Index Geophysics

Items

• Trends and variations in CO, C2H6, and HCN in the Southern Hemisphere point to the declining anthropogenic emissions of CO and C2H6

  We analyse the carbon monoxide (CO), ethane (C₂H₆) and hydrogen cyanide (HCN) partial columns (from the ground to 12 km) derived from measurements by ground-based solar Fourier Transform Spectroscopy at Lauder, New Zealand (45° S, 170° E), and at Arrival Heights, Antarctica (78° S, 167° E), from 1997 to 2009. Significant negative trends are calculated for all species at both locations, based on the daily-mean observed time series, namely CO (−0.94 ± 0.47% yr⁻¹), C₂H₆ (−2.37 ± 1.18% yr⁻¹) and HCN (−0.93 ± 0.47% yr⁻¹) at Lauder and CO (−0.92 ± 0.46% yr⁻¹), C₂H₆ (−2.82 ± 1.37% yr⁻¹) and HCN (−1.41 ± 0.71% yr⁻¹) at Arrival Heights. The uncertainties reflect the 95% confidence limits. However, the magnitudes of the trends are influenced by the anomaly associated with the 1997–1998 El Niño Southern Oscillation event at the beginning of the time series reported. We calculate trends for each month from 1997 to 2009 and find negative trends for all months. The largest monthly trends of CO and C₂H₆ at Lauder, and to a lesser degree at Arrival Heights, occur during austral spring during the Southern Hemisphere tropical and subtropical biomass burning period. For HCN, the largest monthly trends occur in July and August at Lauder and around November at Arrival Heights. The correlations between CO and C₂H₆ and between CO and HCN at Lauder in September to November, when the biomass burning maximizes, are significantly larger that those in other seasons. A tropospheric chemistry-climate model is used to simulate CO, C₂H₆, and HCN partial columns for the period of 1997–2009, using interannually varying biomass burning emissions from GFED3 and annually periodic but seasonally varying emissions from both biogenic and anthropogenic sources. The model-simulated partial columns of these species compare well with the measured partial columns and the model accurately reproduces seasonal cycles of all three species at both locations. However, while the model satisfactorily captures both the seasonality and trends in HCN, it is not able to reproduce the negative trends in either C₂H₆ or CO. A further simulation assuming a 35% decline of C₂H₆ and a 26% decline of CO emissions from the industrial sources from 1997 to 2009 largely captures the observed trends of C₂H₆ and CO partial columns at both locations. Here we attribute trends in HCN exclusively to changes in biomass burning and thereby isolate the influence of anthropogenic emissions as responsible for the long-term decline in CO and C₂H₆. This analysis shows that biomass burning emissions are the main factors in controlling the interannual and seasonal variations of these species. We also demonstrate contributions of biomass burning emission from different southern tropical and sub-tropical regions to seasonal and interannual variations of CO at Lauder; it shows that long-range transport of biomass burning emissions from southern Africa and South America have consistently larger year-to-year contributions to the background seasonality of CO at Lauder than those from other regions (e.g. Australia and South-East Asia). However, large interannual anomalies are triggered by variations in biomass burning emissions associated with large-scale El Niño Southern Oscillation and prolonged biomass burning events, e.g. the Australian bush fires.

• Technical Note: Ozonesonde climatology between 1995 and 2011: description, evaluation and applications

