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Air-chemistry "turbulence": power-law scaling and statistical regularity

With the intent to gain further knowledge on the spectral structures and statistical regularities of surface atmospheric chemistry, the chemical gases (NO, NO2, NOx, CO, SO2, and O3) and aerosol (PM10) measured at 74 air quality monitoring stations over the island of Taiwan are analyzed for the year of 2004 at hourly resolution. They represent a range of surface air quality with a mixed combination of geographic settings, and include urban/rural, coastal/inland, plain/hill, and industrial/agricultural locations. In addition to the well-known semi-diurnal and diurnal oscillations, weekly, and intermediate (20 ~ 30 days) peaks are also identified with the continuous wavelet transform (CWT). The spectra indicate power-law scaling regions for the frequencies higher than the diurnal and those lower than the diurnal with the average exponents of −5/3 and −1, respectively. These dual-exponents are corroborated with those with the detrended fluctuation analysis in the corresponding time-lag regions. These exponents are mostly independent of the averages and standard deviations of time series measured at various geographic settings, i.e., the spatial inhomogeneities. In other words, they possess dominant universal structures. After spectral coefficients from the CWT decomposition are grouped according to the spectral bands, and inverted separately, the PDFs of the reconstructed time series for the high-frequency band demonstrate the interesting statistical regularity, −3 power-law scaling for the heavy tails, consistently. Such spectral peaks, dual-exponent structures, and power-law scaling in heavy tails are important structural information, but their relations to turbulence and mesoscale variability require further investigations. This could lead to a better understanding of the processes controlling air quality.
The fate of saharan dust across the atlantic and implications for a central american dust barrier

Saharan dust was observed over the Caribbean basin during the summer 2007 NASA Tropical Composition, Cloud, and Climate Coupling (TC4) field experiment. Airborne Cloud Physics Lidar (CPL) and satellite observations from MODIS suggest a barrier to dust transport across Central America into the eastern Pacific. We use the NASA GEOS-5 atmospheric transport model with online aerosol tracers to perform simulations of the TC4 time period in order to understand the nature of this barrier. Our simulations are driven by the Modern Era Retrospective-Analysis for Research and Applications (MERRA) meteorological analyses. Compared to observations from MODIS and CALIOP, GEOS-5 reproduces the observed location and magnitude of observed dust events, but our baseline simulation does not develop as strong a barrier to dust transport across Central America as observations suggest. Analysis of the dust transport dynamics and loss processes suggest that while both mechanisms play a role in defining the dust transport barrier, loss processes by wet removal of dust are about twice as important as transport. Sensitivity analyses with our model showed that the dust barrier would not exist without convective scavenging over the Caribbean. The best agreement between our model and the observations was obtained when dust wet removal was parameterized to be more aggressive, treating the dust as we do hydrophilic aerosols.
Denitrification and polar stratospheric cloud formation during the Arctic winter 2009/2010

The sedimentation of HNO3 containing Polar Stratospheric Cloud (PSC) particles leads to a permanent removal of HNO3 and thus to a denitrification of the stratosphere, an effect which plays an important role in stratospheric ozone depletion. The polar vortex in the Arctic winter 2009/2010 was very cold and stable between end of December and end of January. Strong denitrification between 475 to 525 K was observed in the Arctic in mid of January by the Odin Sub Millimetre Radiometer (Odin/SMR). This was the strongest denitrification that had been observed in the entire Odin/SMR measuring period (2001–2010). Lidar measurements of PSCs were performed in the area of Kiruna, Northern Sweden with the IRF (Institutet för Rymdfysik) lidar and with the Esrange lidar in January 2010. The measurements show that PSCs were present over the area of Kiruna during the entire period of observations. The formation of PSCs during the Arctic winter 2009/2010 is investigated using a microphysical box model. Box model simulations are performed along air parcel trajectories calculated six days backward according to the PSC measurements with the ground-based lidar in the Kiruna area. From the temperature history of the backward trajectories and the box model simulations we find two PSC regions, one over Kiruna according to the measurements made in Kiruna and one north of Scandinavia which is much colder, reaching also temperatures below Tice. Using the box model simulations along backward trajectories together with the observations of Odin/SMR, Aura/MLS (Microwave Limb Sounder), CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations) and the ground-based lidar we investigate how and by which type of PSC particles the denitrification that was observed during the Arctic winter 2009/2010 was caused. From our analysis we find that due to an unusually strong synoptic cooling event in mid January, ice particle formation on NAT may be a possible formation mechanism during that particular winter that may have caused the denitrification observed in mid January. In contrast, the denitrification that was observed in the beginning of January could have been caused by the sedimentation of NAT particles that formed on mountain wave ice clouds.
Horizontal variability of aerosol optical depth observed during the ARCTAS airborne experiment

