CO2 Mixing Ratios Research Articles

The radiocarbon composition of tree rings as a tracer of local fossil fuel emissions in the Los Angeles basin: 1980–2008

Quantifying local fossil fuel CO2 emissions in urban areas is challenging due to the heterogeneity in emissions and in atmospheric mixing ratios of CO2. Measurements of the radiocarbon content of urban tree rings are an alternative to large networks of CO2monitoring stations. In this study, we calculated 3‐year averages of CO2 mixing ratios from fossil fuel combustion from 1980 to 2008 using tree rings sampled at six sites within the Los Angeles basin and adjacent mountains. We observed CO2 mixing ratios from fossil fuel combustion of up to 23 μmol·mol−1 in the inland basin and ∼5–10 μmol·mol−1at coastal sites. Although we expected to see increasing trends of fossil fuel‐derived CO2over time, not all sites showed a significant increase. Analysis of correlations between fossil fuel‐derived CO2and socioeconomic variables revealed that fossil fuel‐derived CO2 followed trends in census tract and/or city population or in vehicle statistics at most sites. We also calculated CO/CO2combustion ratios from tree ring radiocarbon and nearby measurements of atmospheric CO mixing ratios. We observed widespread declines in the combustion ratio that support increases in the efficiency of the automobile fleet over the past few decades. This study demonstrates the utility of tree ring radiocarbon measurements for quantifying temporal and spatial patterns in fossil fuel‐derived CO2 emissions in urban areas.

Assimilation of IASI satellite CO fields into a global chemistry transport model for validation against aircraft measurements

Abstract. This work evaluates the IASI CO product against independent in-situ aircraft data from the MOZAIC program and the POLARCAT aircraft campaign. The validation is carried out by analysing the impact of assimilation of eight months of IASI CO columns retrieved for the period of May to December 2008 into the global chemistry transport model LMDz-INCA. A modelling system based on a sub-optimal Kalman filter was developed and a specific treatment that takes into account the representativeness of observations at the scale of the model grid is applied to the IASI CO columns and associated errors before their assimilation in the model. Comparisons of the assimilated CO profiles with in situ CO measurements indicate that the assimilation leads to a considerable improvement of the model simulations in the middle troposphere as compared with a control run with no assimilation. Model biases in the simulation of background values are reduced and improvement in the simulation of very high concentrations is observed. The improvement is due to the transport by the model of the information present in the IASI CO retrievals. Our analysis also shows the impact of assimilation of CO on the representation of transport into the Arctic region during the POLARCAT summer campaign. A considerable increase in CO mixing ratios over the Asian source region was observed when assimilation was used leading to much higher values of CO during the cross-pole transport episode. These higher values are in good agreement with data from the POLARCAT flights that sampled this plume.

Validation of routine continuous airborne CO<sub>2</sub> observations near the Bialystok Tall Tower

Abstract. Since 2002 in situ airborne measurements of atmospheric CO2 mixing ratios have been performed regularly aboard a rental aircraft near Bialystok (53°08´ N, 23°09´ E), a city in northeastern Poland. Since August 2008, the in situ CO2 measurements have been made by a modified commercially available and fully automated non-dispersive infrared (NDIR) analyzer system. The response of the analyzer has been characterized and the CO2 mixing ratio stability of the associated calibration system has been fully tested, which results in an optimal calibration strategy and allows for an accuracy of the CO2 measurements within 0.2 ppm. Besides the in situ measurements, air samples have been collected in glass flasks and analyzed in the laboratory for CO2 and other trace gases. To validate the in situ CO2 measurements against reliable discrete flask measurements, we developed weighting functions that mimic the temporal averaging of the flask sampling process. Comparisons between in situ and flask CO2 measurements demonstrate that these weighting functions can compensate for atmospheric variability, and provide an effective method for validating airborne in situ CO2 measurements. In addition, we show the nine-year records of flask CO2 measurements. The new system, automated since August 2008, has eliminated the need for manual in-flight calibrations, and thus enables an additional vertical profile, 20 km away, to be sampled at no additional cost in terms of flight hours. This sampling strategy provides an opportunity to investigate both temporal and spatial variability on a regular basis.