  An ozone climatology based on ozonesonde measurements taken over the last 17 yr has been constructed for model evaluation and comparisons to other observations. Vertical ozone profiles for 42 stations around the globe have been compiled for the period 1995–2011, in pressure and tropopause-referenced altitudes. For each profile, the mean, standard deviation, median, the half-width are provided, as well as information about interannual variability. Regional aggregates are formed in combining stations with similar ozone characteristics. The Hellinger distance is introduced as a new diagnostic to identify stations that describe similar shapes of ozone probability distribution functions (PDFs). In this way, 12 regions were selected covering at least 2 stations and the variability among those stations is discussed. Significant variability with longitude of ozone distributions in the troposphere and lower stratosphere in the northern mid- and high latitudes is found. The representativeness of regional aggregates is discussed for high northern latitudes, Western Europe, Eastern US, and Japan, using independent observations from surface stations and MOZAIC aircraft data. Good agreement exists between ozonesondes and aircraft observations in the mid-troposphere and between ozonesondes and surface observations for Western Europe. For Eastern US and high northern latitudes, surface ozone values from ozonesondes are biased 10 ppb high compared to independent measurements. An application of the climatology is presented using the NCAR CAM-Chem model. The climatology allows evaluation of the model performance regarding ozone averages, seasonality, interannual variability, and the shape of ozone distributions. The new assessment of the key features of ozone distributions gives deeper insights into the performance of models.

• Quantifying population exposure to airborne particulate matter during extreme events in California due to climate change

  The effect of climate change on population-weighted concentrations of particulate matter (PM) during extreme pollution events was studied using the Parallel Climate Model (PCM), the Weather Research and Forecasting (WRF) model and the UCD/CIT 3-D photochemical air quality model. A "business as usual" (B06.44) global emissions scenario was dynamically downscaled for the entire state of California between the years 2000–2006 and 2047–2053. Air quality simulations were carried out for 1008 days in each of the present-day and future climate conditions using year-2000 emissions. Population-weighted concentrations of PM_0.1, PM_2.5, and PM₁₀ total mass, components species, and primary source contributions were calculated for California and three air basins: the Sacramento Valley air basin (SV), the San Joaquin Valley air basin (SJV) and the South Coast Air Basin (SoCAB). Results over annual-average periods were contrasted with extreme events. <br><br> The current study found that the change in annual-average population-weighted PM_2.5 mass concentrations due to climate change between 2000 vs. 2050 within any major sub-region in California was not statistically significant. However, climate change did alter the annual-average composition of the airborne particles in the SoCAB, with notable reductions of elemental carbon (EC; −3%) and organic carbon (OC; −3%) due to increased annual-average wind speeds that diluted primary concentrations from gasoline combustion (−3%) and food cooking (−4%). In contrast, climate change caused significant increases in population-weighted PM_2.5 mass concentrations in central California during extreme events. The maximum 24-h average PM_2.5 concentration experienced by an average person during a ten-yr period in the SJV increased by 21% due to enhanced production of secondary particulate matter (manifested as NH₄NO₃). In general, climate change caused increased stagnation during future extreme pollution events, leading to higher exposure to diesel engines particles (+32%) and wood combustion particles (+14%) when averaging across the population of the entire state. Enhanced stagnation also isolated populations from distant sources such as shipping (−61%) during extreme events. The combination of these factors altered the statewide population-averaged composition of particles during extreme events, with EC increasing by 23 %, nitrate increasing by 58%, and sulfate decreasing by 46%.

• Comparison of CALIPSO aerosol optical depth retrievals to AERONET measurements, and a climatology for the lidar ratio of dust

