Lyatt Jaeglé

Global partitioning of NOx sources using satellite observations: relative roles of fossil fuel combustion, biomass burning and soil emissions.

We use space-based observations of NO2 columns from the Global Ozone Monitoring Experiment (GOME) to derive monthly top-down NOx emissions for 2000 via inverse modeling with the GEOS-CHEM chemical transport model. Top-down NOx sources are partitioned among fuel combustion (fossil fuel and biofuel), biomass burning and soils by exploiting the spatio-temporal distribution of remotely sensed fires and a priori information on the location of regions dominated by fuel combustion. The top-down inventory is combined with an a priori inventory to obtain an optimized a posteriori estimate of the relative roles of NOx sources. The resulting a posteriori fuel combustion inventory (25.6 TgN year(-1)) agrees closely with the a priori (25.4 TgN year(-1)), and errors are reduced by a factor of 2, from +/- 80% to +/- 40%. Regionally, the largest differences are found over Japan and South Africa, where a posteriori estimates are 25% larger than a priori. A posteriori fuel combustion emissions are aseasonal, with the exception of East Asia and Europe where winter emissions are 30-40% larger relative to summer emissions, consistent with increased energy use during winter for heating. Global a posteriori biomass burning emissions in 2000 resulted in 5.8 TgN (compared to 5.9 TgN year(-1) in the a priori), with Africa accounting for half of this total. A posteriori biomass burning emissions over Southeast Asia/India are decreased by 46% relative to a priori; but over North equatorial Africa they are increased by 50%. A posteriori estimates of soil emissions (8.9 TgN year(-1)) are 68% larger than a priori (5.3 TgN year(-1)). The a posteriori inventory displays the largest soil emissions over tropical savanna/woodland ecosystems (Africa), as well as over agricultural regions in the western U.S. (Great Plains), southern Europe (Spain, Greece, Turkey), and Asia (North China Plain and North India), consistent with field measurements. Emissions over these regions are highest during summer at mid-latitudes and during the rainy season in the Tropics. We estimate that 2.5-4.5 TgN year(-1) are emitted from N-fertilized soils, at the upper end of previous estimates. Soil and biomass burning emissions account for 22% and 14% of global surface NOx emissions, respectively. We infer a significant role for soil NOx emissions at northern mid-latitudes during summer, where they account for nearly half that of the fuel combustion source, a doubling relative to the a priori. The contribution of soil emissions to background ozone is thus likely to be underestimated by the current generation of chemical transport models.

Global 3-D land-ocean-atmosphere model for mercury: Present-day versus preindustrial cycles and anthropogenic enrichment factors for deposition

We develop a mechanistic representation of land-atmosphere cycling in a global 3-D ocean-atmosphere model of mercury (GEOS-Chem). The resulting land-ocean-atmosphere model is used to construct preindustrial and present biogeochemical cycles of mercury, to examine the legacy of past anthropogenic emissions, to map anthropogenic enrichment factors for deposition, and to attribute mercury deposition in the United States. Land emission in the model includes prompt recycling of recently deposited mercury (600 Mg a -1 for present day), soil volatilization (550 Mg a -1 ), and evapotranspiration (550 Mg a -1 ). The spatial distribution of soil concentrations is derived from local steady state between land emission and deposition in the preindustrial simulation, augmented for the present day by a 15% increase in the soil reservoir distributed following the pattern of anthropogenic deposition. Mercury deposition and hence emission are predicted to be highest in the subtropics. Our atmospheric lifetime of mercury against deposition (0.50 year) is shorter than past estimates because of our accounting of Hg(0) dry deposition, but recycling from surface reservoirs results in an effective lifetime of 1.6 years against transfer to long-lived reservoirs in the soil and deep ocean. Present-day anthropogenic enrichment of mercury deposition exceeds a factor of 5 in continental source regions. We estimate that 68% of the deposition over the United States is anthropogenic, including 20% from North American emissions (20% primary and <1% recycled through surface reservoirs), 31% from emissions outside North America (22% primary and 9% recycled), and 16% from the legacy of anthropogenic mercury accumulated in soils and the deep ocean.

