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The Arctic is a critical region in terms of global warming. Environmental changes are already progressing steadily in high northern latitudes, whereby, among other effects, a high potential for enhanced methane (CH4) emissions is induced. With CH4 being a potent greenhouse gas, additional emissions from Arctic regions may intensify global warming in the future through positive feedback. Various natural and anthropogenic sources are currently contributing to the Arctic's CH4 budget; however, the quantification of those emissions remains challenging. Assessing the amount of CH4 emissions in the Arctic and their contribution to the global budget still remains challenging. On the one hand, this is due to the difficulties in carrying out accurate measurements in such remote areas. Besides, large variations in the spatial distribution of methane sources and a poor understanding of the effects of ongoing changes in carbon decomposition, vegetation and hydrology also complicate the assessment. Therefore, the aim of this work is to reduce uncertainties in current bottom-up estimates of CH4 emissions as well as soil oxidation by implementing an inverse modelling approach in order to better quantify CH4 sources and sinks for the most recent years (2008 to 2019). More precisely, the objective is to detect occurring trends in the CH4 emissions and potential changes in seasonal emission patterns. The implementation of the inversion included footprint simulations obtained with the atmospheric transport model FLEXPART (FLEXible PARTicle dispersion model), various emission estimates from inventories and land surface models, and data on atmospheric CH4 concentrations from 41 surface observation sites in the Arctic nations. The results of the inversion showed that the majority of the CH4 sources currently present in high northern latitudes are poorly constrained by the existing observation network. Therefore, conclusions on trends and changes in the seasonal cycle could not be obtained for the corresponding CH4 sectors. Only CH4 fluxes from wetlands are adequately constrained, predominantly in North America. Within the period under study, wetland emissions show a slight negative trend in North America and a slight positive trend in East Eurasia. Overall, the estimated CH4 emissions are lower compared to the bottom-up estimates but higher than similar results from global inversions.

The provinces of Alberta and Saskatchewan account for 70% of Canada's methane emissions from the oil and gas sector. In 2018, the Government of Canada introduced methane regulations to reduce emissions from the sector by 40-45% from the 2012 levels by 2025. Complementary to inventory accounting methods, the effectiveness of regulatory practices to reduce emissions can be assessed using atmospheric measurements and inverse models. Total anthropogenic (oil and gas, agriculture, and waste) emission rates of methane from 2010 to 2017 in Alberta and Saskatchewan were derived using hourly atmospheric methane measurements over a six-month winter period from October to March. Scaling up the winter estimate to annual indicated an anthropogenic emission rate of 3.7 ± 0.7 MtCH4/year, about 60% greater than that reported in Canada's National Inventory Report (2.3 MtCH4). This discrepancy is tied primarily to the oil and gas sector emissions as the reported emissions from livestock operations (0.6 MtCH4) are well substantiated in both top-down and bottom-up estimates and waste management (0.1 MtCH4) emissions are small. The resulting estimate of 3.0 MtCH4 from the oil and gas sector is nearly twice that reported in Canada's National Inventory (1.6 MtCH4).

The two main sources of CH4 from the agricultural sector are enteric fermentation and manure management systems. Canada uses the IPCC Tier-II methodology to estimate CH4 for its national inventory report of GHG emissions to UNFCCC, which is based on a bottom-up approach using activity data and emission factors obtained through site level experimental measurements. However, because of the presence of wetlands in some agricultural regions, it has been challenging to obtain accurate CH4 emission estimates at a regional scale.This study explores the usefulness of S5P methane product for verifying methane emission estimates in eastern Ontario agricultural land. We investigated the spatiotemporal variability of total column methane mixing ratio, as well as other detailed data layers in the TROPOMI product, such as averaging kernels and a prior profiles. The spatial temporal patterns of wetland methane emission derived from the global WetCHARTs dataset, and a prior knowledge of livestock distribution in the region, are used to interpret S5P methane product. Results showed that TROPOMI methane product provides great spatiotemporal coverage that can be used to verify CH4 emissions from agricultural landscape. This will be useful to reduce methane estimation uncertainties at the regional and national scales.

Many stakeholders are seeking methods to reduce carbon dioxide (CO2) emissions in urban areas, however reliable, high-resolution inventories are required to guide these efforts. We present the development of a high-resolution CO2 inventory available for the Greater Toronto Area and surrounding region in southern Ontario, Canada (area of ~ 2.8 × 105 km2, 26 % of the province of Ontario). The new SOCE (Southern Ontario CO2 Emissions) inventory is available at the 2.5 × 2.5 km spatial and hourly temporal resolution and characterizes emissions from seven sectors: Area, Residential natural gas combustion, Commercial natural gas combustion, Point, Marine, On-road and Off-road. To assess the accuracy of the SOCE inventory, we developed an observation-model framework using the GEM-MACH chemistry-transport model run on a high-resolution grid with 2.5 km grid spacing coupled to the Fossil Fuel Data Assimilation System (FFDAS) v2 inventories for anthropogenic CO2 emissions and the European Center for Medium-Range Weather Forecasts (ECMWF) land carbon model C-TESSEL for biogenic fluxes. A run using FFDAS for the southern Ontario region was compared to a run in which its emissions were replaced by the SOCE inventory. Simulated CO2 mixing ratios were compared against in situ measurements made at four sites in southern Ontario, Downsview, Hanlan's Point, Egbert and Turkey Point, in three winter months, January–March, 2016. Model simulations had better agreement with measurements when using the SOCE inventory emissions versus other inventories, quantified using a variety of statistics such as Correlation Coefficient, root mean square error and mean bias. Furthermore, when run with the SOCE inventory, the model had improved ability to capture the typical diurnal pattern of CO2 mixing ratios, particularly at the Downsview, Hanlan's Point and Egbert sites. In addition to improved model-measurement agreement, the SOCE inventory offers a sectoral breakdown of emissions, allowing estimation of average time-of-day and day-of-week contributions of different sectors. Our results show that at night, emissions from Residential and Commercial natural gas combustion and other Area sources can contribute > 80 % of the CO2 enhancement while during the day emissions from the On-road sector dominate, accounting for > 70 % of the enhancement.

In urban environments, carbon dioxide (CO2) is emitted from a variety of anthropogenic and biogenic sources. The isotopic ratio δ13CO2 has been widely used to source apportion CO2 as different sources have distinct isotopic fingerprints; the disadvantage of this technique is that δ13CO2 signatures are often spatially and temporally specific. We present a study characterizing the δ13CO2 signatures of the dominant anthropogenic sources of CO2 in the Greater Toronto Area (GTA). Refined gasoline and diesel fuel were sampled from various stations around the GTA in three separate campaigns (April, July and November 2015) to assess the variability of their δ13CO2 signatures. Mean winter δ13CO2 signatures for refined gasoline were measured to be −27.58 ± 0.52 ‰ and −28.12 ± 0.43 ‰ (uncertainties represent the standard deviation in sample signatures) in April and November respectively while the mean summer signature was measured to be −28.09 ± 0.34 ‰. Diesel fuel samples δ13CO2 signatures from the same campaign periods were measured to be −29.09 ± 0.34 ‰, −29.47 ± 0.29 ‰, and −29.28 ± 0.21 ‰, respectively. We hypothesize that inter-seasonal variability in signatures is likely a result of the use of different parent crude petroleum. We found no significant impacts from octane grade, fuel distributor or municipality the fuel was purchased from on the measured δ13CO2 signatures. Other transportation fuels that were measured include dyed-diesel (δ13CO2 signature = −29.3 ± 0.20 ‰) and jet fuel (δ13CO2 signature = −29.5 ± 0.20 ‰), which were both different than measurements made for the same fuels in other locations globally. To account for emissions from residential and commercial heating and electricity production, a variety of fuels were characterized in this study. The primary heating fuel used in the GTA, natural gas, was measured to have a δ13CH4 signature of −44.2 ± 0.20 ‰. Anthracite coal (a fuel that was used prior to 2014 for electricity) was measured to have a δ13CO2 signature of −23.8 ± 0.20 ‰, which is fairly consistent with coal samples measured elsewhere. With the transition in Ontario from coal to biomass-fueled power generation, softwood, hardwood and mixed wood pellets were sampled from two distributors in the GTA and measured δ13CO2 signatures were −25.0 ± 0.20 ‰, −26.8 ± 0.20 ‰, and −25.8 ± 0.20 ‰, respectively. Using these measured signatures, we performed a sensitivity analysis to quantify the precision required for continuous ambient measurements to separately identify fuel type using δ13CO2 as the sole tracer. The local signatures were also used in a mass balance calculation to quantify the relative contribution of two end-members (with the signatures of −44 ‰ and −28 ‰) to total measured CO2 in the GTA in 2014.

