CO2 Mixing Ratios Research Articles

An analysis of Pluto occultation light curves using an atmospheric radiative–conductive model

We use a radiative–conductive model to least-squares fit Pluto stellar occultation light curve data. This model predicts atmospheric temperature based on surface temperature, surface pressure, surface radius, and CH 4 and CO mixing ratios, from which model light curves are to be calculated. The model improves upon previous techniques for deriving Pluto’s atmospheric thermal structure from stellar occultation light curves by calculating temperature (as a function of height) caused by heating and cooling by species in Pluto’s atmosphere, instead of a general assumption that temperature follows a power law with height or some other idealized function. We are able to fit for model surface radius, surface pressure, and CH 4 mixing ratio with one of the 2006 datasets and for surface pressure and CH 4 mixing ratio for other datasets from the years 1988, 2002, 2006, and 2008. It was not possible to fit for CO mixing ratio and surface temperature because the light curves are not sensitive to these parameters. We determine that the model surface radius, under the assumption of a stratosphere only (i.e. no troposphere) model in radiative–conductive balance, is 1180 - 10 + 20 km . The CH 4 mixing ratio results are more scattered with time and are in the range of 1.8–9.4 × 10 −3. The surface pressure results show an increasing trend from 1988 to 2002, although it is not as dramatic as the factor of 2 from previous studies.

Continuous low-maintenance CO<sub>2</sub>/CH<sub>4</sub>/H<sub>2</sub>O measurements at the Zotino Tall Tower Observatory (ZOTTO) in Central Siberia

Abstract. To monitor the continental carbon cycle, a fully automated low maintenance measurement system is installed at the Zotino Tall Tower Observatory in Central Siberia (ZOTTO, 60°48' N, 89°21' E) since April 2009. A cavity ring-down spectroscopy (CRDS) analyzer continuously measures carbon dioxide (CO2) and methane (CH4) from six heights up to 301 m a.g.l. Buffer volumes in each air line remove short term CO2 and CH4 mixing ratio fluctuations associated with turbulence, and allow continuous, near-concurrent measurements from all tower levels. Instead of drying the air sample, the simultaneously measured water vapor is used to correct the dilution and pressure-broadening effects for the accurate determination of dry air CO2 and CH4 mixing ratios. The stability of the water vapor correction was demonstrated by repeated laboratory and field tests. The effect of molecular adsorption in the wet air lines was shown to be negligible. The low consumption of four calibration tanks that need recalibration only on decadal timescale further reduces maintenance. The measurement precision (accuracy) of 0.04 ppm (0.09 ppm) for CO2 and 0.3 ppb (1.5 ppb) for CH4 is compliant with the WMO recommendations. The data collected so far (until April 2010) reveals a seasonal cycle amplitude for CO2 of 30.4 ppm at the 301 m level.

Fossil fuel CO2 estimation by atmospheric 14C measurement and CO2 mixing ratios in the city of Debrecen, Hungary

A field unit was installed in the city of Debrecen (East Hungary) during the summer of 2008 to monitor urban atmospheric fossil fuel CO2. To establish a reference level simultaneous CO2 sampling has been carried out at a rural site (Hegyhatsal) in Western Hungary. Using the Hungarian background 14CO2 observations from the rural site atmospheric fossil fuel CO2 component for the city of Debrecen was reported in a regional “Hungarian” scale. A well visible fossil fuel CO2 peak (10–15 ppm) with a maximum in the middle of winter 2008 (January) was observed in Debrecen air. Significant local maximum (~20 ppm) in fossil fuel CO2 during Octobers of 2008 and 2009 was also detected. Stable isotope results are in agreement with the 14C based fossil fuel CO2 observations as the winter of 2008 and 2009 was different in atmospheric δ13C variations too. The more negative δ13C of atmospheric CO2 in the winter of 2008 means more fossil carbon in the atmosphere than during the winter of 2009.