A conceptual framework to quantify the influence of convective boundary layer development on carbon dioxide mixing ratios

Abstract. Interpretation of observed diurnal carbon dioxide (CO2) mixing ratios near the surface requires knowledge of the local dynamics of the planetary boundary layer. In this paper, we study the relationship between the boundary layer dynamics and the CO2 budget in convective conditions through a newly derived set of analytical equations. From these equations, we are able to quantify how uncertainties in boundary layer dynamical variables or in the morning CO2 distribution in the mixed-layer or in the free atmosphere (FA) influence the bulk CO2 mixing ratio. We find that the largest uncertainty incurred on the mid-day CO2 mixing ratio comes from the prescribed early morning CO2 mixing ratios in the stable boundary layer, and in the free atmosphere. Errors in these values influence CO2 mixing ratios inversely proportional to the boundary layer depth (h), just like uncertainties in the assumed initial boundary layer depth and surface CO2 flux. The influence of uncertainties in the boundary layer depth itself is one order of magnitude smaller. If we "invert" the problem and calculate CO2 surface exchange from observed or simulated CO2 mixing ratios, the sensitivities to errors in boundary layer dynamics also invert: they become linearly proportional to the boundary layer depth. We demonstrate these relations for a typical well characterized situation at the Cabauw site in The Netherlands, and conclude that knowledge of the temperature and carbon dioxide profiles of the atmosphere in the early morning are of vital importance to correctly interpret observed CO2 mixing ratios during midday.

Analysis of ΔO<sub>2</sub>/ΔCO<sub>2</sub> ratios for the pollution events observed at Hateruma Island, Japan

Abstract. Pollution events extracted from the in situ observations of atmospheric CO2 and O2 mixing ratios at Hateruma Island (HAT, 24° N, 124° E) during the period from October 2006 and December 2008 are examined. The air mass origins for the pollution events are categorized by using back trajectory analysis, and the oxidative ratios (OR = −O2:CO2 molar exchange ratio) for selected pollution events are calculated. We find that there is a significant difference in the average oxidative ratios between events from China (OR = 1.14 ± 0.12, n = 25) and Japan/Korea (OR = 1.37 ± 0.15, n = 16). These values are in a good agreement with the national average oxidative ratios for the emissions from fossil fuel burning and cement production (FFBC) in China (ORFFBC = 1.11 ± 0.03) and Korea/Japan (ORFFBC = 1.36 ± 0.02). Compared with the observation, simulations of the atmospheric O2 and CO2 mixing ratios using Lagrangian particle dispersion models do a good job in reconstructing the average oxidative ratio of the pollution events originating in China but tend to underestimate for events originating in Japan/Korea. A sensitivity test suggests that the simulated atmospheric oxidative ratios at HAT are especially sensitive to changes in Chinese fuel mix.

New source and process apportionment method using a three-dimensional chemical transport model: Process, Age, and Source region Chasing ALgorithm (PASCAL)

We have developed a new source and process apportionment method, the Process, Age, and Source region Chasing ALgorithm (PASCAL), and implemented it in a three-dimensional chemical transport model, the Community Multiscale Air Quality (CMAQ) model. By adding new variables (tagged species), PASCAL traces 1) the source region of emissions (source apportionment), 2) the age of individual species (elapsed time from emissions), 3) net and gross production and loss amounts from individual physical and chemical processes during transport (Lagrangian way), and 4) local production and loss rates at individual grid cells (Eulerian way) for primary and secondary aerosols and their precursor gases. The main advantage of PASCAL is the third one, which can trace accumulated production and loss amounts of individual processes during transport from source regions to each grid cell (Lagrangian type of integration) for both gross (production and loss) and net (gross production − loss) concentrations. Currently the method is applied for mixing ratios of CO and SO2 and mass concentrations of black carbon and sulfate aerosols. This algorithm is not impacted by the non-linearity of chemical reactions and is computationally efficient. CMAQ/PASCAL model calculations were conducted over the East Asian region to test its performance. The overall validity of PASCAL calculations is confirmed for all species, periods, altitudes, and regions. This algorithm will be a useful tool in evaluating source regions as well as formation and loss processes of aerosols in the atmosphere in order to make effective strategies for emissions reduction.

