ALBERT

Description: Small-scale nonlinear chemical and physical processes over pollution source regions affect the global ozone (O3) chemistry, but these processes are not captured by current global chemical transport models (CTMs) and chemistry-climate models that are limited by coarse horizontal resolutions (100–500 km, typically 200 km). These models tend to contain large (and mostly positive) tropospheric O3 biases in the Northern Hemisphere. Here we use a recently built two-way coupling system of the GEOS-Chem CTM to simulate the global tropospheric O3 in 2009. The system couples the global model (at 2.5° long. × 2° lat.) and its three nested models (at 0.667° long. × 0.5° lat.) covering Asia, North America and Europe, respectively. Benefiting from the high resolution, the nested models better capture small-scale processes than the global model alone. In the coupling system, the nested models provide results to modify the global model simulation within respective nested domains while taking the lateral boundary conditions from the global model. Due to the "coupling" effects, the two-way system significantly improves the tropospheric O3 simulation upon the global model alone, as found by comparisons with a suite of ground (1420 sites from WDCGG, GMD, EMEP, and AQS), aircraft (HIPPO and MOZAIC), and satellite measurements (two OMI products). Compared to the global model alone, the two-way coupled simulation enhances the correlation in day-to-day variation of afternoon mean O3 with the ground measurements from 0.53 to 0.68, and it reduces the mean model bias from 10.8 to 6.7 ppb in annual average afternoon O3. Regionally, the coupled model reduces the bias by 4.6 ppb over Europe, 3.9 ppb over North America, and 3.1 ppb over other regions. The two-way coupling brings O3 vertical profiles much closer to the HIPPO (for remote areas) and MOZAIC (for polluted regions) data, reducing the tropospheric (0–9 km) mean bias by 3–10 ppb at most MOZAIC sites and by 5.3 ppb for HIPPO profiles. The two-way coupled simulation also reduces the global tropospheric column ozone by 3.0 DU (9.5 %, annual mean), bringing them closer to the OMI data in all seasons. Simulation improvements are more significant in the northern hemisphere, and are primarily a result of improved representation of urban-rural contrast and other small-scale processes. The two-way coupled simulation also reduces the global tropospheric mean hydroxyl radical by 5 % with enhancements by 5 % in the lifetimes of methyl chloroform (from 5.58 to 5.87 yr) and methane (from 9.63 to 10.12 yr), bringing them closer to observation-based estimates. Improving model representations of small-scale processes are a critical step forward to understanding the global tropospheric chemistry.

Description: Methanol retrievals from nadir-viewing space-based sensors offer powerful new information for quantifying methanol emissions on a global scale. Here we apply an ensemble of aircraft observations over North America to evaluate new methanol measurements from the Tropospheric Emission Spectrometer (TES) on the Aura satellite, and combine the TES data with observations from the Infrared Atmospheric Sounding Interferometer (IASI) on the MetOp-A satellite to investigate the seasonality of methanol emissions from northern midlatitude ecosystems. Using the GEOS-Chem chemical transport model as an intercomparison platform, we find that the TES retrieval performs well when the degrees of freedom for signal (DOFS) are above 0.5, in which case the model : TES regressions are generally consistent with the model : aircraft comparisons. Including retrievals with DOFS below 0.5 degrades the comparisons, as these are excessively influenced by the a priori. The comparisons suggest DOFS 〉 0.5 as a minimum threshold for interpreting retrievals of trace gases with a weak tropospheric signal. We analyze one full year of satellite observations and find that GEOS-Chem, driven with MEGANv2.1 biogenic emissions, underestimates observed methanol concentrations throughout the midlatitudes in springtime, with the timing of the seasonal peak in model emissions 1–2 months too late. We attribute this discrepancy to an underestimate of emissions from new leaves in MEGAN, and apply the satellite data to better quantify the seasonal change in methanol emissions for midlatitude ecosystems. The derived parameters (relative emission factors of 11.0, 1.0, 0.05 and 8.6 for new, growing, mature, and old leaves, respectively, plus a leaf area index activity factor of 0.75 for expanding canopies with leaf area index 〈 2.0) provide a more realistic simulation of seasonal methanol concentrations in midlatitudes on the basis of IASI, TES, and ground-based measurements.