We employed a global high-resolution inverse model to optimize the CH4 emission using Greenhouse gas Observing Satellite (GOSAT) and surface observation data for a period from 2011−2017 for the two main source categories of anthropogenic and natural emissions. We used the Emission Database for Global Atmospheric Research (EDGAR v4.3.2) for anthropogenic methane emission and scaled them by country to match the national inventories reported to the United Nations Framework Convention on Climate Change (UNFCCC). Wetland and soil sink prior fluxes were simulated using the Vegetation Integrative Simulator of Trace gases (VISIT) model. Biomass burning prior fluxes were provided by the Global Fire Assimilation System (GFAS). We estimated a global total anthropogenic and natural methane emissions of 340.9 Tg CH4 yr−1 and 232.5 Tg CH4 yr−1, respectively. Country-scale analysis of the estimated anthropogenic emissions showed that all the top-emitting countries showed differences with their respective inventories to be within the uncertainty range of the inventories, confirming that the posterior anthropogenic emissions did not deviate from nationally reported values. Large countries, such as China, Russia, and the United States, had the mean estimated emission of 45.7 ± 8.6, 31.9 ± 7.8, and 29.8 ± 7.8 Tg CH4 yr−1, respectively. For natural wetland emissions, we estimated large emissions for Brazil (39.8 ± 12.4 Tg CH4 yr−1), the United States (25.9 ± 8.3 Tg CH4 yr−1), Russia (13.2 ± 9.3 Tg CH4 yr−1), India (12.3 ± 6.4 Tg CH4 yr−1), and Canada (12.2 ± 5.1 Tg CH4 yr−1). In both emission categories, the major emitting countries all had the model corrections to emissions within the uncertainty range of inventories. The advantages of the approach used in this study were: (1) use of high-resolution transport, useful for simulations near emission hotspots, (2) prior anthropogenic emissions adjusted to the UNFCCC reports, (3) combining surface and satellite observations, which improves the estimation of both natural and anthropogenic methane emissions over spatial scale of countries.

In this paper, measurements of air pollutants made at a ground site near Fort McKay in the Athabasca oil sands region as part of a multi-platform campaign in the summer of 2013 are presented. The observations included measurements of selected volatile organic compounds (VOCs) by a gas chromatograph &ndash ion trap mass spectrometer (GC-ITMS). This instrument observed a large, analytically unresolved hydrocarbon peak (with retention index between 1100 and 1700) associated with intermediate volatility organic compounds (IVOCs). However, the activities or processes that contribute to the release of these IVOCs in the oil sands region remain unclear. Principal component analysis (PCA) with Varimax rotation was applied to elucidate major source types impacting the sampling site in the summer of 2013. The analysis included 28 variables, including concentrations of total odd nitrogen (NOy), carbon dioxide (CO2), methane (CH4), ammonia (NH3), carbon monoxide (CO), sulfur dioxide (SO2), total reduced sulfur compounds (TRS), speciated monoterpenes (including α- and β-pinene and limonene), particle volume calculated from measured size distributions of particles less than 10 µm and 1 µm in diameter (PM10-1 and PM1), particle-surface bound polycyclic aromatic hydrocarbons (pPAH), and aerosol mass spectrometer composition measurements, including refractory black carbon (rBC) and organic aerosol components. The PCA was complemented by bivariate polar plots showing the joint wind speed and direction dependence of air pollutant concentrations to illustrate the spatial distribution of sources in the area. Using the 95 % cumulative percentage of variance criterion, ten components were identified and categorized by source type. These included emissions by wet tailings ponds, vegetation, open pit mining operations, upgrader facilities, and surface dust. Three components correlated with IVOCs, with the largest associated with surface mining and is likely caused by the unearthing and processing of raw bitumen.

Agriculture is estimated to produce more than 40% of anthropogenic methane (CH 4 ) emissions, contributing to global climate change. Bottom-up, IPCC based methodologies are typically used to estimate the agriculture sector’s contribution, but these estimates are rarely verified beyond the farm gate, due to the challenge of separating interspersed sources. We present flux measurements of CH 4, using eddy covariance (EC), relaxed eddy accumulation (REA) and wavelet covariance obtained using an aircraft-based measurement platform and compare these top-down estimates with bottom-up footprint adjusted inventory estimates of CH 4 emissions for an agricultural region in eastern Ontario, Canada. Top-down CH 4 fluxes agree well (mean ± 1 standard error: EC = 17 ± 4 mg CH 4 m −2 d −1 ; REA = 19 ± 3 mg CH 4 m −2 d −1 , wavelet covariance = 16 ± 3 mg CH 4 m −2 d −1 ), and are not statistically different, but significantly exceed bottom-up inventory estimates of CH 4 emissions based on animal husbandry (8 ± 1 mg CH 4 m −2 d −1 ). The discrepancy between top-down and bottom-up estimates was found to be related to both increasing fractional area of wetlands in the flux footprint, and increasing surface temperature. For the case when the wetland area in the flux footprint was less than 10% fractional coverage, the top-down and bottom-up estimates were within the measurement error. This result provides the first independent verification of agricultural methane emissions inventories at the regional scale. Wavelet analysis, which provides spatially resolved fluxes, was used to attempt to separate CH 4 emissions from managed and unmanaged CH 4 sources. Opportunities to minimize the challenges of verifying agricultural CH 4 emissions inventories using aircraft flux measuring systems are discussed.

A mobile system was used for continuous ambient measurements of stable CH4 isotopes (12CH4 and 13CH4) and ethane (C2H6). This system was used during a winter mobile campaign to investigate the CH4 isotopic signatures and the C2H6/CH4 ratios of the main anthropogenic sources of CH4 in the Canadian province of Alberta. Individual signatures were derived from δ13CH4 and C2H6 measurements in plumes arriving from identifiable single sources. Methane emissions from beef cattle feedlots (n = 2) and landfill (n = 1) had δ13CH4 signatures of −66.7 ± 2.4‰ and −55.3 ± 0.2‰, respectively. The CH4 emissions associated with the oil or gas industry had distinct δ13CH4 signatures, depending on the formation process. Emissions from oil storage tanks (n = 5) had δ13CH4 signatures ranging from −54.9 ± 2.9‰ to −60.6 ± 0.6‰ and non-detectable C2H6, characteristic of secondary microbial methanogenesis in oil-bearing reservoirs. In contrast, CH4 emissions associated with natural gas facilities (n = 8) had δ13CH4 signatures ranging from −41.7 ± 0.7‰ to −49.7 ± 0.7‰ and C2H6/CH4 molar ratios of 0.10 for raw natural gas to 0.04 for processed/refined natural gas, consistent with thermogenic origins. These isotopic signatures and C2H6/CH4 ratios have been used for source discrimination in the weekly atmospheric measurements of stable CH4 isotopes over a two-month winter period at the Lac La Biche (LLB) measurement station, located in Alberta, approximately 200 km northeast of Edmonton. The average signature of −59.5 ± 1.4‰ observed at LLB is likely associated with transport of air after passing over oil industry sources located south of the station.