Aircraft observation of the seasonal variation in the transport of CO2 in the upper atmosphere

A large number of in situ carbon dioxide (CO2) measurements from 5224 flights were taken by commercial airliners from 2005 to 2010. We analyzed the seasonal cycles in tropospheric CO2 in wide areas of the world over the Eurasian continent, the North Pacific, Southeast Asia, and Oceania. In the Northern Hemisphere, large seasonal changes of CO2 in the upper troposphere are found from spring through summer at northern midlatitudes to high latitudes with significant longitudinal differences; seasonally low CO2 mixing ratios are vertically transported from the surface over the Eurasian continent and then transported eastward to the North Pacific. In the Southern Hemisphere, the CO2 in the upper troposphere increases rapidly from April to June, indicating clearly the interhemispheric transport of high CO2 from the Northern Hemisphere winter. The rapid increase in the upper southern lower latitudes is equivalent to about 0.2 Pg increase in carbon. This interhemispheric transport should be adequately represented in general circulation models for source/sink estimates by inverse methods, because it is comparable to the seasonal or net fluxes estimated for a current inversion area size or a typical subcontinental domain. Estimation for transport of CO2 through the high altitudes will be more important than ever with increasing data from aircraft observations.

Error characterization of CO<sub>2</sub> vertical mixing in the atmospheric transport model WRF-VPRM

Abstract. One of the dominant uncertainties in inverse estimates of regional CO2 surface-atmosphere fluxes is related to model errors in vertical transport within the planetary boundary layer (PBL). In this study we present the results from a synthetic experiment using the atmospheric model WRF-VPRM to realistically simulate transport of CO2 for large parts of the European continent at 10 km spatial resolution. To elucidate the impact of vertical mixing error on modeled CO2 mixing ratios we simulated a month during the growing season (August 2006) with different commonly used parameterizations of the PBL (Mellor-Yamada-Janjić (MYJ) and Yonsei-University (YSU) scheme). To isolate the effect of transport errors we prescribed the same CO2 surface fluxes for both simulations. Differences in simulated CO2 mixing ratios (model bias) were on the order of 3 ppm during daytime with larger values at night. We present a simple method to reduce this bias by 70–80% when the true height of the mixed layer is known.

The imprint of surface fluxes and transport on variations in total column carbon dioxide

Abstract. New observations of the vertically integrated CO2 mixing ratio, ⟨CO2⟩, from ground-based remote sensing show that variations in CO2⟩ are primarily determined by large-scale flux patterns. They therefore provide fundamentally different information than observations made within the boundary layer, which reflect the combined influence of large-scale and local fluxes. Observations of both ⟨CO2⟩ and CO2 concentrations in the free troposphere show that large-scale spatial gradients induce synoptic-scale temporal variations in ⟨CO2⟩ in the Northern Hemisphere midlatitudes through horizontal advection. Rather than obscure the signature of surface fluxes on atmospheric CO2, these synoptic-scale variations provide useful information that can be used to reveal the meridional flux distribution. We estimate the meridional gradient in ⟨CO2⟩ from covariations in ⟨CO2⟩ and potential temperature, θ, a dynamical tracer, on synoptic timescales to evaluate surface flux estimates commonly used in carbon cycle models. We find that simulations using Carnegie Ames Stanford Approach (CASA) biospheric fluxes underestimate both the ⟨CO2⟩ seasonal cycle amplitude throughout the Northern Hemisphere midlatitudes and the meridional gradient during the growing season. Simulations using CASA net ecosystem exchange (NEE) with increased and phase-shifted boreal fluxes better fit the observations. Our simulations suggest that climatological mean CASA fluxes underestimate boreal growing season NEE (between 45–65° N) by ~40%. We describe the implications for this large seasonal exchange on inference of the net Northern Hemisphere terrestrial carbon sink.