Chemistry of HOx radicals in the upper troposphere

Aircraft observations from three recent missions (STRAT, SUCCESS, SONEX) are synthesized into a theoretical analysis of the factors controlling the concentrations of HO_x radicals (HO_x=OH+peroxy) and the larger reservoir family HO_y (HO_y=HO_x+2H_2O_2+2CH_3OOH+HNO_2+HNO_4) in the upper troposphere. Photochemical model calculations capture 66% of the variance of observed HOx concentrations. Two master variables are found to determine the variance of the 24 h average HOx concentrations: the primary HO_x production rate, P(HO_x), and the concentration of nitrogen oxide radicals (NO_x=NO+NO_2). We use these two variables as a coordinate system to diagnose the photochemistry of the upper troposphere and map the different chemical regimes. Primary HO_x production is dominated by the O(^1D)+H_2O reaction when [H_2O]>100 ppmv, and by photolysis of acetone (and possibly other convected HO_x precursors) under drier conditions. For the principally northern midlatitude conditions sampled by the aircraft missions, the HO_x yield from acetone photolysis ranges from 2 to 3. Methane oxidation amplifies the primary HO_x source by a factor of 1.1–1.9. Chemical cycling within the HO_x family has a chain length of 2.5–7, while cycling between the HO_x family and its HO_y reservoirs has a chain length of 1.6–2.2. The number of ozone molecules produced per HO_y molecule consumed ranges from 4 to 12, such that ozone production rates vary between 0.3 and 5 ppbv d^(−1) in the upper troposphere. Three chemical regimes (NO_x-limited, transition, NO_x-saturated) are identified to describe the dependence of HO_x concentrations and ozone production rates on the two master variables P(HO_x) and [NO_x]. Simplified analytical expressions are derived to express these dependences as power laws for each regime. By applying an eigenlifetime analysis to the HO_x–NO_x–O_3 chemical system, we find that the decay of a perturbation to HO_y in the upper troposphere (as from deep convection) is represented by four dominant modes with the longest time scale being factors of 2–3 times longer than the steady-state lifetime of HO_y.

Observed OH and HO2 in the upper troposphere suggest a major source from convective injection of peroxides

ER-2 aircraft observations of OH and HO_2 concentrations in the upper troposphere during the NASA/STRAT campaign are interpreted using a photochemical model constrained by local observations of O_3, H_2O, NO, CO, hydrocarbons, albedo and overhead ozone column. We find that the reaction Q(^(1)D) + H_2O is minor compared to acetone photolysis as a primary source of HO_x (= OH + peroxy radicals) in the upper troposphere. Calculations using a diel steady state model agree with observed HO_x concentrations in the lower stratosphere and, for some flights, in the upper troposphere. However, for other flights in the upper troposphere, the steady state model underestimates observations by a factor of 2 or more. These model underestimates are found to be related to a recent (< 1 week) convective origin of the air. By conducting time-dependent model calculations along air trajectories determined for the STRAT flights, we show that convective injection of CH_3OOH and H_2O_2 from the boundary layer to the upper troposphere could resolve the discrepancy. These injections of HO_x reservoirs cause large HO_x increases in the tropical upper troposphere for over a week downwind of the convective activity. We propose that this mechanism provides a major source of HO_x in the upper troposphere. Simultaneous measurements of peroxides, formaldehyde and acetone along with OH and HO_2 are needed to test our hypothesis.

Photochemistry of HO x in the upper troposphere at northern midlatitudes

The factors controlling the concentrations of HOx radicals (= OH + peroxy) in the upper troposphere (8–12 km) are examined using concurrent aircraft observations of OH, HO2, H2O2, CH3OOH, and CH2O made during the Subsonic Assessment Ozone and Nitrogen Oxide Experiment (SONEX) at northern midlatitudes in the fall. These observations, complemented by concurrent measurements of O3, H2O, NO, peroxyacetyl nitrate (PAN), HNO3, CH4, CO, acetone, hydrocarbons, actinic fluxes, and aerosols, allow a highly constrained mass balance analysis of HOx and of the larger chemical family HOy (= HOx + 2 H2O2 + 2 CH3OOH + HNO2 + HNO4). Observations of OH and HO2 are successfully simulated to within 40% by a diel steady state model constrained with observed H2O2 and CH3OOH. The model captures 85% of the observed HOx variance, which is driven mainly by the concentrations of NOx (= NO + NO2) and by the strength of the HOx primary sources. Exceptions to the good agreement between modeled and observed HOx are at sunrise and sunset, where the model is too low by factors of 2–5, and inside cirrus clouds, where the model is too high by factors of 1.2–2. Heterogeneous conversion of NO2 to HONO on aerosols (γNO2 = 10−3) during the night followed by photolysis of HONO could explain part of the discrepancy at sunrise. Heterogeneous loss of HO2 on ice crystals (γice_HO2 = 0.025) could explain the discrepancy in cirrus. Primary sources of HOx from O(1D)+H2O and acetone photolysis were of comparable magnitude during SONEX. The dominant sinks of HOy were OH+HO2 (NOx 50 pptv). Observed H2O2 concentrations are reproduced by model calculations to within 50% if one allows in the model for heterogeneous conversion of HO2 to H2O2 on aerosols (γHO2 = 0.2). Observed CH3OOH concentrations are underestimated by a factor of 2 on average. Observed CH2O concentrations were usually below the 50 pptv detection limit, consistent with model results; however, frequent occurrences of high values in the observations (up to 350 pptv) are not captured by the model. These high values are correlated with high CH3OH and with cirrus clouds. Heterogeneous oxidation of CH3OH to CH2O on aerosols or ice crystals might provide an explanation (γice_CH3OH ∼ 0.01 would be needed).