Description: Extensive undersaturations of carbon tetrachloride (CCl4) in Pacific, Atlantic, and Southern Ocean surface waters indicate that atmospheric CCl4 is consumed in large amounts by the ocean. Observations made on 16 research cruises between 1987 and 2010, ranging in latitude from 60° N to 77° S, show that negative saturations extend over most of the surface ocean. Corrected for physical effects associated with radiative heat flux, mixing, and air injection, these anomalies were commonly of the order of −5 % to −10 %, with no clear relationship with temperature, productivity, or other gross surface water characteristics other than being more negative in association with upwelling. The atmospheric flux required to sustain these undersaturations is 11 (7–14) Gg y−1, a loss rate implying a partial atmospheric lifetime with respect to the oceanic loss of 209 (157–313) y and that ~ 16 (10–21) % of atmospheric CCl4 is lost to the ocean. Although CCl4 hydrolyses in seawater, published hydrolysis rates for this gas are too slow to support such large undersaturations, given our current understanding of air–sea gas exchange rates. The even larger undersaturations in intermediate depth waters associated with reduced oxygen levels, observed in this study and by other investigators, strongly suggest that CCl4 is ubiquitously consumed at mid-depth, presumably by microbiota. Although this subsurface sink creates a gradient that drives a downward flux of CCl4, the gradient alone is not sufficient to explain the observed surface undersaturations. Since known chemical losses are likewise insufficient to sustain the observed undersaturations, this suggests a possible biological sink for CCl4 also in surface or near-surface waters of the ocean.

Description: Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2–3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based: (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx:CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model does not capture the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.

Description: We present a detailed investigation of the factors governing the quantification of formic acid (FA), acetic acid (AA), and their relevant mass analogues by proton-transfer-reaction mass spectrometry (PTR-MS), assess the underlying fragmentation pathways and humidity dependencies, and present a new method for separating FA and AA from their main isobaric interferences. PTR-MS sensitivities towards glycolaldehyde, ethyl acetate, and peroxyacetic acid at m/z 61 are comparable to that for AA; when present, these species will interfere with ambient AA measurements by PTR-MS. Likewise, when it is present, dimethyl ether can interfere with FA measurements. For a reduced electric field (E/N) of 125 Townsend (Td), the PTR-MS sensitivity towards ethanol at m/z 47 is 5–20 times lower than for FA; ethanol will then only be an important interference when present in much higher abundance than FA. Sensitivity towards 2-propanol is

Description: Formic acid (HCOOH) is one of the most abundant acids in the atmosphere, with an important influence on precipitation chemistry and acidity. Here we employ a chemical transport model (GEOS-Chem CTM) to interpret recent airborne and ground-based measurements over the US Southeast in terms of the constraints they provide on HCOOH sources and sinks. Summertime boundary layer concentrations average several parts-per-billion, 2–3× larger than can be explained based on known production and loss pathways. This indicates one or more large missing HCOOH sources, and suggests either a key gap in current understanding of hydrocarbon oxidation or a large, unidentified, direct flux of HCOOH. Model-measurement comparisons implicate biogenic sources (e.g., isoprene oxidation) as the predominant HCOOH source. Resolving the unexplained boundary layer concentrations based (i) solely on isoprene oxidation would require a 3× increase in the model HCOOH yield, or (ii) solely on direct HCOOH emissions would require approximately a 25× increase in its biogenic flux. However, neither of these can explain the high HCOOH amounts seen in anthropogenic air masses and in the free troposphere. The overall indication is of a large biogenic source combined with ubiquitous chemical production of HCOOH across a range of precursors. Laboratory work is needed to better quantify the rates and mechanisms of carboxylic acid production from isoprene and other prevalent organics. Stabilized Criegee intermediates (SCIs) provide a large model source of HCOOH, while acetaldehyde tautomerization accounts for ~ 15% of the simulated global burden. Because carboxylic acids also react with SCIs and catalyze the reverse tautomerization reaction, HCOOH buffers against its own production by both of these pathways. Based on recent laboratory results, reaction between CH3O2 and OH could provide a major source of atmospheric HCOOH; however, including this chemistry degrades the model simulation of CH3OOH and NOx : CH3OOH. Developing better constraints on SCI and RO2 + OH chemistry is a high priority for future work. The model neither captures the large diurnal amplitude in HCOOH seen in surface air, nor its inverted vertical gradient at night. This implies a substantial bias in our current representation of deposition as modulated by boundary layer dynamics, and may indicate an HCOOH sink underestimate and thus an even larger missing source. A more robust treatment of surface deposition is a key need for improving simulations of HCOOH and related trace gases, and our understanding of their budgets.