We present lower/middle tropospheric column-averaged CH4 mole fraction time series measured by nine globally distributed ground-based FTIR (Fourier transform infrared) remote sensing experiments of the Network for the Detection of Atmospheric Composition Change (NDACC). We show that these data are well representative of the tropospheric regional-scale CH4 signal, largely independent of the local surface small-scale signals, and only weakly dependent on upper tropospheric/lower stratospheric (UTLS) CH4 variations. In order to achieve the weak dependency on the UTLS, we use an a posteriori correction method. We estimate a typical precision for daily mean values of about 0.5% and a systematic error of about 2.5%. The theoretical assessments are complemented by an extensive empirical study. For this purpose, we use surface in situ CH4 measurements made within the Global Atmosphere Watch (GAW) network and compare them to the remote sensing data. We briefly discuss different filter methods for removing the local small-scale signals from the surface in situ data sets in order to obtain the in situ regional-scale signals. We find good agreement between the filtered in situ and the remote sensing data. The agreement is consistent for a variety of timescales that are interesting for CH4 source/sink research: day-to-day, monthly, and inter-annual. The comparison study confirms our theoretical estimations and proves that the NDACC FTIR measurements can provide valuable data for investigating the cycle of CH4.

Stable carbon isotopic signatures (δ13C) can provide insight into sectors of anthropogenic activities emitting carbon dioxide (CO2) in situations where signatures of unique end-members are known. We present an atmospheric modelling framework that combines local δ13C signatures of combustion fuels with the Southern Ontario CO2 Emissions (SOCE) inventory to simulate ambient δ13CO2 signatures in the Greater Toronto Area. We demonstrate that the modelled δ13CO2 captures the variability in measured hourly signatures at the Downsview station from January to March, 2016 as well as the diurnal profile of signatures. We then use our ability to model δ13CO2 to assess traditional isotopic mass balance (IMB) and Keeling and Miller-Tans analysis. We performed three IMB to estimate the δ13CO2 signature of the local CO2 enhancement (δ13Cs) for measured and modelled data (using two background estimates: 5th percentile of a 48-hour running average and output from the Copernicus Atmospheric Monitoring Service (CAMS)). We found that when the 5th percentile was used as a background estimate, the δ13Cs was often unrealistic and isotopically heavier compared to that using CAMS. We compared IMB with Keeling analyses based on both overnight and hour-of-day data. For both approaches, when Keeling analyses were run on modelled and measured data, the median δ13C signature of the CO2 sources was more variable and on average heavier than the source attribution in the SOCE inventory. Because this issue occurred using both the measurements and the model simulation, it indicates potential issues with these approaches for independent observational constraints on source attribution.

Reducing the large uncertainties in current estimates of CO2 sources and sinks at regional scales (102–105 km2) is fundamental to improving our understanding of the terrestrial carbon cycle. Continuous high-precision CO2 concentration measurements on a tower within the planetary boundary layer contain information on regional carbon fluxes; however, its spatial representativeness is generally unknown. In this study, we developed a footprint model (Simple Analytical Footprint model based on Eulerian coordinates for scalar Concentration [SAFE-C]) and applied it to two CO2 concentration towers in central Canada: the East Trout Lake 106-m-tall tower (54°21′N, 104°59′W) and the Candle Lake 28-m-high tower (53°59′N, 105°07′W). Results show that the ETL tower’s annual concentration footprints were around 103–105 km2. The monthly footprint climatologies in summer were 1.5–2 times larger than in winter. The impacts of land surface carbon flux associated with heterogeneous distribution of vegetation types on the CO2 concentration measurements were different for the different heights, varied with a range of ±5 % to ±10 % among four heights. This study indicates that concentration footprint climatology analysis is important in interpreting the seasonal, annual and inter-annual variations of tower measured CO2 concentration data and is essential for comparing and scaling regional carbon flux estimates using top-down or bottom-up approaches.

We present one of the first estimates of the global distribution of CO2 surface fluxes using total column CO2 measurements retrieved by the SRON-KIT RemoTeC algorithm from the Greenhouse gases Observing SATellite (GOSAT). We derive optimized fluxes from June 2009 to December 2010. We estimate fluxes from surface CO2 measurements to use as baselines for comparing GOSAT data-derived fluxes. Assimilating only GOSAT data, we can reproduce the observed CO2 time series at surface and TCCON sites in the tropics and the northern extra-tropics. In contrast, in the southern extra-tropics GOSAT XCO2 leads to enhanced seasonal cycle amplitudes compared to independent measurements, and we identify it as the result of a land–sea bias in our GOSAT XCO2 retrievals. A bias correction in the form of a global offset between GOSAT land and sea pixels in a joint inversion of satellite and surface measurements of CO2 yields plausible global flux estimates which are more tightly constrained than in an inversion using surface CO2 data alone. We show that assimilating the bias-corrected GOSAT data on top of surface CO2 data (a) reduces the estimated global land sink of CO2, and (b) shifts the terrestrial net uptake of carbon from the tropics to the extra-tropics. It is concluded that while GOSAT total column CO2 provide useful constraints for source–sink inversions, small spatiotemporal biases – beyond what can be detected using current validation techniques – have serious consequences for optimized fluxes, even aggregated over continental scales.

With the emergence of wide-spread application of new optical techniques to monitor δ13C in atmospheric CO2 there is a growing need to ensure well-calibrated measurements. We characterized one commonly available instrument, a cavity ring-down spectrometer (CRDS) system used for continuous in situ monitoring of atmospheric 13CO2. We found no dependency of δ13C on the CO2 concentration in the range of 303–437 ppm. We designed a calibration scheme according to the diagnosed instrumental drifts and established a quality assurance protocol. We find that the repeatability (1-σ) of measurements is 0.25‰ for 10 min and 0.15‰ for 20 min integrated averages, respectively. Due to a spectral overlap, our instrument displays a cross-sensitivity to CH4 of 0.42 ± 0.024‰ ppm−1. Our ongoing target measurements yield standard deviations of δ13C from 0.22‰ to 0.28‰ for 10 min averages. We furthermore estimate the reproducibility of our system for ambient air samples from weekly measurements of a long-term target gas to be 0.18‰. We find only a minuscule offset of 0.002 ± 0.025‰ between the CRDS and Environment Canada's isotope ratio mass spectrometer (IRMS) results for four target gases used over the course of one year.

第7回極域科学シンポジウム/横断セッション:[IA] ニーオルスン観測拠点設立25周年記念横断セッション—北極域の科学（ニーオルスン、GRENE、ArCS)—12月2日（金）国立極地研究所1階交流アトリウム

Independent verification of bottom-up greenhouse gas (GHG) emission inventories is crucial for a reliable reporting of Kyoto gases to the United Nations Framework Convention on Climate Change. Here, we use a pseudo-data experiment to test if our improved version of the well-known Radon tracer method (RTM) is able to quantitatively retrieve regional GHG fluxes. Using in-situ observations in Egbert, Canada, from 2006 to 2009 for the RTM, we derive night-time fluxes of CH4 and N2O in southern Ontario. The N2O fluxes found have a inter-quartile range of 7.6–31.2 μgN2O/(m2h) with an overall mean of 24.4 ± 5.6 μgN2O/(m2h). Comparison with the EDGAR4.1 inventory revealed an underestimation by a factor of 1.7 ± 0.4 in the inventory, which is explainable by missing natural sources and a missing seasonal cycle in the inventory. Our RTM-based fluxes of CH4 with a inter-quartiles range of 0.19–0.49 mgCH4/(m2h) and a mean of 0.36 ± 0.08 mgCH4/(m2h) lie significantly below the inventory-based estimates of 0.79 ± 0.06 m...