Spatial distribution of near-surface CO over bay of Bengal during winter: role of transport

As part of Integrated Campaign for Aerosols, gases and Radiation Budget (ICARB), cruise-based measurements of near-surface CO were carried out over Bay of Bengal (BoB) covering the latitude–longitude sector 3.5°N–21.0°N and 76.0°E–98.0°E, during winter months of December 2008 to January 2009. These in-situ measured CO mixing ratio varied in the range of 80–480 ppbv over this marine environment with the distinct spatial pattern. The highest mixing ratios were measured over southeast-BoB with mean value of 379±58 ppbv. CO mixing ratios were high over north-BoB compared to southern BoB. These in-situ measurements were compared with the satellite-measured surface CO obtained from Measurements of Pollution in the Troposphere (MOPITT) onboard TERRA and found to be in good agreement over most of the regions, except at southeast-BoB. Surface CO and column CO from MOPITT data showed a similar spatial pattern. Based on the analysis of airmass back-trajectories, satellite-based spatial map of CO distribution over Asian region and Potential Source Contribution Function analysis, different pathways of transport of CO were identified. Transport from northern landmass as well as from south-east Asia has a significant influence in the spatial variation of CO over BoB. Winter-time mixing ratio of CO was found to be higher compared to those measured during other campaigns conducted during February–March 1999, 2001 (pre-monsoon) and September–October, 2002 (post-monsoon).

Co-located column and in situ measurements of CO<sub>2</sub> in the tropics compared with model simulations

Abstract. The first ground-based remote sensing measurements of the column averaged volume mixing ratio of CO2 (XCO2) in tropical South America have been obtained at Paramaribo, Suriname (5.8° N, 55.2° W). The remote sensing observations are complemented by surface air-samples collected at the site, analyzed for CO2 and 13CO2. The surface in-situ measurements are strongly influenced by local sources. From the isotopic composition of the air samples the local source component is suggested to be dominated by the terrestrial biosphere. Using δ13C from the NOAA/ESRL stations Ascension Is. (ASC), 7.9° S, 14.4° W, and Ragged Point (RPB), 13.2° N, 59.4° W, the data has been corrected for the local source component. Due to the migration of the Intertropical Convergence Zone (ITCZ) over the measurement site the sampled air masses belong to the Northern or Southern Hemisphere depending on the time of the year. Comparison to analyzed CO2 fields based on TM3 model simulations using optimized fluxes indicate agreement for the seasonality in XCO2 as well as for the corrected CO2 mixing ratios at the surface for the long dry season, when Paramaribo belongs to the Southern Hemisphere. A slightly worse agreement during the short dry season is attributed to a larger representation error during this time of the year. Overall the comparison indicates that the TM3 model is capable to simulate the seasonal variation of surface concentrations as well as column densities of CO2 correctly at Paramaribo. It has been also shown that the column measurements currently performed at Paramaribo have a limited precision and lack the link to the in situ measurements. Solutions for future improvements have been suggested.

Lorentz half-width, pressure-induced shift and speed-dependent coefficients in oxygen-broadened CO 2 bands at 6227 and 6348 cm −1 using a constrained multispectrum analysis

The McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory (NSO) on Kitt Peak, Arizona, was used to record infrared high resolution absorption spectra of CO 2 spectra broadened by O 2. These spectra were analyzed to measure O 2-broadened half-width coefficients, O 2-induced pressure-shift coefficients and speed dependent parameters for transitions in the 30013←00001 and 30012←00001 bands of 16O 12C 16O located near 6227 and 6348 cm −1, respectively. All spectra were obtained at room temperature using the long path, 6 m base path White cell available at NSO. A multispectrum nonlinear least-squares fitting algorithm employing Voigt line shapes modified to include line mixing and speed dependence was used to fit simultaneously a total of 19 spectra in the 6120–6280 cm −1 (30013←00001) and 6280–6395 cm −1 (30012←00001) spectral regions. 16 of the 19 spectra analyzed in this work were self broadened and three spectra were lean mixtures of CO 2 in O 2. The volume mixing ratios of CO 2 in the three spectra varied between 0.06 and 0.1. Lorentz half-width and pressure-induced shift coefficients were measured for all transitions in the P(50)–R(50) range in both vibrational bands. The results obtained from present analysis have been compared with measurements available in the literature for self-, air-, oxygen- and argon-broadening. No significant differences were observed between the broadening and shift coefficients of the two bands. The N 2-broadened half-width and pressure-shift coefficients were computed from measured air- and O 2-broadened width and shift coefficients.