Field Testing of Cavity Ring-Down Spectroscopy Analyzers Measuring Carbon Dioxide and Water Vapor

Abstract Prevalent methods for making high-accuracy tower-based measurements of the CO2 mixing ratio, notably nondispersive infrared spectroscopy (NDIR), require frequent system calibration and sample drying. Wavelength-scanned cavity ring-down spectroscopy (WS-CRDS) is an emerging laser-based technique with the advantages of improved stability and concurrent water vapor measurements. Results are presented from 30 months of field measurements from WS-CRDS systems at five sites in the upper Midwest of the United States. These systems were deployed in support of the North American Carbon Program’s Mid-Continent Intensive (MCI) from May 2007 to November 2009. Excluding one site, 2σ of quasi-daily magnitudes of the drifts, before applying field calibrations, are less than 0.38 ppm over the entire 30-month field deployment. After applying field calibrations using known tanks sampled every 20 h, residuals from known values are, depending on site, from 0.02 ±0.14 to 0.17 ±0.07 ppm. Eight months of WS-CRDS measurements collocated with a National Oceanographic and Atmospheric Administrations (NOAA)/Earth System Research Laboratory (ESRL) NDIR system at West Branch, Iowa, show median daytime-only differences of −0.13 ±0.63 ppm on a daily time scale.

North American CO<sub>2</sub> exchange: inter-comparison of modeled estimates with results from a fine-scale atmospheric inversion

Abstract. Atmospheric inversion models have the potential to quantify CO2 fluxes at regional, sub-continental scales by taking advantage of near-surface CO2 mixing ratio observations collected in areas with high flux variability. This study presents results from a series of regional geostatistical inverse models (GIM) over North America for 2004, and uses them as the basis for an inter-comparison to other inversion studies and estimates from biospheric models collected through the North American Carbon Program Regional and Continental Interim Synthesis. Because the GIM approach does not require explicit prior flux estimates and resolves fluxes at fine spatiotemporal scales (i.e. 1° × 1°, 3-hourly in this study), it avoids temporal and spatial aggregation errors and allows for the recovery of realistic spatial patterns from the atmospheric data relative to previous inversion studies. Results from a GIM inversion using only available atmospheric observations and a fine-scale fossil fuel inventory were used to confirm the quality of the inventory and inversion setup. An inversion additionally including auxiliary variables from the North American Regional Reanalysis found inferred relationships with flux consistent with physiological understanding of the biospheric carbon cycle. Comparison of GIM results with bottom-up biospheric models showed stronger agreement during the growing relative to the dormant season, in part because most of the biospheric models do not fully represent agricultural land-management practices and the fate of both residual biomass and harvested products. Comparison to earlier inversion studies pointed to aggregation errors as a likely source of bias in previous sub-continental scale flux estimates, particularly for inversions that adjust fluxes at the coarsest scales and use atmospheric observations averaged over long periods. Finally, whereas the continental CO2 boundary conditions used in the GIM inversions have a minor impact on spatial patterns, they have a substantial impact on the continental carbon budget, with a difference of 0.8 PgC yr−1 in the total continental flux resulting from the use of two plausible sets of boundary CO2 mixing ratios. Overall, this inter-comparison study helps to assess the state of the science in estimating regional-scale CO2 fluxes, while pointing towards the path forward for improvements in future top-down and bottom-up modeling efforts.

Attribution and evolution of ozone from Asian wild fires using satellite and aircraft measurements during the ARCTAS campaign