We infer CO2 surface fluxes using satellite observations of mid-tropospheric CO2 from the Tropospheric Emission Spectrometer (TES) and measurements of CO2 from surface flasks in a time-independent inversion analysis based on the GEOS-Chem model. Using TES CO2 observations over oceans, spanning 40° S–40° N, we find that the horizontal and vertical coverage of the TES and flask data are complementary. This complementarity is demonstrated by combining the datasets in a joint inversion, which provides better constraints than from either dataset alone, when a posteriori CO2 distributions are evaluated against independent ship and aircraft CO2 data. In particular, the joint inversion offers improved constraints in the tropics where surface measurements are sparse, such as the tropical forests of South America. Aggregating the annual surface-to-atmosphere fluxes from the joint inversion for the year 2006 yields −1.13±0.21 Pg C for the global ocean, −2.77±0.20 Pg C for the global land biosphere and −3.90±0.29 Pg C for the total global natural flux (defined as the sum of all biospheric, oceanic, and biomass burning contributions but excluding CO2 emissions from fossil fuel combustion). These global ocean and global land fluxes are shown to be near the median of the broad range of values from other inversion results for 2006. To achieve these results, a bias in TES CO2 in the Southern Hemisphere was assessed and corrected using aircraft flask data, and we demonstrate that our results have low sensitivity to variations in the bias correction approach. Overall, this analysis suggests that future carbon data assimilation systems can benefit by integrating in situ and satellite observations of CO2 and that the vertical information provided by satellite observations of mid-tropospheric CO2 combined with measurements of surface CO2, provides an important additional constraint for flux inversions.

Quasicontinuous measurements of carbon monoxide (CO) recorded over three years at Mount Waliguan (WLG), a global baseline station in remote western China, were examined using back trajectory analysis. The data include a revision to correct the working reference scale to the WMO2000 scale and corrections for drift in the reference gases. Between July 2004 and June 2007, CO exhibited large fluctuations and the 5 %, 50 % and 95 %-percentiles of relevant CO mixing ratios were 102 ppb, 126 ppb and 194 ppb. Approximately 50 % of all observed data were selected as CO background data using a mathematical procedure of robust local regression, with the remainder affected by regional-scale pollution. The monthly mean background CO mixing ratios showed a minimum in summer and a maximum in late winter, although all seasons were affected by short-term enhancements that exceeded background levels. The CO data were compared to values observed at the high alpine research station at Jungfraujoch, Switzerland. Smaller seasonal amplitudes were observed at WLG compared to the Jungfraujoch due to lower winter and spring CO levels, however, episodic enhancements of polluted air were greater at WLG. The air parcels arriving at WLG came predominately from the west, except in summer when advection from the east and southeast prevailed. Transport from the east or southeast typically brought polluted air to the site, having passed over populated urban areas upwind. A large number of elevated CO mixing ratios could also be associated with advection from the northwest of WLG via the central Xinjiang Uygur Autonomous Region (XUAR) and the Ge'ermu urban area where growing industrial activities as well as crops residue burning provide sources of CO. Air masses passing over northwestern Gansu were associated with relatively high CO values suggesting an anthropogenic influence, which was likely due to anthropogenic emissions from northwestern China (based on back-trajectory and potential source contribution analysis and on the INTEX-B: intercontinental Chemical Transport Experiment-Phase B). Background conditions were observed most frequently in air parcels from remote Tibet west of WLG. The probability that air parcels pass over regions of clean or polluted regions was further identified using potential source contribution function (PSCF) analysis.

Emissions of sulphur hexafluoride (SF6), one of the strongest greenhouse gases on a per molecule basis, are targeted to be collectively reduced under the Kyoto Protocol. Because of its long atmospheric lifetime (estimated as 800 to 3200 years), the accumulation of SF6 in the atmosphere is a direct measure of its global emissions. Examination of our extended data set of globally distributed high-precision SF6 observations shows an increase in SF6 abundance from near zero in the 1970s to a global mean of 6.7 ppt by the end of 2008. In-depth evaluation of our long-term data records shows that the global source of SF6 decreased after 1995, most likely due to SF6 emission reductions in industrialised countries, but increased again after 1998. By subtracting those emissions reported by Annex I countries to the United Nations Framework Convention of Climatic Change (UNFCCC) from our observation-inferred SF6 source leaves a surprisingly large gap of more than 70–80% of non-reported SF6 emissions in the last decade. This suggests a strong under-estimation of emissions in Annex I countries and underlines the urgent need for independent atmospheric verification of greenhouse gases emissions accounting.

Existing estimates of methane fluxes from North American wetlands vary widely in both magnitude and distribution. In light of these disagreements, this study uses atmospheric methane observations from the US and Canada to analyze seven different bottom-up, wetland methane estimates reported in a recent model comparison project. We first use synthetic data to explore how well atmospheric observations can constrain wetland fluxes. We find that observation sites can identify an atmospheric pattern from Canadian wetlands but not reliably from US wetlands. The network can also identify the spatial distribution of fluxes in Canada at multi-province spatial scales. Based upon these results, we then use real data to evaluate the magnitude, temporal distribution, and spatial distribution of each model estimate. Most models overestimate the magnitude of fluxes across Canada. Most predict a seasonality that is too narrow, potentially indicating an over-sensitivity to air or soil temperatures. In addition, the LPJ-Bern model has a spatial distribution that is most consistent with atmospheric observations. Unlike most models, LPJ-Bern utilizes land cover maps, not just remote sensing inundation data, to estimate wetland coverage. A flux model with a constant spatial distribution outperforms most other existing flux estimates across Canada.

In this paper, the continuous (1994–2001) and discrete air sample (1991–2001) measurements of atmospheric CH 4 from the Waliguan Baseline Observatory located in western China (36°17′N, 100°54′E, 3816 m asl) are presented and characterized. The CH 4 time series show large episodic events on the order of 100 ppb throughout the year. During spring, a diurnal cycle with average amplitude of 7 ppb and a morning maximum and late afternoon minimum is observed. In winter, a diurnal cycle with average amplitude of 14 ppb is observed with an afternoon maximum and morning minimum. Unlike most terrestrial observational sites, no obvious diurnal patterns are present during the summer or autumn. A background data selection procedure was developed based on local horizontal and vertical winds. A selected hourly data set representative of “baseline” conditions was derived with approximately 50% of the valid hourly data. The range of CH 4 mixing ratios, annual means, annual increases and mean annual cycle at Waliguan during the 1992–2001 were derived from discrete and continuous data representative of “baseline” conditions and compared to air samples collected at other Northern Hemisphere sites. The range of CH 4 monthly means of 1746–1822 ppb, average annual means of 1786.7±10.8 ppb and mean annual increase of 4.5±4.2 ppb yr −1 at Waliguan were inline with measurements from sites located between 30° and 60°N. There were variations observed in the CH 4 annual increase patterns at Waliguan that were slightly different from the global pattern. The mean CH 4 annual cycle at Waliguan shows an unusual pattern of two gentle peaks in summer and February along with two small valleys in early winter and spring and a mean peak-to-peak amplitude of ∼11 ppb, much smaller than amplitudes observed at most other mid- and high-northern latitude sites. The Waliguan CH 4 data are strongly influenced by continental Asian CH 4 emissions and provide key information for global atmospheric CH 4 models.