Sources and chemistry of NOx in the upper troposphere over the United States

The origin of NOx in the upper troposphere over the central United States is examined using aircraft observations obtained during the SUCCESS campaign in April–May of 1996. Correlations between NOy (sum of NOx and its oxidation products) and CO at 8–12 km altitude indicate that NOx originates primarily from convective transport of polluted boundary layer air. Lightning and aircraft emissions appear to be only minor sources of NOx. Chemical steady state model calculations constrained by local observations of NO underestimate the measured NOx/NOy concentration ratio at 8–12 km altitude by a factor of two on average. The magnitude of the underestimate is correlated with concentrations of condensation nuclei, which we take as a proxy for the age of air in the upper troposphere. We conclude that the NOx/NOy ratio is maintained above chemical steady state by frequent convective injections of fresh NOx from the polluted boundary layer and by the long lifetime of NOx in the upper troposphere (5–10 days). In contrast to previous studies, we find no evidence for fast heterogeneous recycling from HNO3 to NOx in the upper troposphere.

Observations of Reactive Gaseous Mercury in the Free Troposphere at the Mount Bachelor Observatory

August 2005. The mean mercury concentrations (at standard conditions) were 1.54 ng/m 3 (GEM), 5.2 pg/m 3 (PHg), and 43 pg/m 3 (RGM). RGM enhancements, up to 600 pg/m 3 , occurred at night and were linked to a diurnal pattern of upslope and downslope flows that mixed in boundary layer air during the day and free tropospheric air at night. During the night, RGM was inversely correlated (P < 0.0001) with CO (r = � 0.36), GEM (r = � 0.73), and H2 O( r =� 0.44), was positively correlated with ozone (r = 0.38), and could not be linked to recent anthropogenic emissions from local sources or long-range transport. Principal component analysis and a composite of change in RGM versus change in GEM during RGM enhancements indicate that a nearly quantitative shift in speciation is associated with increases in ozone and decreases in water vapor and CO. This argues that high concentrations of RGM are present in the free troposphere because of in situ oxidation of GEM to RGM. A global chemical transport model reproduces the RGM mean and diurnal pattern but underestimates the magnitude of the largest observed enhancements. Since the only modeled, in situ RGM production mechanisms are oxidation of GEM by ozone and OH, this implies that there are faster reaction rates or additional RGM production mechanisms in the free troposphere.

Airborne in-situ OH and HO2 observations in the cloud-free troposphere and lower stratosphere during SUCCESS

The hydroxyl (OH) and hydroperoxyl (HO2) radicals were measured for the first time throughout the troposphere and in the lower stratosphere with a new instrument aboard the NASA DC-8 aircraft during the 1996 SUCCESS mission. Typically midday OH was 0.1-0.5 pptv and HO2 was 3-15 pptv. Comparisons with a steady-state model yield the following conclusions. First, even in the lower stratosphere OH was sensitive to the albedo of low clouds and distant high clouds. Second, although sometimes in agreement with models, observed OH and HO2 were more than 4 times larger at other times. Evidence suggests that for the California upper troposphere on 10 May this discrepancy was due to unmeasured HOx sources from Asia. Third, observed HO2/OH had the expected inverse dependence with NO, but was inexplicably higher than modeled HO2/OH by an average of 30%. Finally, small-scale, midday OH and HO2 features were strongly linked to NO variations.

Sources and budgets for CO and O3 in the northeastern Pacific during the spring of 2001: Results from the PHOBEA-II Experiment

Reference LMCA-ARTICLE-2006-009doi:10.1029/2002JD003121View record in Web of Science Record created on 2006-06-01, modified on 2016-08-08

Sources of HOx and production of ozone in the upper troposphere over the United States

The sources of HO x (OH+peroxy radicals) and the associated production of ozone at 8-12 km over the United States are examined by modeling observations of OH, HO 2 , NO, and other species during the SUCCESS aircraft campaign in April-May 1996. The HO x concentrations measured in SUCCESS are up to a factor of 3 higher than can be calculated from oxidation of water vapor and photolysis of acetone. The highest discrepancy was seen in the outflow of a convective storm. We show that convective injection of peroxides (CH 3 OOH and H 2 O 2 ) and formaldehyde (CH 2 O) from the boundary layer to the upper troposphere could resolve this discrepancy. More generally, the data collected over the central United States during SUCCESS suggest that local convection was a major source of HO x and NO x to the upper troposphere. The OH and HO 2 observations together with the observations of NO allow us to directly calculate the ozone production in the upper troposphere and its dependence on NO x . We find an average net ozone production of 2 ppbv day -1 between 8 and 12 km over the continental United States in the spring. Ozone production was NO x -limited under essentially all the conditions encountered in SUCCESS. The high levels of HO x present in the upper troposphere stimulate ozone production and increase the sensitivity of ozone to NO x emissions from aircraft and other sources.