  We compared CALIPSO column aerosol optical depths at 0.532 μm to measurements at 147 AERONET sites, synchronized to within 30 min of satellite overpass times during a 3-yr period. We found 677 suitable overpasses, and a CALIPSO bias of −13% relative to AERONET for the entire data set; the corresponding absolute bias is −0.029, and the standard deviation of the mean (SDOM) is 0.014. Consequently, the null hypothesis is rejected at the 97% confidence level, indicating a statistically significant difference between the datasets. However, if we omit CALIPSO columns that contain dust from our analysis, the relative and absolute biases are reduced to −3% and −0.005 with a standard error of 0.016 for 449 overpasses, and the statistical confidence level for the null hypothesis rejection is reduced to 27%. We also analyzed the results according to the six CALIPSO aerosol subtypes and found relative and absolute biases of −29% and −0.1 for atmospheric columns that contain the dust subtype exclusively, but with a relatively high correlation coefficient of <i>R</i> = 0.58; this indicates the possibility that the assumed lidar ratio (40 sr) for the CALIPSO dust retrievals is too low. Hence, we used the AERONET size distributions, refractive indices, percent spheres, and forward optics code for spheres and spheroids to compute a lidar ratio climatology for AERONET sites located in the dust belt. The highest lidar ratios of our analysis occur in the non-Sahel regions of Northern Africa, where the median lidar ratio at 0.532 μm is 55.4 sr for 229 retrievals. Lidar ratios are somewhat lower in the African Sahel (49.7 sr for 929 retrievals), the Middle East (42.6 sr for 489 retrievals), and Kanpur, India (43.8 sr for 67 retrievals). We attribute this regional variability in the lidar ratio to the regional variability of the real refractive index of dust, as these two parameters are highly anti-correlated (correlation coefficients range from −0.51 to −0.85 for the various regions). The AERONET refractive index variability is consistent with the variability of illite concentration in dust across the dust belt.

• Humidity-dependent phase state of SOA particles from biogenic and anthropogenic precursors

  The physical phase state (solid, semi-solid, or liquid) of secondary organic aerosol (SOA) particles has important implications for a number of atmospheric processes. We report the phase state of SOA particles spanning a wide range of oxygen to carbon ratios (O / C), used here as a surrogate for SOA oxidation level, produced in a flow tube reactor by photo-oxidation of various atmospherically relevant surrogate anthropogenic and biogenic volatile organic compounds (VOCs). The phase state of laboratory-generated SOA was determined by the particle bounce behavior after inertial impaction on a polished steel substrate. The measured bounce fraction was evaluated as a function of relative humidity and SOA oxidation level (O / C) measured by an Aerodyne high resolution time of flight aerosol mass spectrometer (HR-ToF AMS). <br><br> The main findings of the study are: (1) biogenic and anthropogenic SOA particles are found to be amorphous solid or semi-solid based on the measured bounced fraction (BF), which was typically higher than 0.6 on a 0 to 1 scale. A decrease in the BF is observed for most systems after the SOA is exposed to relative humidity of at least 80% RH, corresponding to a RH at impaction of 55%. (2) Long-chain alkanes have a low BF (indicating a "liquid-like", less viscous phase) particles at low oxidation levels (BF < 0.2 ± 0.05 for O / C = 0.1). However, BF increases substantially upon increasing oxidation. (3) Increasing the concentration of sulphuric acid (H₂SO₄) in solid SOA particles (here tested for longifolene SOA) causes a decrease in BF levels. (4) In the majority of cases the bounce behavior of the various SOA systems did not show correlation with the particle O / C. Rather, the molar mass of the gas-phase VOC precursor showed a positive correlation with the resistance to the RH-induced phase change of the formed SOA particles.

• Ozone production in summer in the megacities of Tianjin and Shanghai, China: a comparative study

  Rapid economic growth has given rise to a significant increase in ozone precursor emissions in many regions of China, especially in the densely populated North China Plain (NCP) and Yangtze River Delta (YRD). Improved understanding of ozone formation in response to different precursor emissions is imperative to address the highly nonlinear ozone problem and to provide a solid scientific basis for efficient ozone abatement in these regions. A comparative study on ozone photochemical production in summer has thus been carried out in the megacities of Tianjin (NCP) and Shanghai (YRD). Two intensive field campaigns were carried out respectively at an urban and a suburban site of Tianjin, in addition to routine monitoring of trace gases in Shanghai, providing data sets of surface ozone and its precursors including nitrogen oxides (NO_x) and various non-methane hydrocarbons (NMHCs). Ozone pollution in summer was found to be more severe in the Tianjin region than in the Shanghai region, based on either the frequency or the duration of high ozone events. Such differences might be attributed to the large amount of highly reactive NMHCs in Tianjin. Industry related species like light alkenes were of particular importance in both urban and suburban Tianjin, while in Shanghai aromatics dominated. In general, the ozone problem in Shanghai is on an urban scale. Stringent control policies on local emissions would help reduce the occurrence of high ozone concentrations. By contrast, ozone pollution in Tianjin is probably a regional problem. Combined efforts to reduce ozone precursor emissions on a regional scale must be undertaken to bring the ozone problem under control.

• Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene

  Peroxy radical reactions (RO₂ + RO₂) from the NO₃-initiated oxidation of isoprene are studied with both gas chromatography and a chemical ionization mass spectrometry technique that allows for more specific speciation of products than in previous studies of this system. We find high nitrate yields (~ 80%), consistent with other studies. We further see evidence of significant hydroxyl radical (OH) formation in this system, which we propose comes from RO₂ + HO₂ reactions with a yield of ~38–58%. An additional OH source is the second generation oxidation of the nitrooxyhydroperoxide, which produces OH and a dinitrooxyepoxide with a yield of ~35%. The branching ratio of the radical propagating, carbonyl- and alcohol-forming, and organic peroxide-forming channels of the RO₂ + RO₂ reaction are found to be ~18–38%, ~59–77%, and ~3–4%, respectively. HO₂ formation in this system is lower than has been previously assumed. Addition of RO₂ to isoprene is suggested as a possible route to the formation of several isoprene C₁₀-organic peroxide compounds (ROOR). The nitrooxy, allylic, and C₅ peroxy radicals present in this system exhibit different behavior than the limited suite of peroxy radicals that have been studied to date.

• Emissions of mercury in southern Africa derived from long-term observations at Cape Point, South Africa

  Mercury emissions in South Africa have so far been estimated only by a bottom-up approach from activities and emission factors for different processes. In this paper we derive GEM/CO (GEM being gaseous elemental mercury, Hg⁰), GEM/CO₂, GEM/CH₄, CO/CO₂, CH₄/CO₂, and CH₄/CO emission ratios from plumes observed during long-term monitoring of these species at Cape Point between March 2007 and December 2009. The average observed GEM/CO, GEM/CO₂, GEM/CH₄, CO/CO₂, CH₄/CO₂, and CH4/CO emission ratios were 2.40 ± 2.65 pg m⁻³ ppb⁻¹ (<i>n</i> = 47), 62.7 ± 80.2 pg m⁻³ ppm⁻¹ (<i>n</i> = 44), 3.61 ± 4.66 pg m⁻³ ppb⁻¹ (<i>n</i> = 46), 35.6 ± 25.4 ppb ppm⁻¹ (<i>n</i> = 52), 20.2 ± 15.5 ppb ppm⁻¹ (<i>n</i> = 48), and 0.876 ± 1.106 ppb ppb⁻¹ (<i>n</i> = 42), respectively. The observed CO/CO₂, CH₄/CO₂, and CH₄/CO emission ratios agree within the combined uncertainties of the observations and emissions with the ratios calculated from EDGAR (version 4.2) CO₂, CO, and CH₄ inventories for South Africa and southern Africa (South Africa, Lesotho, Swaziland, Namibia, Botswana, Zimbabwe, and Mozambique) in 2007 and 2008 (inventories for 2009 are not available yet). Total elemental mercury emission of 13.1, 15.2, and 16.1 t Hg yr⁻¹ are estimated independently using the GEM/CO, GEM/CO₂, and GEM/CH₄ emission ratios and the annual mean CO, CO₂, and CH₄ emissions, respectively, of South Africa in 2007 and 2008. The average of these independent estimates of 14.8 t GEM yr⁻¹ is much less than the total emission of 257 t Hg yr⁻¹ shown by older inventories which are now considered to be wrong. Considering the uncertainties of our emission estimate, of the emission inventories, and the fact that emission of GEM represents 50–78 % of all mercury emissions, our estimate is comparable to the currently cited GEM emissions in 2004 and somewhat smaller than emissions in 2006. A further increase of mercury emissions due to increasing electricity consumption will lead to a more pronounced difference. A quantitative assessment of the difference and its significance, however, will require emission inventories for the years of observations (2007–2009) as well as better data on the speciation of the total mercury emissions in South Africa.