Continuous and flask measurements of atmospheric CO 2 taken at Sable Island from August 1992 to April 1993 are presented and characterised as a function of air mass origin. The atmospheric environment over Sable Island (43°56′N, 60°01′W) is continuously influenced by the complex meteorology of synoptic systems moving off North America. This makes the interpretation of the Sable Island CO 2 data difficult. However, trajectory analysis shows distinct quantitative differences between the statistics of CO 2 measurements associated with air masses from “North America” (regions of high anthropogenic and terrestrial biospheric fluxes associated with much of the United States and the southern half of Canada) and of those associated with air masses from the “Arctic/North Atlantic” (regions of few terrestrial fluxes and oceans associated with the northern half of Canada and the Atlantic Ocean). When the continuous CO 2 data are segregated into these two trajectory sectors for the period of observation, air masses originating in the North American sector show a higher CO 2 mixing ratio by ∼2 ppm in winter and lower by ∼3 ppm in summer, compared to air masses arriving from the other sector. Furthermore, the continuous Sable Island CO 2 measurements show a detectable monthly mean (August/September) diurnal cycle with an amplitude of ∼2 ppm, with a minimum occurring on average around noon local time. Given the timing of the observed diurnal minimum and the lack of vegetation on the island, this indicates that the diurnal pattern observed at Sable Island is a diffused remnant of diurnal cycles transported from the main North American continent. These characteristic details are not captured by the discrete flask sampling program on the island. DOI: 10.1034/j.1600-0889.2003.00051.x

The role of formaldehyde in the atmospheric chemistry of the Arctic marine boundary layer has been studied during both polar day and night at Alert, Nunavut, Canada. Formaldehyde concentrations were determined during two separate field campaigns (PSE 1998 and ALERT2000) from polar night to the light period. The large differences in the predominant chemistry and transport issues in the dark and light periods are examined here. Formaldehyde concentrations during the dark period were found to be dependent on the transport of air masses to the Alert site. Three regimes were identified during the dark period, including background (free-tropospheric) air, transported polluted air from Eurasia, and halogen-processed air transported across the dark Arctic Ocean. In the light period, background formaldehyde levels were compared to a calculation of the steady-state formaldehyde concentrations under background and low-ozone conditions. We found that, for sunlit conditions, the ambient formaldehyde concentrations cannot be reproduced by known gas-phase chemistry. We suggest that snowpack photochemistry contributes to production and emission of formaldehyde in the light period, which could account for the high concentrations observed at Alert.

We present a 3 year record of continuous gas chromatographic nitrous oxide (N2O) observations performed at the urban station Heidelberg (Germany) together with weekly flask data from a remote continental site, Schauinsland (Black Forest, Germany), and two-weekly integrated data from the maritime background station Izana (Canary Islands). These data are supplemented by continuous atmospheric radon 222 observations. Mean rates of increase of N2O of 0.70–0.78 ppb yr−1 were observed over the continent and in maritime background air (Izana). The well-mixed continental mixing ratio was found to be higher by only 1.1 ppb (Schauinsland) and 2.4 ppb (Heidelberg) than for maritime background air. Specially tailored data selection of the Heidelberg record allowed the changing influence of a regional N2O point source (adipic acid production, BASF AG) to be clearly identified. The radon (222Rn) tracer method was applied to nighttime N2O observations at Heidelberg to estimate mean regional emissions, which changed from (161 ± 32) μg N2O-N m−2 h−1 in 1996–1997 to (77 ± 10) μg N2O-N m−2 h−1 in 1998 as a consequence of 90% emission reduction from BASF. An estimate of the continental N2O flux from southwestern Europe based on further selected Heidelberg data (only well-mixed, late afternoon situations) and observations from the Schauinsland station yielded mean N2O fluxes of (43 ± 5) μg N2O-N m−2 h−1 and (42 ± 4) μg N2O-N m−2 h−1. These results compare well with statistical emissions inventories, when taking into account possible systematic errors of the radon tracer method of 30–35%.

As part of the Polar Sunrise Experiments (PSE) 1995, we report our results on measurement of non-methane hydrocarbons (NMHC) collected at Alert, Northwest Territories, Canada (82.5° N, 62.3° W) from Julian days 57 to 113, 1995 along with our data on continuous methane and ozone measurements during the same period. The concentration of NMHCs such as alkanes correlated well with that of methane during the dark period before polar sunrise. However, no correlation was observed after the sunrise. Several ozone depletion events and concurrent decreases in hydrocarbon concentrations relative to their background levels were observed. In all ozone depletion periods, concentration changes of alkanes and toluene were consistent with the occurrence of Cl-atom reactions. The characteristics of alkane isomer concentration changes suggest the dominance of HO chemistry prior to, and a switch to Cl chemistry after, the polar sunrise (during the ozone depletion events). The changes in ethyne concentration from their background level were in excess of those expected from Cl-atom kinetics alone and are attributed to additional Br-atom reactions. The time integral for Br mixing ratios is a few orders of magnitudes higher than that for Cl-atoms, suggesting much higher Br-atom concentrations compared to Cl-atom concentrations, if they are present simultaneously.

A 7-year record (1990–1996) of continuous atmospheric methane (CH4) measurements is presented from a remote midcontinental monitoring station at Fraserdale, Ontario (49°53′N, 81°34′W). Ninety-six air samples per day were measured with a fully automated gas chromatograph with flame ionization detection. Five-day Lagrangian back trajectories over the 7-year period were used to establish a climatology in the region of the station. The site is predominantly influenced by air flow from northern and high-latitude regions and therefore uniquely positioned to monitor wetland emissions. During winter, CH4 concentration time series from Fraserdale often match the short-term variability observed at the high Arctic monitoring station at Alert, Northwest Territories (82°27′N, 61°31′W). During summer, due to diurnal changes of vertical mixing in the boundary layer, large diurnal cycles in CH4 mixing ratio up to 150 ppb are observed. The data selected for the afternoon, when the boundary layer is well-mixed, are representative of a larger spatial scale. The mean annual cycle of CH4 at Fraserdale determined using these selected data is significantly different from annual cycles at other mid- and high-northern latitude sites thus providing key information for global atmospheric CH4 models. In late summer the annual cycle at Fraserdale shows a distinct secondary maximum in CH4. This is the result of advection of air with enhanced CH4 due to emissions from the extensive wetland areas to the north and northwest. The average growth rate (using selected data) for the period was 5.6 ppb yr−1 with a growth rate pattern that is slightly different and out of phase with growth rate changes observed at other high-latitude observing sites by 2 to 6 months.

The isotopic composition of carbon monoxide (13C, 14C, 18O) and methane (13C, D) was measured on air samples collected between Vladivostok and Moscow using the Trans-Siberian railroad during August 1996. Apart from short term fluctuations in the direct vicinity of sources, continuous measurements of CO and CH4 showed sustained, elevated mixing ratios over several hundreds of kilometers indicating the large scale influencing of traversed air masses by significant sources. Persistent, enhanced CH4 levels were found over the west Siberian lowlands concurrent with significantly depleted δ13C and δD values. The derived isotopic signature of the CH4 source (δ13C = −62.5±4.7‰ V-PDB; δD = −311±14‰ V-SMOW) clearly indicates the dominance of biogenic CH4, with the west Siberian wetlands being the most likely candidate. A second major feature in the data set is the enormous enhancement of CO (up to 1500 nmol/mol) east of Chita, extending over a 2000 km section along the river Amur. The 14CO measurements and back trajectory analyses identify biomass burning as the origin of the highly elevated CO. This is further supported by the δ18O(CO) and the δ13C/δD signature of the accompanying moderate CH4 enhancement.

