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Consistent validation of satellite CO2 estimates is a prerequisite for using multiple satellite CO2measurements for joint flux inversion and establishing a long-term atmospheric CO2 data record. Wevalidate recent satellite observation of OCO-2 v7 and ACOS-GOSAT v7.3 using similar analysis as previouswork (Kulawik et al. (2016) and Frankenberg et al. (2106)) through comparisons to the HIAPER Pole-to-Pole Observations (HIPPO) and the Total Carbon Column Observing Network (TCCON) to estimate biasesand errors affecting the understanding of carbon cycle science. CarbonTracker RT is also compared tothe validation data, and additionally used to evaluate the mismatch between the HIPPO observationtimeframe and the OCO-2 record, which are offset by 3-7 years. Some key metrics that are validatedinclude the seasonal cycle phase and amplitude, latitudinal gradient by season, regional biases, anderrors with respect to averaging.

The chemical composition of the lowermost stratosphere exhibits both spatial and temporal variability depending upon the relative strength of (1) isentropic transport from the tropical tropopause layer (TTL), (2) diabatic descent from the midlatitude and northern midlatitude stratosphere followed by equatorward isentropic transport, and (3) diabatic ascent from the troposphere through convection. In situ measurements made in the lowermost stratosphere over Florida illustrate the additional impact of equatorward flow around the monsoon anticyclone. This flow carries, along with older stratospheric air, the distinct signature of deep midlatitude convection. We use simultaneous in situ measurements of water vapor (H2O), ozone (O3), total odd nitrogen (NOy), carbon dioxide (CO2), and carbon monoxide (CO) in the framework of a simple box model to quantify the composition of the air sampled in the lowermost stratosphere during the mission on the basis of tracer mixing ratios ascribed to the source regions for these transport pathways. The results show that in the summer, convection has a significant impact on the composition of air in the lowermost stratosphere, being the dominant source of water vapor up to the 380 K isentrope. The implications of these results extend from the potential for heterogeneous ozone loss resulting from the increased frequency and lifetime of cirrus near the local tropopause, to air with increased water vapor that as part of the equatorward flow associated with the North American monsoon can become part of the general circulation.

Accurate mean ages for stratospheric air have been derived from a spatially and temporally comprehensive set of in situ observations of CO2, CH4, and N2O obtained from 1992 to 1998 from the NASA ER-2 aircraft and balloon flights. Errors associated with the tropospheric CO2 seasonal cycle and interannual variations in the CO2 growth rate are less than 0.5 year throughout the stratosphere and less than 0.3 year for air older than 2 years (N2O less than 275 ppbv), indicating that the age spectra are broad enough to attenuate these influences over the time period covered by these observations. The distribution of mean age with latitude and altitude provides detailed, quantitative information about the general circulation of the stratosphere. At 20 km, sharp meridional gradients in the mean age are observed across the subtropics. Between 20 and 30 km, the average difference in mean age between the tropics and midlatitudes is approximately 2 years, with slightly smaller differences at higher and lower altitudes. The mean age in the midlatitude middle stratosphere (approx. 25-32 km) is relatively constant with respect to altitude at 5 plus or minus 0.5 years. Comparison with earlier balloon observations of CO2 dating back to the 1970s indicates that the mean age of air in this region has remained within 11 year of its current value over the last 25 years. A climatology of mean age is derived from the observed compact relationship between mean age and N2O. These characteristics of the distribution of mean age in the stratosphere will serve as critically needed diagnostics for models of stratospheric transport.

Two in situ CO2 analyzers have been developed for deployment on the NASA ER-2 aircraft and on stratospheric balloons. The ER-2 instrument has had more than 150 flights during 21 deployments from 1992 to 2000, resulting in a dataset with nearly pole-to-pole coverage that includes data from all seasons in both hemispheres except austral summer. In-flight calibrations show that the typical long-term (i.e. flight-to-flight) precision of the instruments is better than plus or minus 0.1 ppmv. The flight standards are traceable to standards held by the Scripps Institute of Oceanography and the National Oceanic and Atmospheric Administration's Climate Monitoring and Diagnostics Laboratory. The balloon instrument has had 8 balloon flights since September 1996, providing the first in situ observations of CO2 above approx. 21 km. In addition, the balloon instrument has been flown onboard a Cessna Citation II aircraft for sampling between the surface and 10 km. In this paper, the instrumentation and calibration procedures for both instruments are described in detail. An intercomparison of the two instruments during the Photochemistry of Ozone Loss in the Arctic Region In Summer (POLARIS) project showed that, on average, the instruments agreed to within 0.05 ppmv.

The origin of air in the lowermost stratosphere is investigated with measurements from the NASA ER-2 aircraft. Air with high water vapor mixing ratios was observed in the stratosphere at theta approximately 330-380 K near 40 N in May 1995, indicating the influence of intrusions of tropospheric air. Assuming that observed tracer-tracer relationships reflect mixing lines between tropospheric and stratospheric air masses, we calculate mixing ratios of H2O (12-24 ppmv) and CO2 for the admixed tropospheric air at theta = 352-364 K. Temperatures on the 355 K surface 20-40 N were low enough to dehydrate air to these values. While most ER-2 CO2 data in both hemispheres are consistent with tropical or subtropical air entering the lowermost stratosphere, measurements from May 1995 for theta < 362 K suggest that entry of air from the midlatitude upper troposphere can occur in conjunction with mixing processes near the tropopause.