We present statistics on the horizontal variability of aerosol optical depth (AOD) directly measured from the NASA P-3 aircraft. Our measurements during two contrasting phases (in Alaska and Canada) of the ARCTAS mission arguably constrain the variability in most aerosol environments common over the globe. In the Canada phase, which features local emissions, 499 nm AOD has a median relative standard deviation (stdrel, med) of 19 % and 9 % and an autocorrelation (r) of 0.37 and 0.71 over 20 km and 6 km horizontal segments, respectively. In the Alaska phase, which features long-range transport, the variability is considerably lower (stdrel, med = 3 %, r = 0.92 even over 35.2 km). Compared to the magnitude of AOD, its wavelength dependence varies less in the Canada phase, more in the Alaska phase. We translate these findings from straight-line flight tracks into grid boxes and points, to help interpretation and design of satellite remote sensing, suborbital observations and transport modeling.
Minor effect of physical size sorting on iron solubility of transported mineral dust

Observations show that the fractional solubility of Fe (FS-Fe, percentage of dissolved to total Fe) in dust aerosol increases considerably from 0.1 % in regions of high dust mass concentration to 80 % in remote regions where concentrations are low. Here, we combined laboratory geochemical measurements with global aerosol model simulations to test the hypothesis that the increase in FS-Fe is due to physical size sorting during transport. We determined the FS-Fe and fractional solubility of Al (FS-Al) in size-fractionated dust generated from two representative soil samples collected from known Saharan dust source regions using a customized dust re-suspension and collection system. The results show that the FS-Fe is size-dependent and ranges from 0.1–0.3 % in the coarse size fractions (>1 μm) to ~0.2–0.8 % in the fine size fractions (<1 μm). The FS-Al shows a similar size distribution to that of the FS-Fe. The size-resolved FS-Fe data were then combined with simulated dust mass concentration and size distribution data from a global aerosol model, GLOMAP, to calculate the FS-Fe of dust aerosol over the tropical and subtropical North Atlantic Ocean. We find that the calculated FS-Fe in the dust aerosol increases systematically from ~0.1 % at high dust mass concentrations (e.g., >100 μg m−3) to ~0.2 % at low concentrations (<100 μg m–3) due to physical size sorting (i.e., particle gravitational settling). These values are one to two orders of magnitude smaller than those observed on cruises across the tropical and sub-tropical North Atlantic Ocean under an important pathway of Saharan dust plumes for similar dust mass concentrations. Even when the FS-Fe of sub-micrometer size fractions (0.18–0.32 μm, 0.32–0.56 μm, and 0.56–1.0 μm) in the model is increased by a factor of 10 over the measured values, the calculated FS-Fe of the dust is still more than an order of magnitude lower than that measured in the field. Therefore, the physical sorting of dust particles alone is unlikely to be an important factor in the observed inverse relationship between the FS-Fe and FS-Al and the atmospheric mineral dust mass concentrations. The results suggest that processes such as chemical reactions and/or mixing with combustion particles are the main mechanisms to cause the increased FS-Fe in long-range transported dust aerosols.
New particle formation infrequently observed in Himalayan foothills – why?

