO. The well-developed two-core structure in the meridional wind illustrates the limitations of application of the zonal mean concept in studying stratospheric circulation.
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Stratospheric turbulence is important for the mixing of trace species and the energy balance, but direct measurements are sparse due to the required resolution and accuracy. Recently, turbulence parameters such as the energy dissipation rate ε were inferred from standard radiosonde data by means of a Thorpe analysis. To this end, layers with vertically decreasing potential temperature are analysed, which is expected to indicate turbulence. Such an application assumes a proportionality between the Thorpe length <i>L</i><sub>T</sub> and the Ozmidov scale <i>L</i><sub>O</sub>. While this relation is accepted for the ocean, experimental evidence for such proportionality in the stratosphere is sparse. We have developed a high-resolution (8 kHz) turbulence measurement system called LITOS (Leibniz Institute Turbulence Observations in the Stratosphere), which for the first time resolves the inner scale of turbulence in the stratosphere. Therewith the energy dissipation rate ε can be determined by spectral analysis. This independent value for ε enables us to check the relation <i>L</i><sub>O</sub> ∝ <i>L</i><sub>T</sub>. In our measurements no such proportionality can be seen, although the mean of the ratio <i>L</i><sub>O</sub>/<i>L</i><sub>T</sub> is close to what is assumed in radiosonde analyses. Dissipation rates for individual layers obtained from radiosondes deviate up to a factor of ~3000 from those obtained by spectral analysis. Some turbulent layers measured by LITOS are not observed by the radiosonde at all, and vice versa. However, statements about the statistical mean seem to be possible by Thorpe analysis.
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Rainfall is one of the most important aspects of climate, but the extent to which atmospheric ice nuclei (IN) influence its formation, quantity, frequency, and location is not clear. Microorganisms and other biological particles are released following rainfall and have been shown to serve as efficient IN, in turn impacting cloud and precipitation formation. Here we investigated potential long-term effects of IN on rainfall frequency and quantity. Differences in IN concentrations and rainfall after and before days of large rainfall accumulation (i.e., key days) were calculated for measurements made over the past century in southeastern and southwestern Australia. Cumulative differences in IN concentrations and daily rainfall quantity and frequency as a function of days from a key day demonstrated statistically significant increasing logarithmic trends (<i>R</i><sup>2</sup> > 0.97). Based on observations that cumulative effects of rainfall persisted for about 20 days, we calculated cumulative differences for the entire sequence of key days at each site to create a historical record of how the differences changed with time. Comparison of pre-1960 and post-1960 sequences most commonly showed smaller rainfall totals in the post-1960 sequences, particularly in regions downwind from coal-fired power stations. This led us to explore the hypothesis that the increased leaf surface populations of IN-active bacteria due to rain led to a sustained but slowly diminishing increase in atmospheric concentrations of IN that could potentially initiate or augment rainfall. This hypothesis is supported by previous research showing that leaf surface populations of the ice-nucleating bacterium <i>Pseudomonas syringae</i> increased by orders of magnitude after heavy rain and that microorganisms become airborne during and after rain in a forest ecosystem. At the sites studied in this work, aerosols that could have initiated rain from sources unrelated to previous rainfall events (such as power stations) would automatically have reduced the influences on rainfall of those whose concentrations were related to previous rain, thereby leading to inhibition of feedback. The analytical methods described here provide means to map and delimit regions where rainfall feedback mediated by microorganisms is suspected to occur or has occurred historically, thereby providing rational means to establish experimental set-ups for verification.