[1] Nitrous oxide (N2O) concentrations and 222Rn activities are measured semi-continuously at three stations in France: Gif-sur-Yvette (a semi-urban station near Paris), Trainou tower (a rural station) and Puy-de-Dome (a mountain site). From 2002 to 2011, we have found a mean rate of N2O increase of 0.7 pbb a−1. The analysis of the mean diurnal N2O and 222Rn cycles shows maximum variabilities at the semi-urban site of Gif-sur-Yvette (0.96 ppb for N2O and 2 Bq m−3 for 222Rn) compared to the rural site of Trainou tower (0.32 ppb for N2O and 1.3 Bq m−3 for 222Rn). The use of 222Rn as a tracer for vertical mixing and atmospheric transport, combined with the semi-continuous N2O measurements, allows estimation of N2O emissions by applying the Radon-Tracer-Method. Mean N2O emissions values between 0.34 ± 0.12 and 0.51 ± 0.18 g(N2O) m−2 a−1 and 0.52 ± 0.18 g(N2O) m−2 a−1were estimated in the catchment area of Gif-sur-Yvette and Trainou, respectively. The mean annual N2O fluxes at Gif-sur-Yvette station correlate well with annual precipitation. A 25% increase in precipitation corresponds to a 32% increase in N2O flux. The N2O fluxes calculated with the Radon-Tracer-Method show a seasonal cycle, which indicates a strong contribution from the agricultural source, with the application of fertilizers in the early spring inducing a strong increase in N2O emissions. Finally, the results of the Radon-Tracer-Method agree well with the national and global emission inventories, accounting for the uncertainties of both methods.

We present the first estimate of the global distribution of CO_2 surface 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 CO_2 mixing 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 CO_2 column.

[1] In a prior study, a decade-long dataset of ground-based aerosol and carbon monoxide measurements from Barrow, Alaska (71°N, 157°W) was used to show that surface air in the Arctic is clean during the summer, less due to inhibited transport of pollutants from mid-latitudes, and more because of efficient wet scavenging at temperatures near freezing. Here, the analysis is extended to light-absorbing aerosols, such as black carbon, and to measurements from Alert, Canada (82°N, 62°W). The data imply that both light scattering and light absorbing aerosols have similar seasonal cycles, independent of location, and they are controlled nearly equally by wet scavenging. Removal is particularly efficient at high relative humidities and warm temperatures, which suggests that a future warmer and wetter Arctic may also be cleaner. Assuming aerosol pollutants generally have a warming effect in the Arctic, such an increase in wet scavenging would represent a negative Arctic climate feedback.

To strengthen scientific management and sharing of greenhouse gas data obtained from atmospheric background stations in China, it is important to ensure the standardization of observations and establish the data treatment and quality control procedure so as to maintain consistency in atmospheric carbon dioxide (CO2) and methane (CH4) measurements from different background stations. An automated gas chromatographic system (Hewlett Packard 5890GC employing flame ionization detection) for in situ measurements of atmospheric CO2 and CH4 has been developed since 1994 at the China Global Atmosphere Watch Baseline Observatory at Mt. Waliguan, in Qinhai. In this study, processing and quality control flow of CO2 and CH4 data acquired by HP ChemStation are discussed in detail, including raw data acquisition, data merge, time series inspection, operator flag, principal investigator flag, and the comparison of the GC measurement with the flask method. Atmosphere CO2 and CH4 mixing ratios were separated as background and non-background data using a robust local regression method, approximately 72% and 44% observed values had been filtered as background data for CO2 and CH4, respectively. Comparison of the CO1 and CH, in situ data to the flask sampling data were in good agreement, the relative deviations are within +/- 0.5% for CO2 and for CH4. The data has been assimilated into global database (Globalview-CO2, Globalview-CH4), submitted to the World Data Centre for Greenhouse Gases (WDCGG), and applied to World Meteorological Organization (WMO) Greenhouse Gas Bulletin and assessment reports of the United Nations Intergovernmental Panel on Climate Change (IPCC).

[1] For over 20 years, atmospheric measurements of CO2 dry air mole fractions have been used to derive estimates of CO2 surface fluxes. Historically, only a few research laboratories made these measurements. Today, many laboratories are making CO2 observations using a variety of analysis techniques and, in some instances, using different calibration scales. As a result, the risk of biases in individual CO2 mole fraction records, or even in complete monitoring networks, has increased over the last decades. Ongoing experiments comparing independent, well-calibrated measurements of atmospheric CO2 show that biases can and do exist between measurement records. Biases in measurements create artificial spatial and temporal CO2 gradients, which are then interpreted by an inversion system, leading to erroneous flux estimates. Here we evaluate the impact of a constant bias introduced into the National Oceanic and Atmospheric Administration (NOAA) quasi-continuous measurement record at the Park Falls, Wisconsin (LEF), tall tower site on CarbonTracker flux estimates. We derive a linear relationship between the magnitude of the introduced bias at LEF and the CarbonTracker surface flux responses. Temperate North American net flux estimates are most sensitive to a bias at LEF in our CarbonTracker inversion, and its linear response rate is 68 Tg C yr−1 (∼10% of the estimated North American annual terrestrial uptake) for every 1 ppm of bias in the LEF record. This sensitivity increases when (1) measurement biases approached assumed model errors and (2) fewer other measurement records are available to anchor the flux estimates despite the presence of bias in one record. Flux estimate errors are also calculated beyond North America. For example, biospheric uptake in Europe and boreal Eurasia combined increases by 25 Tg C yr−1 per ppm CO2 to partially compensate for changes in the North American flux totals. These results illustrate the importance of well-calibrated, high-precision CO2 dry air mole fraction measurements, as well as the value of an effective strategy for detecting bias in measurements. This study stresses the need for a monitoring network with the necessary density to anchor regional, continental, and hemispheric fluxes more tightly and to lessen the impact of potentially undetected biases in observational networks operated by different national and international research programs.

The Hudson Bay Lowlands (HBL) is the second largest boreal wetland ecosystem in the world and an important natural source of global atmospheric methane. We quantify the HBL methane emissions by using the GEOS-Chem chemical transport model to simulate aircraft measurements over the HBL from the ARCTAS and pre-HIPPO campaigns in May–July 2008, together with continuous 2004–2008 surface observations at Fraserdale (southern edge of HBL) and Alert (Arctic background). The difference in methane concentrations between Fraserdale and Alert is shown to be a good indicator of HBL emissions, and implies a sharp seasonal onset of emissions in late May (consistent with the aircraft data), a peak in July–August, and a seasonal shut-off in September. The model, in which seasonal variation of emission is mainly driven by surface temperature, reproduces well the observations in summer but its seasonal shoulders are too broad. We suggest that this reflects the suppression of emissions by snow cover and greatly improve the model simulation by accounting for this effect. Our resulting best estimate for HBL methane emissions is 2.3 Tg a−1, several-fold higher than previous estimates (Roulet et al., 1994; Worthy et al., 2000).

This paper documents a global Bayesian variational inversion of CO2 surface fluxes during the period 1988–2008. Weekly fluxes are estimated on a 3.75° × 2.5° (longitude-latitude) grid throughout the 21 years. The assimilated observations include 128 station records from three large data sets of surface CO2 mixing ratio measurements. A Monte Carlo approach rigorously quantifies the theoretical uncertainty of the inverted fluxes at various space and time scales, which is particularly important for proper interpretation of the inverted fluxes. Fluxes are evaluated indirectly against two independent CO2 vertical profile data sets constructed from aircraft measurements in the boundary layer and in the free troposphere. The skill of the inversion is evaluated by the improvement brought over a simple benchmark flux estimation based on the observed atmospheric growth rate. Our error analysis indicates that the carbon budget from the inversion should be more accurate than the a priori carbon budget by 20% to 60% for terrestrial fluxes aggregated at the scale of subcontinental regions in the Northern Hemisphere and over a year, but the inversion cannot clearly distinguish between the regional carbon budgets within a continent. On the basis of the independent observations, the inversion is seen to improve the fluxes compared to the benchmark: the atmospheric simulation of CO2 with the Bayesian inversion method is better by about 1 ppm than the benchmark in the free troposphere, despite possible systematic transport errors. The inversion achieves this improvement by changing the regional fluxes over land at the seasonal and at the interannual time scales. This work was performed using HPC resources from GENCI‐ (CCRT/CINES/IDRIS; grant 2009‐ t2009012201). It was cofunded by the European Commission under the EU Seventh Research Framework Programme (grant agreements 212196, COCOS, and 218793, MACC).