A model of the daily carbon balance of a black spruce/feathermoss boreal forest ecosystem was developed and results compared to preliminary data from the 1994 BOREAS field campaign in northern Manitoba, Canada. The model, driven by daily weather conditions, simulated daily soil climate status (temperature and moisture profiles), spruce photosynthesis and respiration, moss photosynthesis and respiration, and litter decomposition. Model agreement with preliminary field data was good for net ecosystem exchange (NEE), capturing both the asymmetrical seasonality and short-term variability. During the growing season simulated daily NEE ranged from -4 g C m(exp -2) d(exp -1) (carbon uptake by ecosystem) to + 2 g C m(exp -2) d(exp -1) (carbon flux to atmosphere), with fluctuations from day to day. In the early winter simulated NEE values were + 0.5 g C m(exp -2) d(exp -1), dropping to + 0.2 g C m(exp -2) d(exp -1) in mid-winter. Simulated soil respiration during the growing season (+ 1 to + 5 g C m(exp -2) d(exp -1)) was dominated by metabolic respiration of the live moss, with litter decomposition usually contributing less than 30% and live spruce root respiration less than 10% of the total. Both spruce and moss net primary productivity (NPP) rates were higher in early summer than late summer. Simulated annual NEE for 1994 was -51 g C m(exp -2) y(exp -1), with 83% going into tree growth and 17% into the soil carbon accumulation. Moss NPP (58 g C m(exp -2) d(exp -1)) was considered to be litter (i.e. soil carbon input; no net increase in live moss biomass). Ecosystem respiration during the snow-covered season (84 g Cm(exp -2)) was 58% of the growing season net carbon uptake. A simulation of the same site for 1968-1989 showed about 10-20% year-to-year variability in heterotrophic respiration (mean of + 113 g C m-2 y@1). Moss NPP ranged from 19 to 114 g C m(exp -2) y(exp -1); spruce NPP from 81 to 150 g C nt-2 y,@l; spruce growth (NPP minus litterfall) from 34 to 103 g C m(exp -2) y(exp -1); NEE ranged from +37 to -142 g C m(exp -2) y(exp -1). Values for these carbon balance terms in 1994 were slightly smaller than the 1969 - 89 means. Higher ecosystem productivity years (more negative NEE) generally had early springs and relatively wet summers; lower productivity years had late springs and relatively dry summers.

Instrumentation on the NASA ER-2 high-altitude aircraft has been used to observe engine exhaust from the same aircraft while operating in the lower stratosphere. Encounters with the exhaust plume occurred approximately 10 min after emission with spatial scales near 2 km and durations of up to 10 s. Measurements include total reactive nitrogen, NO(y), the component species NO and NO2, CO2, H2O, CO, N2O, condensation nuclei, and meteorological parameters. The integrated amounts of CO2 and H2O during the encounters are consistent with the stoichiometry of fuel combustion (1:1 molar). Emission indices (EI) for NO(x) (= NO + NO2), CO, and N2O are calculated using simultaneous measurements of CO2. EI values for NO(x) near 4 g/(kg fuel) are in good agreement with values scaled from limited ground-based tests of the ER-2 engine. Non-NO(x) species comprise less than about 20% of emitted reactive nitrogen, consistent with model evaluations. In addition to demonstrating the feasibility of aircraft plume detection, these results increase confidence in the projection of emissions from current and proposed supersonic aircraft fleets and hence in the assessment of potential long-term changes in the atmosphere.

The effect of NO(x) (NO + NO2) from aircraft engine exhaust on ozone and climate is of increasing concern as a result of anticipated growth in the world's subsonic aircraft fleet and new international efforts to build a supersonic transport (SST). Knowledge of NO(x) emissions currently relies on limited ground based testing of combustors and engines and on scaling relations to extrapolate emission values to upper atmosphere conditions. Direct observations made in the engine exhaust plume of the NASA ER-2 high altitude aircraft cruising at subsonic speeds in the lower midlatitude stratosphere are presented. Results demonstrate the technical feasibility of detecting aircraft plumes within minutes after emission with sufficient completeness and precision to calculate emission indices for reactive nitrogen and other species. Furthermore, the combined results increase confidence in using ground based observations to assess the atmospheric impact of some aircraft emissions.

Balloon profiles of chlorine monoxide (ClO), nitric oxide (NO), and ozone (O3) were measured on March 11, 1992 from 100 to 10 mb over Greenland (67.0 deg N, 50.6 deg W). Measurements from SAGE II indicate that the aerosol surface area in the region was enhanced by sulfur from the eruption of Mt. Pinatubo, reaching 50 times background near 20 km. Concentrations of ClO were enhanced and concentrations of NO were suppressed relative to low aerosol conditions consistent with the effects of hydrolysis of N2O5 on the surface of sulfuric acid aerosols. The data are consistent with a value of 2 x 10(exp -4) for the reaction probability of the heterogeneous hydrolysis of ClONO2, indicating a minor role for this reaction at as temperature of 220 K. At these temperatures, we find no evidence for the catastrophic loss of ozone predicted to occur under conditions of enhanced aerosol surface area.