Circumpolar measurements of speciated mercury, ozone and carbon monoxide in the boundary layer of the Arctic Ocean

Abstract. Using the Swedish icebreaker Oden as a platform, continuous measurements of airborne mercury (gaseous elemental mercury (Hg0), divalent gaseous mercury species HgIIX2(g) (acronym RGM) and mercury attached to particles (PHg)) and some long-lived trace gases (carbon monoxide CO and ozone O3) were performed over the North Atlantic and the Arctic Ocean. The measurements were performed for nearly three months (July–September 2005) during the Beringia 2005 expedition (from Göteborg, Sweden via the proper Northwest Passage to the Beringia region Alaska – Chukchi Penninsula – Wrangel Island and in-turn via a north-polar transect to Longyearbyen, Spitsbergen). The Beringia 2005 expedition was the first time that these species have been measured during summer over the Arctic Ocean going from 60° to 90° N. During the North Atlantic transect, concentration levels of Hg0, CO and O3 were measured comparable to typical levels for the ambient mid-hemispheric average. However, a rapid increase of Hg0 in air and surface water was observed when entering the ice-covered waters of the Canadian Arctic archipelago. Large parts of the measured waters were supersaturated with respect to Hg0, reflecting a strong disequilibrium. Heading through the sea ice of the Arctic Ocean, a fraction of the strong Hg0 pulse in the water was transferred with some time-delay into the air samples collected ~20 m above sea level. Several episodes of elevated Hg0 in air were encountered along the sea ice route with higher mean concentration (1.81±0.43 ng m−3) compared to the marine boundary layer over ice-free Arctic oceanic waters (1.55±0.21 ng m−3). In addition, the bulk of the variance in the temporal series of Hg0 concentrations was observed during July. The Oden Hg0 observations compare in this aspect very favourably with those at the coastal station Alert. Atmospheric boundary layer O3 mixing ratios decreased when initially sailing northward. In the Arctic, an O3 minimum around 15–20 ppbV was observed during summer (July–August). Alongside the polar transect during the beginning of autumn, a steady trend of increasing O3 mixing ratios was measured returning to initial levels of the expedition (>30 ppbV). Ambient CO was fairly stable (84±12 ppbV) during the expedition. However, from the Beaufort Sea and moving onwards steadily increasing CO mixing ratios were observed (0.3 ppbV day−1). On a comparison with coeval archived CO and O3 data from the Arctic coastal strip monitoring sites Barrow and Alert, the observations from Oden indicate these species to be homogeneously distributed over the Arctic Ocean. Neither correlated low ozone and Hg0 events nor elevated concentrations of RGM and PHg were at any extent sampled, suggesting that atmospheric mercury deposition to the Arctic basin is low during the Polar summer and autumn.

Effects of the solar eclipse on 15 January 2010 on the surface O<sub>3</sub>, NO, NO<sub>2</sub>, NH<sub>3</sub>, CO mixing ratio and the meteorological parameters at Thiruvanathapuram, India

Abstract. In this paper, we present the effect of total solar eclipse on surface O3, NO, NO2, NH3, CO mixing ratio and the meteorological parameters on 15 January 2010 at Thiruvanathapuram, India. On the day of total solar eclipse (i.e., 15 January 2010), the decrease in mixing ratio of surface O3 and NO2 is observed after the beginning of the solar eclipse events (11:15 to 15:30). Decrease in surface O3 may be due to decreased efficiency of the photochemical ozone formation, whereas, mixing ratio of NO and NH3 have been changed following the night time chemistry. Surface O3 reduced to 20.3 ppb after 22 min of full phase of the eclipse. During the solar eclipse period, the ambient temperature and wind speed have decreased, whereas, relative humidity has increased as expected.

The orbital motion, absolute mass and high-altitude winds of exoplanet HD 209458b

For extrasolar planets discovered using the radial velocity method, the spectral characterization of the host star leads to a mass estimate of the star and subsequently of the orbiting planet. If the orbital velocity of the planet could be determined, the masses of both star and planet could be calculated using Newton's law of gravity, just as in the case of stellar double-line eclipsing binaries. Here we report high-dispersion ground-based spectroscopy of a transit of the extrasolar planet HD 209458b. We see a significant wavelength shift in absorption lines from carbon monoxide in the planet's atmosphere, which we conclude arises from a change in the radial component of the planet's orbital velocity. The masses of the star and planet are 1.00 +/- 0.22M(Sun) and 0.64 +/- 0.09M(Jup) respectively. A blueshift of the carbon monoxide signal of approximately 2 km s(-1) with respect to the systemic velocity of the host star suggests the presence of a strong wind flowing from the irradiated dayside to the non-irradiated nightside of the planet within the 0.01-0.1 mbar atmospheric pressure range probed by these observations. The strength of the carbon monoxide signal suggests a carbon monoxide mixing ratio of (1-3) x 10(-3) in this planet's upper atmosphere.