[1] The rate of increase in global atmospheric methane (CH4) abundance has steadily declined since the late 1980s with near zero increase from 1999 through 2006. At the Canadian Baseline Observatory at Alert, Canada (82°28′N, 62°30′W), continuous measurements of methane (CH4) and carbon dioxide (CO2) have been made since 1987. During winter, both gases are frequently highly correlated during well-defined episodes lasting from 2 to 5 days. We observe a gradual decrease in the ratios of CH4/CO2 during these episodes from ∼16 ppb CH4 (ppm CO2)−1 to ∼12 ppb CH4 (ppm of CO2)−1 over the entire record. An atmospheric transport model with prescribed CO2 and CH4 source distributions is used to partition simulated CH4 events into contributions by region. We show that anthropogenic emissions from Europe and Siberia account for more than 85% of the CO2 and CH4 enhancements simulated at Alert, but without a change in CH4 emissions, modeled CH4/CO2 ratios remain constant. To reproduce the observed trend in the ratio of CH4/CO2, the model requires a reduction in emissions of CH4 on the order of 30 Tg (13.6 to 33.4 Tg) in Europe and Siberia over the observational period. This is about twice the drop reported by the Emission Database for Global Atmospheric Research (EDGAR) emissions inventory and large enough to account for the leveling off of the global atmospheric CH4 burden observed over the past 20 years.

regional GPP from mixing ratio measurements, we also compared the estimates of regional GPP with estimates made using eddy covariance (EC) flux measurements, although their respective source areas are different. They had similar seasonal patterns, but the regional estimates were consistently smaller than the local EC flux derived GPP throughout the growing season in 2003. These estimates of annual regional GPP were 649–664 g C m � 2 for 2003 while the EC-derived annual GPP was 819–847 g C m � 2 . The annual difference was about 20–25%. The EC flux footprint of the tower was relatively homogeneous old black spruce while the concentration footprint, which was a few orders of magnitude larger than the flux footprint, covered boreal evergreen and deciduous broadleaf forests, grassland, cropland, and lakes. Nonforested land occupied about 10–50% of the concentration footprint depending on wind direction and speed and was less productive than the black spruce forest. The discrepancies between regional and local GPP estimates reflected the differences in underlying land surfaces represented by the different footprint areas.

We present an estimate of net CO 2 exchange between the terrestrial biosphere and the atmosphere across North America for every week in the period 2000 through 2005. This estimate is derived from a set of 28,000 CO 2 mole fraction observations in the global atmosphere that are fed into a state-of-the-art data assimilation system for CO 2 called CarbonTracker. By design, the surface fluxes produced in CarbonTracker are consistent with the recent history of CO 2 in the atmosphere and provide constraints on the net carbon flux independent from national inventories derived from accounting efforts. We find the North American terrestrial biosphere to have absorbed −0.65 PgC/yr (1 petagram = 10 15 g; negative signs are used for carbon sinks) averaged over the period studied, partly offsetting the estimated 1.85 PgC/yr release by fossil fuel burning and cement manufacturing. Uncertainty on this estimate is derived from a set of sensitivity experiments and places the sink within a range of −0.4 to −1.0 PgC/yr. The estimated sink is located mainly in the deciduous forests along the East Coast (32%) and the boreal coniferous forests (22%). Terrestrial uptake fell to −0.32 PgC/yr during the large-scale drought of 2002, suggesting sensitivity of the contemporary carbon sinks to climate extremes. CarbonTracker results are in excellent agreement with a wide collection of carbon inventories that form the basis of the first North American State of the Carbon Cycle Report (SOCCR), to be released in 2007. All CarbonTracker results are freely available at http://carbontracker.noaa.gov .

Firn air and ice have been sampled and analyzed for trace gases (CO2, N2O, CH4, and CO) and isotopes (14C, 13C, and 18O of CO2; 3H of ice) at 3 m intervals from the surface to the depth of closure at 60 m on the Devon Island Ice Cap, a low-elevation permanent glacier in the Canadian Arctic Islands, to investigate firn diffusion and the effects of summer melting. The 14CO2 profile from the permeable firn includes the 1963 thermonuclear peak at a depth of 53.9 ± 1.5 m. The twofold increase and rapid decay that characterize the recent atmospheric history for 14CO2 provide a robust atmospheric scenario that is used with a firn air diffusion model to inversely construct the firn diffusivity profile. The results show a permeable but essentially nondiffusive zone from 50 to 60 m depth. A firn-ice age profile was produced from density measurements, and accumulation rates were calibrated with the depth of the 1963 thermonuclear 3H peak. The average ages for CO2 in the sampled firn air profile were determined by a new method based on the rate of 18O exchange between CO2 and the ice matrix. Calibrated with the 1963 peak for thermonuclear 14CO2, a 21.2-year reaction halftime is calculated for exchange taking place at the firn temperature of -22.8°C on Devon. This gives an average age of 54.9 (+6.0/-12.0) years for firn air at 60 m depth in 140-year-old ice. Thus CO2 has a mean age 85 years younger than associated ice at the point of occlusion. The measured δ18OCO2 in firn air provides no indication of alteration by summer melting, which is attributed to a high degree of convective and diffusive flushing of the upper firn as shown by diffusion modeling. This suggests that ice sheets with summer melt layers can reliably preserve atmospheric trace gas signals. Copyright 2007 by the American Geophysical Union.

[1] Ecosystem CO2 exchange with the atmosphere and the planetary boundary layer (PBL) dynamics are correlated diurnally and seasonally. The strength of this kind of covariation is quantified as the rectifier effect, and it affects the vertical gradient of CO2 and thus the global CO2 distribution pattern. An 11-year (1990–1996, 1999–2002), continuous CO2 record from Fraserdale, Ontario (49°52′29.9″N, 81°34′12.3″W), along with a coupled vertical diffusion scheme (VDS) and ecosystem model named Boreal Ecosystem Productivity Simulator (BEPS), are used to investigate the interannual variability of the rectifier effect over a boreal forest region. The coupled model performed well (r2 = 0.70 and 0.87, at 40 m at hourly and daily time steps, respectively) in simulating CO2 vertical diffusion processes. The simulated annual atmospheric rectifier effect varies from 3.99 to 5.52 ppm, while the diurnal rectifying effect accounted for about a quarter of the annual total (22.8∼28.9%).The atmospheric rectification of CO2 is not simply influenced by terrestrial source and sink strengths, but by seasonal and diurnal variations in the land CO2 flux and their interaction with PBL dynamics. Air temperature and moisture are found to be the dominant climatic factors controlling the rectifier effect. The annual rectifier effect is highly correlated with annual mean temperature (r2 = 0.84), while annual mean air relative humidity can explain 51% of the interannual variation in rectification. Seasonal rectifier effect is also found to be more sensitive to climate variability than diurnal rectifier effect.