Abstract. We use ozone and carbon monoxide measurements from the Tropospheric Emission Spectrometer (TES), model estimates of Ozone, CO, and ozone pre-cursors from the Real-time Air Quality Modeling System (RAQMS), and data from the NASA DC8 aircraft to characterize the source and dynamical evolution of ozone and CO in Asian wildfire plumes during the spring ARCTAS campaign 2008. On the 19 April, NASA DC8 O3 and aerosol Differential Absorption Lidar (DIAL) observed two biomass burning plumes originating from North-Western Asia (Kazakhstan) and South-Eastern Asia (Thailand) that advected eastward over the Pacific reaching North America in 10 to 12 days. Using both TES observations and RAQMS chemical analyses, we track the wildfire plumes from their source to the ARCTAS DC8 platform. In addition to photochemical production due to ozone pre-cursors, we find that exchange between the stratosphere and the troposphere is a major factor influencing O3 concentrations for both plumes. For example, the Kazakhstan and Siberian plumes at 55 degrees North is a region of significant springtime stratospheric/tropospheric exchange. Stratospheric air influences the Thailand plume after it is lofted to high altitudes via the Himalayas. Using comparisons of the model to the aircraft and satellite measurements, we estimate that the Kazakhstan plume is responsible for increases of O3 and CO mixing ratios by approximately 6.4 ppbv and 38 ppbv in the lower troposphere (height of 2 to 6 km), and the Thailand plume is responsible for increases of O3 and CO mixing ratios of approximately 11 ppbv and 71 ppbv in the upper troposphere (height of 8 to 12 km) respectively. However, there are significant sources of uncertainty in these estimates that point to the need for future improvements in both model and satellite observations. For example, it is challenging to characterize the fraction of air parcels from the stratosphere versus those from the fire because of the low sensitivity of the TES CO estimates used to mark stratospheric air versus air parcels affected by the smoke plume. Model transport uncertainties, such as too much dispersion, results in a broad plume structure from the Kazakhstan fires that is approximately 2 km lower than the plume observed by aircraft. Consequently, the model and TES data do not capture the photochemical production of ozone in the Kazakhstan plume that is apparent in the aircraft in situ data. However, ozone and CO distributions from TES and RAQMS model estimates of the Thailand plume are within the uncertainties of the TES data. Therefore, the RAQMS model is better able to characterize the emissions from this fire, the mixing of ozone from the stratosphere to the plume, and the photochemical production and transport of ozone and ozone pre-cursors as the plume moves across the Pacific.

Modeling of CO2 fluxes between atmosphere and boreal forest

Difficulties in estimating terrestrial ecosystem CO2 fluxes on regional scales have significantly limited our understanding of the global carbon cycle. We present a method of using tall-tower-based CO2 concentrations for estimating CO2 fluxes over a forested region. With long-term measurements of the CO2 mixing ratio at a 300-m-tall tower, regional CO2 fluxes were estimated for several months, from the first obtained data. Estimates of a monthly-integrated surface CO2 flux over the region were obtained by the analysis of average gradients and estimates of the rate of vertical mixing between the atmospheric boundary layer (ABL) and the free troposphere. For the comparison of the ABL budget method and field measurements a zero-dimensional mathematical model of the ecosystem of Siberian boreal forests was used. The model is a system of ordinary differential equations with additional conditions superimposed on the parameters. The main occurring processes are described – photosynthesis, respiration, seasonal changes of active phytomass, water balance of trees, the influence of light, humidity, and temperature on photosynthesis and respiration.

Relative contribution of transport/surface flux to the seasonal vertical synoptic CO2 variability in the troposphere over Narita

ABSTRACTFrequent CO2 measurements obtained by commercial aircraft provide a unique, quasi-continuous record of free-tropospheric CO2 variability. Vertically-resolved synoptic-scale fluctuations of CO2 over Narita International Airport (lat 35.8°N, 140.4°E, 43 m above sea-level) were investigated from November 2005 to March 2009, and combined with analyses of results from a transport model simulation for the year 2007 to retrieve information on sources contributing to the observed variability. The synoptic-scale variability of the observed CO2 mixing ratio, represented by the standard deviation (SD) from the fitted curves, increased in the upper troposphere in the spring, with a noticeable increase at all altitudes in the summer. This seasonal/altitudinal change of the observed SD was shown to be statistically significant throughout the observation period, and the model result agreed with the observation except for the underestimation of the summertime SD. Tagged simulations were conducted to evaluate the relative contribution of the regional fluxes to the synoptic-scale variability over Narita. The results indicate that the major contribution to the free troposphere (FT) variability was made by the fluxes in East Asia, while the Japanese fluxes contributed mostly to the variability in the planetary boundary layer (PBL). A sensitivity analysis was performed to evaluate the relative influence of transport and of flux magnitude on the CO2 SD over Narita for 2007. It was found that a change in the surface flux magnitude could affect the altitudinal distribution of the annual SD over Narita as follows: 41 and 3% at 9 km, 61 and 4% at 5 km, 19 and 83% at 0.5 km when the fossil fuel flux from East Asia and Japan was doubled, respectively. These results are qualitative in nature (since SD is a non-linear function of concentration and flux), but do indicate that the CO2 SD over Narita is more sensitive to the fluctuation in the atmospheric transport (synoptic-scale meteorological variability) in the FT, while showing much more sensitivity to the magnitude of local fluxes in the PBL. The results also point to the fact that vertical profiles of atmospheric CO2 variability at the synoptic scale could potentially provide a useful additional constraint in the inversion analysis of regional CO2 fluxes.