A regional high-resolution carbon flux inversion of North America for 2004

Abstract. Resolving the discrepancies between NEE estimates based upon (1) ground studies and (2) atmospheric inversion results, demands increasingly sophisticated techniques. In this paper we present a high-resolution inversion based upon a regional meteorology model (RAMS) and an underlying biosphere (SiB3) model, both running on an identical 40 km grid over most of North America. Current operational systems like CarbonTracker as well as many previous global inversions including the Transcom suite of inversions have utilized inversion regions formed by collapsing biome-similar grid cells into larger aggregated regions. An extreme example of this might be where corrections to NEE imposed on forested regions on the east coast of the United States might be the same as that imposed on forests on the west coast of the United States while, in reality, there likely exist subtle differences in the two areas, both natural and anthropogenic. Our current inversion framework utilizes a combination of previously employed inversion techniques while allowing carbon flux corrections to be biome independent. Temporally and spatially high-resolution results utilizing biome-independent corrections provide insight into carbon dynamics in North America. In particular, we analyze hourly CO2 mixing ratio data from a sparse network of eight towers in North America for 2004. A prior estimate of carbon fluxes due to Gross Primary Productivity (GPP) and Ecosystem Respiration (ER) is constructed from the SiB3 biosphere model on a 40 km grid. A combination of transport from the RAMS and the Parameterized Chemical Transport Model (PCTM) models is used to forge a connection between upwind biosphere fluxes and downwind observed CO2 mixing ratio data. A Kalman filter procedure is used to estimate weekly corrections to biosphere fluxes based upon observed CO2. RMSE-weighted annual NEE estimates, over an ensemble of potential inversion parameter sets, show a mean estimate 0.57 Pg/yr sink in North America. We perform the inversion with two independently derived boundary inflow conditions and calculate jackknife-based statistics to test the robustness of the model results. We then compare final results to estimates obtained from the CarbonTracker inversion system and at the Southern Great Plains flux site. Results are promising, showing the ability to correct carbon fluxes from the biosphere models over annual and seasonal time scales, as well as over the different GPP and ER components. Additionally, the correlation of an estimated sink of carbon in the South Central United States with regional anomalously high precipitation in an area of managed agricultural and forest lands provides interesting hypotheses for future work.

Greenhouse gas relationships in the Indian summer monsoon plume measured by the CARIBIC passenger aircraft

Abstract. During the Indian summer monsoon period 2008, regular measurement flights were performed by the CARIBIC aircraft between Germany and India. Measurements included whole air sampling and subsequent analysis for greenhouse gases (CH4, CO2, N2O, SF6) and in-situ measurements of CO, O3, and H2O. For all these tracers a distinct monsoon signature was observed in the longitude range 50–80° E south of 40° N at flight altitudes 8–12.5 km. The formation of a monsoon plume with enhanced mixing ratios was observed for CH4, N2O, SF6, CO and H2O. The plume began to develop in May and persisted through September, and maximum mixing ratios and maximum spatial extension of the plume were observed in August. For CO2 and O3 a minimum was observed. The amplitude of the CO2 seasonal cycle was larger than at comparable latitudes outside the monsoon region, and the CO2 spring maximum was observed with a delay of one month. Different tracer relationships show strong spatial variations across the plume. The comparison with NOAA ground station data shows a clear enhancement for CH4, N2O, SF6 and CO and a decrease in CO2 mixing ratios. Assuming seasonally invariant SF6 emissions based on the EDGAR 4.0 inventory, monthly emissions were estimated for the period June–September for CH4, N2O, and CO, and the CO2 uptake was estimated. While for N2O an emission decrease during the monsoon period was derived, emissions of CH4 were highest in September indicating a different seasonal cycle of emissions. Net CO2 uptake by the vegetation was largest in September.