Continuous methane concentration records and stable isotope observations measured in the suburbs of Heidelberg, Germany, are presented. While delta13C-CH4 shows a significant trend of -0.14 permil per year, towards more depleted values, no trend is observed in the concentration data. Comparison of the Heidelberg records with clean air observations in the North Atlantic at Izana station (Tenerife) allows the determination of the continental methane excess at Heidelberg, decreasing by 20% from 190 ppb in 1992 to 150 ppb in 1997. The isotope ratio which is associated with this continental methane pile-up in the Heidelberg catchment area shows a significant trend to more depleted values from delta13C (source) = -47.4 ± 1.2 permil in 1992 to 52.9 ± 0.4 permil in 1995/96, pointing to a significant change in the methane source mix. Total methane emissions in the Heidelberg catchment area are estimated using the 222Radon (222Rn) tracer method: from the correlations of half hourly 222Rn and CH4 mixing ratios from 1995 to 1997, and the mean 222Rn exhalation rate from typical soils in the Rhine valley, a mean methane flux of 0.24 ± 0.5 g CH4 km-2 s-1 is derived. For the Heidelberg catchment area with an estimated radius of approximately 150 km, Core Inventories Air 1990 (CORINAIR90) emission estimates yield a flux of 0.47 g CH4 km-2 s-1, which is about 40% higher than the 222Rn derived number if extrapolated to 1990. The discrepancy can be explained by over-estimated emissions from waste management in the CORINAIR90 statistical assessment. The observed decrease in total emissions can be accounted for by decreasing contributions from fossil sources (mainly coal mining) and from cattle breeding. This finding is also supported by the observed decrease in mean source isotopic signatures.

Global high-precision atmospheric Δ 14 CO 2 records covering the last two decades are presented, and evaluated in terms of changing (radio)carbon sources and sinks, using the coarse-grid carbon cycle model GRACE. Dedicated simulations of global trends and interhemispheric differences with respect to atmospheric CO 2 as well as δ 13 CO 2 and Δ 14 CO 2 , are shown to be in good agreement with the available observations (1940–2008). While until the 1990s the decreasing trend of Δ 14 CO 2 was governed by equilibration of the atmospheric bomb 14 C perturbation with the oceans and terrestrial biosphere, the largest perturbation today are emissions of 14 C-free fossil fuel CO 2 . This source presently depletes global atmospheric Δ 14 CO 2 by 12–14‰ yr -1 , which is partially compensated by 14 CO 2 release from the biosphere, industrial 14 C emissions and natural 14 C production. Fossil fuel emissions also drive the changing north–south gradient, showing lower Δ 14 C in the northern hemisphere only since 2002. The fossil fuel-induced north–south (and also troposphere–stratosphere) Δ 14 CO 2 gradient today also drives the tropospheric Δ 14 CO 2 seasonality through variations of air mass exchange between these atmospheric compartments. Neither the observed temporal trend nor the Δ 14 CO 2 north–south gradient may constrain global fossil fuel CO 2 emissions to better than 25%, due to large uncertainties in other components of the (radio)carbon cycle.DOI: 10.1111/j.1600-0889.2009.00446.x

Atmospheric CO 2 measurements show strong synoptic variability. To understand the contribution of the synoptic signals on atmospheric CO 2 inversion, we simulate the cases of biospheric fluxes with and without synoptic variations (referred to as ‘Synoptic’ and ‘Reference’, respectively) using an atmospheric transport model, and then perform inversion analyses with these biospheric CO 2 concentration fields. Results show the monthly and annually averaged CO 2 concentration anomalies (Synoptic–Reference) are functions of the distance from the continental biospheric source regions. Remote sites (like Mauna Loa) show averaged monthly amplitude of ∼0.2 ppm, while continental sites show averaged monthly amplitudes of 1–2 ppm with maximum monthly amplitudes up to 7 ppm. Spatial scales of these monthly mean synoptic anomaly patterns may exceed 1000 km. These CO 2 concentration patterns are the results of the interaction of the synoptic CO 2 flux field and atmospheric transport, and may be referred to as the synoptic Rectifier Effect. Inversion CO 2 fluxes for 1992–1995 are obtained using biospheric background fields with and without synoptic biospheric flux variations. The maximum magnitude differences in estimated monthly flux for land and ocean regions are ∼0.4 and ∼0.2 GtC month −1 , respectively. The average land sink increases by 0.19 GtC yr −1 while the average ocean sink decreases by 0.30 GtC yr −1 . DOI: 10.1111/j.1600-0889.2006.00219.x

Estimating global carbon fluxes by inverting atmospheric CO 2 through the use of atmospheric transport models has shown the importance of the covariance between biospheric fluxes and atmospheric transport on the carbon budget. This covariance or coupling occurs on many time scales. This study examines the coupling of the biosphere and the atmosphere on the meso- and synoptic scales using a coupled atmosphere–biosphere regional model covering Canada. The results are compared with surface and light aircraft measurement campaigns at two boreal forest sites in Canada (Fraserdale and BERMS). Associated with cold and warm frontal features, the model results showed that the biospheric fluxes are strongly coupled to the atmosphere through radiative forcing. The presence of cloud near frontal regions usually results in reduced photosynthetic uptake, producing CO 2 concentration gradients across the frontal regions on the order of 10 parts per million (ppm). Away from the frontal region, the biosphere is coupled to the mesoscale variations in similar ways, resulting in mesoscale variations in CO 2 concentrations of about 5 ppm. The CO 2 field is also coupled strongly to the atmospheric dynamics. In the presence of frontal circulation, the CO 2 near the surface can be transported to the mid to upper troposphere. Mesoscale circulation also plays a significant part in transporting the CO 2 from the planetary boundary layer (PBL) to the mid-troposphere. In the absence of significant mesoscale or synoptic scale circulation, the CO 2 in the PBL has minimal exchange with the free troposphere, leading to strong gradients across the top of the PBL. We speculate that the ubiquity of the common synoptic and mesoscale processes in the atmosphere may contribute significantly to the rectifier effect and hence CO 2 inversion calculations. DOI: 10.1111/j.1600-0889.2004.00104.x

Time series of in-situ CO 2 data from Fraserdale (50°N, 81°W) in the northern Ontario boreal forest is described, together with an analysis of observed variations occurring on daily to interannual timescales. Atmospheric CO 2 measurements at Fraserdale reflect a complex interaction between the daily cycle of the vegetative carbon flux and the daily evolution of the boundary layer mixing dynamics. This is particularly evident during the growing season, when CO 2 concentrations are influenced strongly by local and regional biospheric activities. In addition, the atmospheric CO 2 measurements at Fraserdale are greatly influenced by the direction of atmospheric transport, and reflect the complex heterogeneous distribution of ecosystem types around the site. Averaged over the 7-yr period from 1990 to 1996, the seasonal cycle associated with air from west and northwest of the site shows an amplitude of ∼19 ppm, while that associated with air from the south and southwest shows an amplitude of ∼23 ppm; the seasonal minimum, on average, occurs about a week earlier in the latter case than in the former. This is reflective of the fact that many of the deciduous trees are located to the south and southwest of Fraserdale. Furthermore, its location in the boreal forest causes the seasonal minimum to occur on average in early August at Fraserdale, compared to late August observed at Alert and at many other background stations in the high-latitude Northern Hemisphere. At the Fraserdale site there is no statistically significant indication, during the 1990–1996 study period, of changes in the length of the growing season (as measured by zero crossing points in the seasonal cycle). DOI: 10.1034/j.1600-0889.2003.00062.x

In situ measurements of carbon dioxide, methane, black carbon, peroxyacetylnitrate, condensation nuclei, and radon were made from the Canadian Baseline Atmospheric Monitoring Observatory at Alert, Northwest Territories, Canada (82°28′N, 62°30′W′) during the “Polar Sunrise Experiment” (January 16 to April 20, 1992). The time series of methane, carbon dioxide, peroxyacetylnitrate, and black carbon were frequently highly correlated during January and February during well-defined episodes lasting from 2 to 5 days. This is consistent with data from earlier years. Shortly after polar sunrise, the temporal variability in both trace gases and aerosols diminished. Using a definition of black carbon concentrations exceeding 100 ng m−3, 11 long-range transport episodes were defined. Lagrangian 5-day back trajectories along with the concentration data were classified into six geographical sectors to characterize the major episodes. The winter variability is related to synoptic meteorology, weak vertical mixing, and rapid air mass transport originating from Siberian and/or European source regions. Measurements of the radon daughter (222Rn) activity in the atmosphere were used to further explore the transport of continental material across the Arctic basin.