Network design for mesoscale inversions of CO2 sources and sinks

ABSTRACTRecent instrumental deployments of regional observation networks of atmospheric CO2 mixing ratios have been used to constrain carbon sources and sinks using inversion methodologies. In this study, we performed sensitivity experiments using observation sites from the Mid Continent Intensive experiment to evaluate the required spatial density and locations of CO2 concentration towers based on flux corrections and error reduction analysis. In addition, we investigated the impact of prior flux error structures with different correlation lengths and biome information. We show here that, while the regional carbon balance converged to similar annual estimates using only two concentration towers over the region, additional sites were necessary to retrieve the spatial flux distribution of our reference case (using the entire network of eight towers). Local flux corrections required the presence of observation sites in their vicinity, suggesting that each tower was only able to retrieve major corrections within a hundred of kilometres around, despite the introduction of spatial correlation lengths (~100 to 300 km) in the prior flux errors. We then quantified and evaluated the impact of the spatial correlations in the prior flux errors by estimating the improvement in the CO2 model-data mismatch of the towers not included in the inversion. The overall gain across the domain increased with the correlation length, up to 300 km, including both biome-related and non-biome-related structures. However, the spatial variability at smaller scales was not improved. We conclude that the placement of observation towers around major sources and sinks is critical for regional-scale inversions in order to obtain reliable flux distributions in space. Sparser networks seem sufficient to assess the overall regional carbon budget with the support of flux error correlations, indicating that regional signals can be recovered using hourly mixing ratios. However, the smaller spatial structures in the posterior fluxes are highly constrained by assumed prior flux error correlation lengths, with no significant improvement at only a few hundreds of kilometres away from the observation sites.

Global CO2fluxes inferred from surface air-sample measurements and from TCCON retrievals of the CO2total column

[1] We present the first estimate of the global distribution of CO2surface fluxes from 14 stations of the Total Carbon Column Observing Network (TCCON). The evaluation of this inversion is based on 1) comparison with the fluxes from a classical inversion of surface air-sample-measurements, and 2) comparison of CO2mixing ratios calculated from the inverted fluxes with independent aircraft measurements made during the two years analyzed here, 2009 and 2010. The former test shows similar seasonal cycles in the northern hemisphere and consistent regional carbon budgets between inversions from the two datasets, even though the TCCON inversion appears to be less precise than the classical inversion. The latter test confirms that the TCCON inversion has improved the quality (i.e., reduced the uncertainty) of the surface fluxes compared to the assumed or prior fluxes. The consistency between the surface-air-sample-based and the TCCON-based inversions despite remaining flaws in transport models opens the possibility of increased accuracy and robustness of flux inversions based on the combination of both data sources and confirms the usefulness of space-borne monitoring of the CO2 column.