A fraction of the Himalayan aerosols originate from secondary sources, which are currently poorly quantified. To clarify the climatic importance of regional secondary particle formation in the Himalayas, data from 2005 to 2010 of continuous aerosol measurements at a high-altitude (2180 m) Indian Himalayan site, Mukteshwar, were analyzed. For this period, the days were classified, and the particle formation and growth rates were calculated for clear new particle formation (NPF) event days. The NPF events showed a pronounced seasonal cycle. The frequency of the events peaked in spring, when the ratio between event and non-event days was 53 %, whereas the events were truly sporadic on any other seasons. The annual mean particle formation and growth rates were 0.40 cm−3 s−1 and 2.43 nm h−1, respectively. The clear annual cycle was found to be mainly controlled by the seasonal evolution of the Planetary Boundary Layer (PBL) height together with local meteorological conditions. Spring NPF events were connected with increased PBL height, and therefore characterised as boundary layer events, while the rare events in other seasons represented lower free tropospheric particle formation. This provides insight on the vertical extent of NPF in the atmosphere.
Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state

Ozone (O3) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O3 loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO2, O3, JNO2, J(O1D), HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel Marion-Dufresne (28° S–57° S, 46° W–34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ>1). The deviations observed under low NOx conditions (5–25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NOx mixing ratio and JNO2 intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NOx (NO + NO2) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO2 radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°–60° S over the Atlantic Ocean.
A high spatial resolution retrieval of NO 2 column densities from OMI: method and evaluation

We present a new retrieval of tropospheric NO2 vertical column density from the Ozone Monitoring Instrument (OMI) based on high spatial and temporal resolution terrain and profile inputs. We compare our NO2 product, the Berkeley High-Resolution (BEHR) product, with operational retrievals and find that the operational retrievals are biased high (30 %) over remote areas and biased low (8 %) over urban regions. Additionally, we find non-negligible impacts on the retrieved NO2 column for terrain pressure (±20 %), albedo (±40 %), and NO2 vertical profile (−75 %–+10 %). We validate the operational and BEHR products using boundary layer aircraft observations from the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS-CA) field campaign which occurred in June 2008 in California. Results indicate that columns derived using our boundary layer extrapolation method show good agreement with satellite observations (R2 = 0.65–0.83; N = 68) and provide a more robust validation of satellite-observed NO2 column than those determined using full vertical spirals (R2 = 0.26; N = 5) as in previous work. Agreement between aircraft observations and the BEHR product (R2 = 0.83) is better than agreement with the operational products (R2 = 0.65–0.72). We also show that agreement between satellite and aircraft observations can be further improved (e.g. BEHR: R2 = 0.91) using cloud information from the Moderate Resolution Imaging Spectroradiometer (MODIS) instrument instead of the OMI cloud product. These results indicate that much of the variance in the operational products can be attributed to coarse resolution terrain pressure, albedo, and profile parameters implemented in the retrievals.
A model study of the impact of source gas changes on the stratosphere for 1850–2100