Revisit to the Nuclear Spin Temperature of NH$_{3}$ in Comet C/2001 Q4 (NEAT) Based on High-Dispersion Spectra of Cometary NH$_{2}$

Abstract The Ortho-to-Para abundance ratio (OPR) of cometary molecules is considered to be one of primordial characters of comeary ices, which has information concerning their formation. In order to determine the OPR of cometary ammonia (NH$_{3}$), high-dispersion spectra in the optical wavelength region have been the most powerful tool, since NH$_{2}$ is a photo-dissociation product of NH$_{3}$, and NH$_{2}$ has a strong electronic transition in the optical region. Here we present an improved procedure to derive the OPR of NH$_{2}$ (OPR of NH$_{3}$ is derived from that of NH$_{2}$) from the high-dispersion spectra of NH$_{2}$ in comets. We consider (1) the contamination of NH$_{2}$ lines by the C$_{2}$ Swan-band lines, (2) the influence by the telluric absorption lines, and (3) multiple measurements of OPR from different vibronic bands of NH$_{2}$ in the optical region, to achieve a more accurate determination of OPRs than that in previous studies. We applied the new method to the spectrum of comet C/2001 Q4 (NEAT) for which the OPR of NH$_{2}$ was determined in the previous study. The derived OPR of NH$_{2}$ is 3.23$ \pm $0.03, and this is more accurate than before. The OPR of NH$_{3}$ is estimated to be 1.12$ \pm $0.02, which corresponds to a nuclear spin temperature ($T_\mathrm{spin}$) of 30$^{+2}_{-1} $K. The $T_\mathrm{spin}$ value of NH$_{3}$ is basically consistent with the temperature inferred from the mixing ratio of CO with respect to H$_{2}$O found in the same comet.

Tracer measurements in the tropical tropopause layer during the AMMA/SCOUT-O3 aircraft campaign

Abstract. We present airborne in situ measurements made during the AMMA (African Monsoon Multidisciplinary Analysis)/SCOUT-O3 campaign between 31 July and 17 August 2006 on board the M55 Geophysica aircraft, based in Ouagadougou, Burkina Faso. CO2 and N2O were measured with the High Altitude Gas Analyzer (HAGAR), CO was measured with the Cryogenically Operated Laser Diode (COLD) instrument, and O3 with the Fast Ozone ANalyzer (FOZAN). We analyse the data obtained during five local flights to study the dominant transport processes controlling the tropical tropopause layer (TTL, here ~350–375 K) and lower stratosphere above West-Africa: deep convection up to the level of main convective outflow, overshooting of deep convection, and horizontal inmixing across the subtropical tropopause. Besides, we examine the morphology of the stratospheric subtropical barrier. Except for the flight of 13 August, distinct minima in CO2 mixing ratios indicate convective outflow of boundary layer air in the TTL. The CO2 profiles show that the level of main convective outflow was mostly located at potential temperatures between 350 and 360 K, and for 11 August reached up to 370 K. While the CO2 minima indicate quite significant convective influence, the O3 profiles suggest that the observed convective signatures were mostly not fresh, but of older origin (several days or more). When compared with the mean O3 profile measured during a previous campaign over Darwin in November 2005, the O3 minimum at the main convective outflow level was less pronounced over Ouagadougou. Furthermore O3 mixing ratios were much higher throughout the whole TTL and, unlike over Darwin, rarely showed low values observed in the regional boundary layer. Signatures of irreversible mixing following overshooting of convective air were scarce in the tracer data. Some small signatures indicative of this process were found in CO2 profiles between 390 and 410 K during the flights of 4 and 8 August, and in CO data at 410 K on 7 August. However, the absence of expected corresponding signatures in other tracer data makes this evidence inconclusive, and overall there is little indication from the observations that overshooting convection has a profound impact on gas-phase tracer TTL composition during AMMA. We find the amount of photochemically aged air isentropically mixed into the TTL across the subtropical tropopause to be not significant. Using the N2O observations we estimate the fraction of aged extratropical stratospheric air in the TTL to be 0.0±0.1 up to 370 K during the local flights. Above the TTL this fraction increases to 0.3±0.1 at 390 K. The subtropical barrier, as indicated by the slope of the correlation between N2O and O3 between 415 and 490 K, does not appear as a sharp border between the tropics and extratropics, but rather as a gradual transition region between 10° N and 25° N where isentropic mixing between these two regions may occur.