Field determination of biomass burning emission ratios and factors via open-path FTIR spectroscopy and fire radiative power assessment: headfire, backfire and residual smouldering combustion in African savannahs

Abstract. Biomass burning emissions factors are vital to quantifying trace gas release from vegetation fires. Here we evaluate emissions factors for a series of savannah fires in Kruger National Park (KNP), South Africa using ground-based open path Fourier transform infrared (FTIR) spectroscopy and an IR source separated by 150–250 m distance. Molecular abundances along the extended open path are retrieved using a spectral forward model coupled to a non-linear least squares fitting approach. We demonstrate derivation of trace gas column amounts for horizontal paths transecting the width of the advected plume, and find for example that CO mixing ratio changes of ~0.01 μmol mol−1 [10 ppbv] can be detected across the relatively long optical paths used here. Though FTIR spectroscopy can detect dozens of different chemical species present in vegetation fire smoke, we focus our analysis on five key combustion products released preferentially during the pyrolysis (CH2O), flaming (CO2) and smoldering (CO, CH4, NH3) processes. We demonstrate that well constrained emissions ratios for these gases to both CO2 and CO can be derived for the backfire, headfire and residual smouldering combustion (RSC) stages of these savannah fires, from which stage-specific emission factors can then be calculated. Headfires and backfires often show similar emission ratios and emission factors, but those of the RSC stage can differ substantially. The timing of each fire stage was identified via airborne optical and thermal IR imagery and ground-observer reports, with the airborne IR imagery also used to derive estimates of fire radiative energy (FRE), allowing the relative amount of fuel burned in each stage to be calculated and "fire averaged" emission ratios and emission factors to be determined. These "fire averaged" metrics are dominated by the headfire contribution, since the FRE data indicate that the vast majority of the fuel is burned in this stage. Our fire averaged emission ratios and factors for CO2 and CH4 agree well with those from prior studies conducted in the same area using e.g. airborne plume sampling. We also concur with past suggestions that emission factors for formaldehyde in this environment appear substantially underestimated in widely used databases, but see no evidence to support suggestions by Sinha et al. (2003) of a major overestimation in the emission factor of ammonia in works such as Andreae and Merlet (2001) and Akagi et al. (2011). We also measure somewhat higher CO and NH3 emission ratios and factors than are usually reported for this environment, which is interpreted to result from the OP-FTIR ground-based technique sampling a greater proportion of smoke from smouldering processes than is generally the case with methods such as airborne sampling. Finally, our results suggest that the contribution of burning animal (elephant) dung can be a significant factor in the emissions characteristics of certain KNP fires, and that the ability of remotely sensed fire temperatures to provide information useful in tailoring modified combustion efficiency (MCE) and emissions factor estimates maybe rather limited, at least until the generally available precision of such temperature estimates can be substantially improved. One limitation of the OP-FTIR method is its ability to sample only near-ground level smoke, which may limit application at more intense fires where the majority of smoke is released into a vertically rising convection column. Nevertheless, even in such cases the method potentially enables a much better assessment of the emissions contribution of the RSC stage than is typically conducted currently.

Interannual variability of ozone and carbon monoxide at the Whistler high elevation site: 2002–2006

Abstract. In spring 2002, an atmospheric measurement site was established at the peak of Whistler Mountain in British Columbia, Canada to measure trace gases, particle chemistry and physics, and meteorology. This paper uses continuous measurements from March 2002 to December 2006 to investigate the influence of trans-Pacific transport and North American forest fires on both O3 and CO at Whistler. Annual mean mixing ratios of O3 and CO were 41 ppbv (monthly means of 35–48 ppbv) and 145 ppbv (monthly means of 113–177 ppbv) respectively with both species exhibiting an annual cycle of late-winter to early-spring maxima and summer minima. The absence of a broad summer O3 peak differs from previously-reported high altitude sites in the western US. The highest monthly-averaged O3 and CO mixing ratios relative to the 5-yr monthly means were seen in fall 2002 and spring 2003 with increased O3 and CO of 10 % and 25 % respectively. These increases correspond to anomalously-high values reported at other Northern Hemisphere sites and are attributed to fires in the Russian Federation. Air mass back trajectory analysis is used to associate the mean enhancements of O3 and CO with trans-Pacific transported or North American air masses relative to the Pacific background. Mean values of the enhancements for March to June in trans-Pacific air masses were 6 ppbv and 16 ppbv for O3 and CO respectively. In summers 2002–2006, higher CO and O3 mixing ratios were almost always observed in North American air masses and this relative enhancement co-varied for each year with the western US and Canada total wildfire area. The greatest enhancements in O3 and CO were seen in 2004, a record year for forest fires in Alaska and the Yukon Territory with average O3 and CO mixing ratios 13 and 43 ppbv above background values.