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This paper evaluates and discusses the quality of the stratospheric ozone analyses delivered in near real time by the MACC (Monitoring Atmospheric Composition and Climate) project during the 3-year period between September 2009 and September 2012. Ozone analyses produced by four different chemical data assimilation (CDA) systems are examined and compared: the Integrated Forecast System coupled to the Model for OZone And Related chemical Tracers (IFS-MOZART); the Belgian Assimilation System for Chemical ObsErvations (BASCOE); the Synoptic Analysis of Chemical Constituents by Advanced Data Assimilation (SACADA); and the Data Assimilation Model based on Transport Model version 3 (TM3DAM). The assimilated satellite ozone retrievals differed for each system; SACADA and TM3DAM assimilated only total ozone observations, BASCOE assimilated profiles for ozone and some related species, while IFS-MOZART assimilated both types of ozone observations. <br><br> All analyses deliver total column values that agree well with ground-based observations (biases < 5%) and have a realistic seasonal cycle, except for BASCOE analyses, which underestimate total ozone in the tropics all year long by 7 to 10%, and SACADA analyses, which overestimate total ozone in polar night regions by up to 30%. The validation of the vertical distribution is based on independent observations from ozonesondes and the ACE-FTS (Atmospheric Chemistry Experiment – Fourier Transform Spectrometer) satellite instrument. It cannot be performed with TM3DAM, which is designed only to deliver analyses of total ozone columns. Vertically alternating positive and negative biases are found in the IFS-MOZART analyses as well as an overestimation of 30 to 60% in the polar lower stratosphere during polar ozone depletion events. SACADA underestimates lower stratospheric ozone by up to 50% during these events above the South Pole and overestimates it by approximately the same amount in the tropics. The three-dimensional (3-D) analyses delivered by BASCOE are found to have the best quality among the three systems resolving the vertical dimension, with biases not exceeding 10% all year long, at all stratospheric levels and in all latitude bands, except in the tropical lowermost stratosphere. <br><br> The northern spring 2011 period is studied in more detail to evaluate the ability of the analyses to represent the exceptional ozone depletion event, which happened above the Arctic in March 2011. Offline sensitivity tests are performed during this month and indicate that the differences between the forward models or the assimilation algorithms are much less important than the characteristics of the assimilated data sets. They also show that IFS-MOZART is able to deliver realistic analyses of ozone both in the troposphere and in the stratosphere, but this requires the assimilation of observations from nadir-looking instruments as well as the assimilation of profiles, which are well resolved vertically and extend into the lowermost stratosphere.
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The global budget of tropospheric carbonyl sulfide (OCS) is believed to be at equilibrium because background air concentrations have remained roughly stable over at least the last decade. Since the uptake of OCS by leaves (associated with photosynthesis) and soils have been revised significantly upwards recently, an equilibrated budget can only be obtained with a compensatory source of OCS. It has been assumed that the missing source of OCS comes from the low-latitude ocean, following the incident solar flux. The present work uses parameterizations of major production and removal processes of organic compounds in the NEMO-PISCES (Nucleus for European Modelling of the Ocean, Pelagic Interaction Scheme for Carbon and Ecosystem Studies) ocean general circulation and biogeochemistry model to assess the marine source of OCS. In addition, the OCS photo-production rates computed with the NEMO-PISCES model~were evaluated independently using the UV absorption coefficient of chromophoric dissolved organic matter (derived from satellite ocean color data) and apparent quantum yields available in the literature. Our simulations show global direct marine emissions of OCS in the range of 573–3997 GgS yr<sup>−1</sup>, depending mostly on the quantification of the absorption rate of chromophoric dissolved organic matter. The high estimates of that range are unlikely, as they correspond to a formulation that most likely overestimate photo-production process. Low and medium (813 GgS yr<sup>−1</sup>) estimates derived from the NEMO-PISCES model are however consistent spatially and temporally~with the suggested missing source of Berry et al. (2013), allowing us thus to close the global budget of OCS given the recent estimates of leaf and soil OCS uptake.
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Recent epidemiological evidence supports the hypothesis that health effects from inhalation of ambient particulate matter (PM) are governed by more than just the mass of PM inhaled. Both specific chemical components and sources have been identified as important contributors to mortality and hospital admissions, even when these end points are unrelated to PM mass. Sources may cause adverse health effects via their ability to produce reactive oxygen species in the body, possibly due to the transition metal content of the PM. Our goal is to quantify the oxidative potential of ambient particle sources collected during two seasons in Fresno, CA, using the dithiothreitol (DTT) assay. We collected PM from different sources or source combinations into different ChemVol (CV) samplers in real time using a novel source-oriented sampling technique based on single-particle mass spectrometry. We segregated the particles from each source-oriented mixture into two size fractions – ultrafine <i>D</i><sub>p</sub> ≤ 0.17 μm) and submicron fine (0.17 μm ≤ <i>D</i><sub>p</sub> ≤ 1.0 μm) – and measured metals and the rate of DTT loss in each PM extract. We find that the mass-normalized oxidative potential of different sources varies by up to a factor of 8 and that submicron fine PM typically has a larger mass-normalized oxidative potential than ultrafine PM from the same source. Vehicular emissions, regional source mix, commute hours, daytime mixed layer, and nighttime inversion sources exhibit the highest mass-normalized oxidative potential. When we apportion DTT activity for total PM sampled to specific chemical compounds, soluble copper accounts for roughly 50% of total air-volume-normalized oxidative potential, soluble manganese accounts for 20%, and other unknown species, likely including quinones and other organics, account for 30%. During nighttime, soluble copper and manganese largely explain the oxidative potential of PM, while daytime has a larger contribution from unknown (likely organic) species.