Description: We report here on two cases of poleward-propagating large-scale traveling ionospheric disturbances (LSTIDs) in China during a medium-scale storm between 27 May and 1 June 2011. The observations were conducted by making use of the Global Positioning System network and ionosondes in China and Southeast Asia. One northeastward-propagating LSTID occurred on the morning of 30 May, while the other was observed during the nighttime of 1 June. Both poleward-traveling LSTIDs occurred during the storm's recovery phase in southern China's low-latitude region (geomagnetic latitude ~ 7.3–24° N) and experienced severe dissipation during their propagation from south to north. Although the initial relative amplitude of the nighttime LSTID was ~ 60% larger than that of the morning event, the nighttime event dissipated more quickly than the morning event because of a strong nighttime enhancement in background total electronic content (TEC) during storm time, which led to strong ion-drag dissipation during the evening. The poleward-propagating LSTIDs exhibit a narrower latitudinal range, a smaller amplitude, and a slightly higher elevation compared with the equatorward-moving LSTIDs observed in the same region. Given these features, the poleward-propagating LSTIDs were likely excited by some local source near southern China. Excitation of secondary LSTIDs during the dissipation of some primary medium-scale disturbances from the lower atmosphere is a possible mechanism.

Description: Although the electron density profiles (EDPs) from Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC) measurement have been validated by ionosonde data at a number of locations during the solar minimum period, the performance of COSMIC measurements at different latitudes has not been well evaluated, particularly during the solar maximum period. In this paper the COSMIC ionospheric peak parameters (peak electron density of the F region – NmF2; peak height of the F region – hmF2) are validated by the ionosonde data from an observation chain in China during the solar maximum period of 2011–2013. The validations show that the COSMIC measurement generally agrees well with the ionosonde observation. The error in NmF2 from COSMIC and ionosonde measurements varies with latitude. At midlatitude stations, the differences between COSMIC NmF2s and those of ionosondes are very slight. However, COSMIC NmF2 overestimates (underestimates) that of the ionosonde at the north (south) of the equatorial ionization anomaly (EIA) crest. The relative errors of hmF2s are much lower than those of NmF2s at all stations, which indicates the EDP retrieval algorithm of the COSMIC measurement has a better performance in determining the ionospheric peak height. The root mean square errors (RMSEs) of NmF2s (hmF2s) are higher (lower) during the daytime than during the nighttime at all stations. Correlation analysis shows that the correlations for both NmF2s and hmF2s are comparably good (correlation coefficients 〉 0.9) at midlatitude stations, while correlations of NmF2 (correlation coefficients 〉 0.9) are higher than those of hmF2 (correlation coefficients 〉 0.8) at low-latitude stations.

Description: We analyze the data recorded during December 2011–November 2012 by a digital ionosonde and a GPS (Global Positioning System) scintillation and (total electron content) TEC receiver collocated at Sanya (109.6° E, 18.3° N; dip lat. 12.8° N), a low-latitude station in the Chinese longitude sector, to carry out a comparative study of ionospheric scintillations and spread F. A good consistency between the temporal variations of GPS scintillation (represented by the S4 index) and of ionogram spread F (represented by the QF index) is found in the pre-midnight period during equinox. However in the post-midnight period during equinox and in the period from post-sunset to pre-sunrise during June solstice, moderate spread F is seen without concurrent GPS scintillation. The possible cause responsible for the difference between post-midnight GPS scintillation and spread F during equinox could be due to the decaying of 400 m scale irregularities associated with equatorial spread F. Regarding the irregularities producing moderate QF and low S4 indices during June solstice, we suggest that the frequently observed sporadic E (Es) layer and the medium-scale traveling ionospheric disturbances (MSTIDs) over Sanya could play important roles in triggering the June solstitial spread-F events.

Description: Four successive storms with freezing rain and snow blanketed South China from 10 January–2 February 2008, when the precipitation increased more than 200%–300% above the average for the corresponding period. The unusual atmospheric circulation associated with these disasters was caused by many complex physical processes, one of which was the active southern branch of currents over low latitude ocean areas which provided plenty of water vapor for South China. The ground-based GPS Precipitable Water Vapor (PWV) measurements on the Tibetan Plateau, supported by the China and Japan Intergovernmental Cooperation Program (JICA), has compensated for the lack of conventional observations of atmospheric water vapor in this area and provided a good opportunity to analyze the character of the water vapor transport in the four heavy precipitation processes. It was found that the GPS stations located on the southeastern Tibetan Plateau were on the route of the water vapor transport during 25 January–29 January and 31 January–2 February when two heavy precipitation events occurred over South China. The increasing trend from the one to two days pre-observation by the GPS stations was then associated with the heavy precipitation. Precipitation during 10 January–16 January and 18 January–22 January was significantly related to the abnormal variation of the one day pre-observation by the GPS stations located on the northeastern Tibetan Plateau. This research indicates that ground-based GPS measurements are applicable to data assimilation in operational numerical models.