A comparison of different inverse carbon flux estimation approaches for application on a regional domain

Abstract. We have implemented six different inverse carbon flux estimation methods in a regional carbon dioxide (CO2) flux modeling system for the Netherlands. The system consists of the Regional Atmospheric Mesoscale Modeling System (RAMS) coupled to a simple carbon flux scheme which is run in a coupled fashion on relatively high resolution (10 km). Using an Ensemble Kalman filter approach we try to estimate spatiotemporal carbon exchange patterns from atmospheric CO2 mole fractions over the Netherlands for a two week period in spring 2008. The focus of this work is the different strategies that can be employed to turn first-guess fluxes into optimal ones, which is known as a fundamental design choice that can affect the outcome of an inversion significantly. Different state-of-the-art approaches with respect to the estimation of net ecosystem exchange (NEE) are compared quantitatively: (1) where NEE is scaled by one linear multiplication factor per land-use type, (2) where the same is done for photosynthesis (GPP) and respiration (R) separately with varying assumptions for the correlation structure, (3) where we solve for those same multiplication factors but now for each grid box, and (4) where we optimize physical parameters of the underlying biosphere model for each land-use type. The pattern to be retrieved in this pseudo-data experiment is different in nearly all aspects from the first-guess fluxes, including the structure of the underlying flux model, reflecting the difference between the modeled fluxes and the fluxes in the real world. This makes our study a stringent test of the performance of these methods, which are currently widely used in carbon cycle inverse studies. Our results show that all methods struggle to retrieve the spatiotemporal NEE distribution, and none of them succeeds in finding accurate domain averaged NEE with correct spatial and temporal behavior. The main cause is the difference between the structures of the first-guess and true CO2 flux models used. Most methods display overconfidence in their estimate as a result. A commonly used daytime-only sampling scheme in the transport model leads to compensating biases in separate GPP and R scaling factors that are readily visible in the nighttime mixing ratio predictions of these systems. Overall, we recommend that the estimate of NEE scaling factors should not be used in this regional setup, while estimating bias factors for GPP and R for every grid box works relatively well. The biosphere parameter inversion performs good compared to the other inversions at simultaneously producing space and time patterns of fluxes and CO2 mixing ratios, but non-linearity may significantly reduce the information content in the inversion if true parameter values are far from the prior estimate. Our results suggest that a carefully designed biosphere model parameter inversion or a pixel inversion of the respiration and GPP multiplication factors are from the tested inversions the most promising tools to optimize spatiotemporal patterns of NEE.

Carbon dioxide variability during cold front passages and fair weather days at a forested mountaintop site

Abstract This study describes temporal carbon dioxide (CO2) changes at a new meteorological site on a mountaintop in the Virginia Blue Ridge Mountains during the first year of measurements. Continental mountaintop locations are increasingly being used for CO2 monitoring, and investigations are needed to better understand measurements made at these locations. We focus on CO2 mixing ratio changes on days with cold front passages and on fair weather days. Changes in CO2 mixing ratios are largest during cold front passages outside the growing season and on clear, fair weather days in the growing season. 67% (60%) of the frontal passages during the non-growing (growing) season have larger postfrontal than prefrontal CO2 mixing ratios. The increase in CO2 mixing ratio around the frontal passage is short-lived and coincides with changes in CO and O3. The CO2 increase can therefore be used as an additional criterion to determine the timing of frontal passages at the mountaintop station. The CO2 increase can be explained by an accumulation of trace gases along frontal boundaries. The magnitude and duration of the CO2 increase is affected by the wind speed and direction that determine the source region of the postfrontal air. Southward-moving fronts result in the largest prolonged period of elevated CO2, consistent with the postfrontal advection of air from the Northeastern United States where anthropogenic contributions are relatively large compared to other areas in the footprint of the mountaintop station. These anthropogenic contributions to the CO2 changes are confirmed through concurrent CO measurements and output from NOAA’s CarbonTracker model.