Spatially-resolved high-resolution spectroscopy of Venus 1. Variations of CO 2, CO, HF, and HCl at the cloud tops

Variations of the upper cloud boundary and the CO, HF, and HCl mixing ratios were observed using the CSHELL spectrograph at NASA IRTF. The observations were made in three sessions (October 2007, January 2009, and June 2009) at early morning and late afternoon on Venus in the latitude range of ±60°. CO 2 lines at 2.25 μm reveal variations of the cloud aerosol density (∼25%) and scale height near 65 km. The measured reflectivity of Venus at low latitudes is 0.7 at 2.25 μm and 0.028 at 3.66 μm, and the effective CO 2 column density is smaller at 3.66 μm than those at 2.25 μm by a factor of 4. This agrees with the almost conservative multiple scattering at 2.25 μm and single scattering in the almost black aerosol at 3.66 μm. The expected difference is just a factor of (1 − g) −1 = 4, where g = 0.75 is the scattering asymmetry factor for Venus’ clouds. The observed CO mixing ratio is 52 ± 4 ppm near 08:00 and 40 ± 4 ppm near 16:30 at 68 km, and the higher ratio in the morning may be caused by extension of the CO morningside bulge to the cloud tops. The observed weak limb brightening in CO indicates an increase of the CO mixing ratio with altitude. HF is constant at 3.5 ± 0.2 ppb at 68 km in both morningside and afternoon observations and in the latitude range ±60°. Therefore the observations do not favor a bulge of HF, though HF is lighter than CO. Probably a source in the upper atmosphere facilitates the bulge formation. The recent measurements of HCl near 70 km are controversial (0.1 and 0.74 ppm) and require either a strong sink or a strong source of HCl in the clouds. The HCl lines of the (2-0) band are blended by the solar and telluric lines. Therefore we observed the P8 lines of the (1-0) band at 3.44 μm. These lines are spectrally clean and result in the HCl mixing ratio of 0.40 ± 0.03 ppm at 74 km. HCl does not vary with latitude within ±60°. Our observations support a uniformly mixed HCl throughout the Venus atmosphere.

First multi-year occultation observations of CO<sub>2</sub> in the MLT by ACE satellite: observations and analysis using the extended CMAM

Abstract. This paper presents the first global set of observations of CO2 in the mesosphere and lower thermosphere (MLT) obtained by the ACE-FTS instrument on SCISAT-I, a small Canadian satellite launched in 2003. The observations use the solar occultation technique and document the fall-off in the mixing ratio of CO2 in the MLT region. The beginning of the fall-off of the CO2, or "knee" occurs at about 78 km and lies higher than in the CRISTA-1 measurements (~70 km) but lower than in the SABER 1.06 (~80 km) and much lower than in rocket measurements. We also present the measurements of CO obtained concurrently which provide important constraints for analysis. We have compared the ACE measurements with simulations of the CO2 and CO distributions in the vertically extended version of the Canadian Middle Atmosphere Model (CMAM). Applying standard chemistry we find that we cannot get agreement between the model and ACE CO2 observations although the CO observations are adequately reproduced. There appears to be about a 10 km offset compared to the observed ACE CO2, with the model "knee" occurring too high. In analyzing the disagreement, we have investigated the variation of several parameters of interest (photolysis rates, formation rate for CO2, and the impact of uncertainty in turbulent eddy diffusion) in order to explore parameter space for this problem. Our conclusions are that there must be a loss process for CO2, about 2–4~times faster than photolysis that will sequester the carbon in some form other than CO and we have speculated on the role of meteoritic dust as a possible candidate. In addition, from this study we have highlighted a possible important role for unresolved vertical eddy diffusion in 3-D models in determining the distribution of candidate species in the mesosphere which requires further study.

Increasing synoptic scale variability in atmospheric CO<sub>2</sub> at Hateruma Island associated with increasing East-Asian emissions

Abstract. In-situ observations of atmospheric CO2 and CH4 at Hateruma Island (24.05° N, 123.80° E, 47 m a.s.l), Japan shows large synoptic scale variations during a 6-month period from November to April, when the sampled air is predominantly of continental origin due to the Asian winter monsoon. Synoptic scale variations are extracted from the daily averaged values for the years between 1996 and 2007, along with the annual standard deviations (σCO2 and σCH4 for CO2 and CH4, respectively) for the relevant 6-month period. During this 6-month period the absolute mixing ratios of CO2 and CH4 at Hateruma are also elevated compared to those at two sites in the central North Pacific Ocean. The temporal change in σCO2 shows a systematic increase over the 12-year period, with elevated excursions in 1998 and 2003; there is no clear increase in σCH4. We also find that the σCO2/σCH4 ratio increases gradually from 1996 to 2002 and rapidly after 2002 without any extreme deviations that characterised σCO2. The σCO2/σCH4 ratio correlates closely with the recent rapid increase in fossil carbon emissions from China, as indicated in the Carbon Dioxide Information Analysis Center (CDIAC) database. This methodology can be applied to multiple chemical tracers of sufficient lifetime, for tracking overall changes in regional emissions.