The long-term stratospheric impacts due to emissions of CO2, CH4, N2O, and ozone depleting substances (ODSs) are investigated using an updated version of the Goddard two-dimensional (2-D) model. Perturbation simulations with the ODSs, CO2, CH4, and N2O varied individually are performed to isolate the relative roles of these gases in driving stratospheric changes over the 1850–2100 time period. We also show comparisons with observations and the Goddard Earth Observing System chemistry-climate model simulations for the time period 1960–2100 to illustrate that the 2-D model captures the basic processes responsible for long-term stratospheric change. The ODSs, CO2, CH4, and N2O impact ozone via several mechanisms. ODS and N2O loading decrease stratospheric ozone via the increases in atmospheric halogen and odd nitrogen species, respectively. CO2 loading impacts ozone by: (1) cooling the stratosphere which increases ozone via the reduction in the ozone chemical loss rates, and (2) accelerating the Brewer-Dobson circulation (BDC) which redistributes ozone in the lower stratosphere. The net result of CO2 loading is an increase in global ozone in the total column and upper stratosphere. CH4 loading impacts ozone by: (1) increasing atmospheric H2O and the odd hydrogen species which decreases ozone via the enhanced HOx-ozone loss rates; (2) increasing the H2O cooling of the middle atmosphere which reduces the ozone chemical loss rates, partially offsetting the enhanced HOx-ozone loss; (3) converting active to reservoir chlorine via the reaction CH4+Cl→HCl+CH3 which leads to more ozone; and (4) increasing the NOx-ozone production in the troposphere. The net result of CH4 loading is an ozone decrease above 40–45 km, and an increase below 40–45 km and in the total column. The 2-D simulations indicate that prior to 1940, the ozone increases due to CO2 and CH4 loading outpace the ozone losses due to increasing N2O and carbon tetrachloride (CCl4) emissions, so that total column and upper stratospheric global ozone reach broad maxima during the 1920s–1930s. This precedes the significant ozone depletion during ~1960–2050 driven by the ODS loading. During the latter half of the 21st century as ODS emissions diminish, CO2, N2O, and CH4 loading will all have significant impacts on global total ozone based on the Intergovernmental Panel on Climate Change (IPCC) A1B (medium) scenario, with CO2 having the largest individual effect. Sensitivity tests illustrate that due to the strong chemical interaction between methane and chlorine, the CH4 impact on total ozone becomes significantly more positive with larger ODS loading. The model simulations also show that changes in stratospheric temperature, BDC, and age of air during 1850–2100 are controlled mainly by the CO2 and ODS loading. The simulated acceleration of the BDC causes the global average age of air above 22 km to decrease by ~1 yr from 1860–2100. The photochemical lifetimes of N2O, CFCl3, CF2Cl2, and CCl4 decrease by 11–13 % during 1960–2100 due to the acceleration of the BDC, with much smaller lifetime changes (<4 %) caused by changes in the photochemical loss rates.
Observations of hydroxyl and peroxy radicals and the impact of BrO at Summit, Greenland in 2007 and 2008

The Greenland Summit Halogen-HOx (GSHOX) Campaign was performed in spring 2007 and summer 2008 to investigate the impact of halogens on HOx (= OH + HO2) cycling above the Greenland Ice Sheet. Chemical species including hydroxyl and peroxy radicals (OH and HO2 + RO2), ozone (O3), nitrogen oxide (NO), nitric acid (HNO3), nitrous acid (HONO), reactive gaseous mercury (RGM), and bromine oxide (BrO) were measured during the campaign. The median midday values of HO2 + RO2 and OH concentrations observed by chemical ionization mass spectrometry (CIMS) were 2.7 × 108 molec cm−3 and 3.0 × 106 molec cm−3 in spring 2007, and 4.2 × 108 molec cm−3 and 4.1 × 106 molec cm−3 in summer 2008. A basic photochemical 0-D box model highly constrained by observations of H2O, O3, CO, CH4, NO, and J values predicted HO2 + RO2 (R = 0.90, slope = 0.87 in 2007; R = 0.79, slope = 0.96 in 2008) reasonably well and under predicted OH (R = 0.83, slope = 0.72 in 2007; R = 0.76, slope = 0.54 in 2008). Constraining the model to HONO observations did not significantly improve the ratio of OH to HO2 + RO2 and the correlation between predictions and observations. Including bromine chemistry in the model constrained by observations of BrO improved the correlation between observed and predicted HO2 + RO2 and OH, and brought the average hourly OH and HO2 + RO2 predictions closer to the observations. These model comparisons confirmed our understanding of the dominant HOx sources and sinks in this environment and indicated that BrO impacted the OH levels at Summit. Although, significant discrepancies between observed and predicted OH could not be explained by the measured BrO. Finally, observations of enhanced RGM were found to be coincident with under prediction of OH.