• Summer ammonia measurements in a densely populated Mediterranean city

  Real-time measurements of ambient concentrations of gas-phase ammonia (NH₃) were performed in Barcelona (NE Spain) in summer between May and September 2011. Two measurement sites were selected: one in an urban background traffic-influenced area (UB) and the other in the historical city centre (CC). Levels of NH₃ were higher at CC (5.6 ± 2.1 μg m⁻³ or 7.5 ± 2.8 ppbv) compared with UB (2.2 ± 1.0 μg m⁻³ or 2.9 ± 1.3 ppbv). This difference is attributed to the contribution from non-traffic sources such as waste containers, sewage systems, humans and open markets more dense in the densely populated historical city centre. Under high temperatures in summer these sources had the potential to increase the ambient levels of NH₃ well above the urban-background-traffic-influenced UB measurement station. Measurements were used to assess major local emissions, sinks and diurnal evolution of NH₃. The measured levels of NH₃, especially high in the old city, may contribute to the high mean annual concentrations of secondary sulfate and nitrate measured in Barcelona compared with other cities in Spain affected by high traffic intensity. Ancillary measurements, including PM₁₀, PM_2.5, PM₁ levels (Particulate Matter with aerodynamic diameter smaller than 10 μm, 2.5 μm, and 1 μm), gases and black carbon concentrations and meteorological data, were performed during the measurement campaign. The analysis of specific periods (3 special cases) during the campaign revealed that road traffic was a significant source of NH₃. However, its effect was more evident at UB compared with CC where it was masked given the high levels of NH₃ from non-traffic sources measured in the old city. The relationship between SO₄^2&minus; daily concentrations and gas-fraction ammonia (NH₃/(NH₃ + NH₄⁺)) revealed that the gas-to-particle phase partitioning (volatilization or ammonium salts formation) also played an important role in the evolution of NH₃ concentration in summer in Barcelona.

• Mixing of Asian mineral dust with anthropogenic pollutants over East Asia: a model case study of a super-duststorm in March 2010

  Mixing of Asian mineral dust with anthropogenic pollutants allows pollutants (e.g. sulfate and nitrate) to be transported over longer distances (e.g. to the northern Pacific, even to North America) along with dust particles. This mixing therefore affects the atmospheric and oceanic environment at local, regional and even continental scales. In this study, we used a three-dimensional regional chemical transport model (Nested Air Quality Predicting Modeling System, NAQPMS) to examine the degree of mixing between Asian mineral dust and anthropogenic pollutants in a super-duststorm event during 19–22 March 2010. Influences of the mixing processes on regional atmospheric environmental and oceanic biogeochemical cycles were also investigated. A comparison with measurements showed that the model reproduced well the trajectory of long-range dust transport, the vertical dust profile, and the chemical evolution of dust particles. We found that along-path mixing processes during the long-range transport of Asian dust led to increasingly polluted particles. As a result, ~60% of the sulfate and 70–95% of the nitrate in the downwind regions was derived from active mixing processes of minerals with pollutants sourced from the North China Plain and enhanced by transport over South China. This mixing had a significant impact on the regional-scale atmospheric composition and oceanic biogeochemical cycle. Surface HNO₃, SO₂ and O₃ were decreased by up to 90%, 40% and 30%, respectively, due to the heterogeneous reactions on dust particles. Fe solubility rose from ~0.5% in the Gobi region to ~3–5% in the northwestern Pacific, resulting from oxidization of SO₂ on dust particles. Total Fe(II) deposition in the ocean region of East Asia reached 327 tons during the 4-day dust event, and created a calculated primary productivity of ~520 mgC m⁻² d⁻¹ in the Kuril Islands, which can support almost 100% of the observed mean marine primary productivity in spring in this region (526 mgC m⁻² d⁻¹).