Climate variability as reflected in a regional atmospheric CO2 record

This paper analyses a 15-year long atmospheric CO2 mixing ratio record measured at a mid-continental, low-elevation station (Hegyh´ats´al, Hungary) to reveal the effect of regional climate variability. While the long-term trend and the temporal fluctuation of the growth rate of CO2 mixing ratio followthe global tendencies to a large extent, the shorter-term variations show special features. We present the distorted seasonal cycle caused by the seasonality in the atmospheric vertical mixing and the tendentious change in its shape, which can be attributed to the gradual warming and to the resulted prolongation of the growing season. The decreasing summer diurnal amplitude and the decreasing seasonal amplitude in the mixing ratio, furthermore the higher than average summer CO2 mixing ratio growth rate in the first period of the measurements (1994–2003) with generally rising temperature and decreasing precipitation are explained as the consequence of the reduced activity of the biosphere in the influence area of the station and that of the reduced biomass under environmental conditions getting increasingly unfavourable. The explanation is supported by the colocated tall tower surface–atmosphere CO2 exchange measurements and by the crop yield statistics of the dominantly agricultural region around the station.

Estimation of Long-Term Trends in the Tropospheric 14CO2 Activity Concentration

Fossil CO2 emissions have been diluting the global 14C/C ratio of atmospheric CO2 (Suess effect). We estimated the 14CO2 amount in the atmosphere (and its trend) utilizing the calculated 14CO2 activity concentration in the atmosphere (aacn, reported in mBq m–3). This parameter, calculated from Δ14CO2 and the CO2 mixing ratio (reported in micromoles of CO2 per mole of air), is connected with the 14CO2 quantity in the volume or mass unit of air, which is not influenced by the Suess effect. This parameter can only be influenced by processes linked to 14CO2 emissions/uptake, e.g. associated with atmosphere-biosphere or atmosphere-ocean CO2 exchange as well as by anthropogenic emissions of 14CO2. Results obtained from measurements at Schauinsland station, Germany, indicate a stable amount of 14CO2 in the atmosphere since the early 1990s.

Impact of entrainment from overshooting thermals on land–atmosphere interactions during summer 1999

The depth of the planetary boundary layer (PBL) or mixed layer is important for carbon dioxide source/sink estimation because the response of atmospheric carbon dioxide concentration to a given amount of surface flux is inversely proportional to this depth. The PBL depth is affected by entrainment from overshooting thermals that is often underestimated in mesoscale meteorological models. An experiment was performed for the late summer of 1999 that includes a parameterization of PBL top entrainment that is based on a downward buoyancy flux at the top of the PBL. Simulations with this parameterization produce a warmer, drier and deeper boundary layer than a control simulation. The monthly mean diurnal cycle of PBL depth at a location in northernWisconsin is better simulated with this enhanced entrainment when compared to observations. The altered atmospheric conditions cause the vegetation’s stomata to respond and possibly close in an evolved response to limit water loss, thus reducing transpiration and shifting the Bowen ratio. The stomatal closing also reduces carbon assimilation, consequently altering horizontal and vertical carbon gradients. The overall effect of enhanced PBL entrainment is to alter time–mean regional gradients in CO2 mixing ratio by as much as 7 ppmv over 1000 km.

Atmospheric Fossil Fuel CO2 Measurement Using a Field Unit in a Central European City During the Winter of 2008/09

A high-precision atmospheric CO2 monitoring station was developed as a field unit. Within this, an integrating CO2 sampling system was applied to collect samples for radiocarbon measurements. One sampler was installed in the second largest city of Hungary (Debrecen station) and 2 independent 14CO2 sampling lines were installed ∼300 km from Debrecen in a rural site at Hegyhátsál station as independent background references, where high-precision atmospheric CO2 mixing ratios have been measured since 1994. Fossil fuel CO2 content in the air of the large Hungarian city of Debrecen was determined during the winter of 2008 using both the measurements of CO2 mixing ratio and 14C content of air. Fossil fuel CO2 was significantly enhanced at Debrecen relative to the clean-air site at Hegyhátsál.