From 2007 to 2013, the globally averaged mole fraction of methane in the atmosphere increased by 5.7 ± 1.2 ppb yr−1. Simultaneously, δ13CCH4 (a measure of the 13C/12C isotope ratio in methane) has ...shifted to significantly more negative values since 2007. Growth was extreme in 2014, at 12.5 ± 0.4 ppb, with a further shift to more negative values being observed at most latitudes. The isotopic evidence presented here suggests that the methane rise was dominated by significant increases in biogenic methane emissions, particularly in the tropics, for example, from expansion of tropical wetlands in years with strongly positive rainfall anomalies or emissions from increased agricultural sources such as ruminants and rice paddies. Changes in the removal rate of methane by the OH radical have not been seen in other tracers of atmospheric chemistry and do not appear to explain short‐term variations in methane. Fossil fuel emissions may also have grown, but the sustained shift to more 13C‐depleted values and its significant interannual variability, and the tropical and Southern Hemisphere loci of post‐2007 growth, both indicate that fossil fuel emissions have not been the dominant factor driving the increase. A major cause of increased tropical wetland and tropical agricultural methane emissions, the likely major contributors to growth, may be their responses to meteorological change.
Plain Language Summary
Atmospheric methane, which is a powerful greenhouse gas, is increasing rapidly. In the 20th century, methane growth was primarily driven by emissions from fossil fuel sources, such as the natural gas industry and coal mining. Then, in the early years of the 21st century, came a period of stability in methane. However, since 2007, growth has resumed, with especially strong growth in 2014. Evidence from carbon isotopes implies that the primary cause of the new growth is an increase in biogenic emissions, probably from wetlands and also agricultural sources, such as rice fields and cattle. The evidence presented in this research study, from a wide range of measurement sites both in the northern and southern hemispheres, suggests increased tropical emissions, for example from tropical wetlands, may be a principal cause of the global rise in methane. Contributions to the growth may also come from agricultural sources and perhaps some fossil fuel emissions also.
Key Points
Atmospheric methane is growing rapidly
Isotopic evidence implies that the growth is driven by biogenic sources
Growth is dominated by tropical sources
We describe an assimilation system for atmospheric methane (CH4 ), CarbonTracker-CH4 , and demonstrate the diagnostic value of global or zonally averaged CH4 abundances for evaluating the results. We ...show that CarbonTracker-CH4 is able to simulate the observed zonal average mole fractions and capture inter-annual variability in emissions quite well at high northern latitudes (53-90° N). In contrast, CarbonTracker-CH4 is less successful in the tropics where there are few observations and therefore misses significant variability and is more influenced by prior flux estimates. CarbonTracker-CH4 estimates of total fluxes at high northern latitudes are about 81 ± 7 Tg CH4 yr-1 , about 12 Tg CH4 yr-1 (13%) lower than prior estimates, a result that is consistent with other atmospheric inversions. Emissions from European wetlands are decreased by 30%, a result consistent with previous work by Bergamaschi et al. (2005); however, unlike their results, emissions from wetlands in boreal Eurasia are increased relative to the prior estimate. Although CarbonTracker-CH4 does not estimate an increasing trend in emissions from high northern latitudes for 2000 through 2010, significant inter-annual variability in high northern latitude fluxes is recovered. Exceptionally warm growing season temperatures in the Arctic occurred in 2007, a year that was also anonymously wet. Estimated emissions from natural sources were greater than the decadal average by 4.4 ± 3.8 Tg CH4 yr-1 in 2007. CarbonTracker-CH4 estimates for temperate latitudes are only slightly increased over prior estimates, but about 10 Tg CH4 yr-1 is redistributed from Asia to North America. This difference exceeds the estimated uncertainty for North America (±3.5 Tg CH4 yr-1 ). We used time invariant prior flux estimates, so for the period from 2000 to 2006, when the growth rate of global atmospheric CH4 was very small, the assimilation does not produce increases in natural or anthropogenic emissions in contrast to bottom-up emission data sets. After 2006, when atmospheric CH4 began its recent increases, CarbonTracker-CH4 allocates some of the increases to anthropogenic emissions at temperate latitudes, and some to tropical wetland emissions. For temperate North America the prior flux increases by about 4 Tg CH4 yr-1 during winter when biogenic emissions are small. Examination of the residuals at some North American observation sites suggests that increased gas and oil exploration may play a role since sites near fossil fuel production are particularly hard for the inversion to fit and the prior flux estimates at these sites are apparently lower and lower over time than what the atmospheric measurements imply. The tropics are not currently well resolved by CarbonTracker-CH4 due to sparse observational coverage and a short assimilation window. However, there is a small uncertainty reduction and posterior emissions are about 18% higher than prior estimates. Most of this increase is allocated to tropical South America rather than being distributed among the global tropics. Our estimates for this source region are about 32 ± 4 Tg CH4 yr-1 , in good agreement with the analysis of Melack et al. (2004) who obtained 29 Tg CH4 yr-1 for the most productive region, the Amazon Basin.
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.
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.
•Mobile and continuous measurements of stable carbon isotopes in specific CH4 source plumes in Alberta.•CH4 isotopic signatures were accurately derived using an AirCore coupled to a CRDS instrument.•The enriched isotopic values of CH4 from the natural gas industry show thermogenic origin.•The depleted isotopic values of CH4 from the oil industry show microbial origin.•Isotopic signature information will have a profound implication on modelling activities for CH4 emission estimates in Canada.
This paper demonstrates that the secondary hydroxyl can be functionalized in preference to the primary hydroxyl of a 1,2-diol. The site selectivity is achieved by using an enantioselective organic ...catalyst that is able to bond to the diol reversibly and covalently. The reaction has been parlayed into a divergent kinetic resolution on a racemic mixture, providing access to highly enantioenriched secondary-protected 1,2-diols in a single synthetic step.
Ex‐changing places: A highly enantioselective desymmetrization of 1,2‐diols has been developed in which the catalyst utilizes reversible covalent bonding to the substrate to achieve both high ...selectivity and rate acceleration (see scheme, PMP=pentalmethylpiperidine, TBS=tert‐butyldimethylsilyl). Induced intramolecularity is responsible for the enhanced rate, thus allowing the reaction to be performed at room temperature.
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.
The synthesis of β-amino-aldehydes has been achieved through enantioselective hydroformylation of PMP-protected allylic amines. The reaction is accomplished by using a scalemic scaffolding ligand ...that covalently and reversibly binds to the substrate. These ligands behave like chiral auxiliaries because they are covalently attached to the substrate during hydroformylation; however, similar to traditional asymmetric ligands, they can be used in catalytic quantities. The directed hydroformylation of disubstituted olefins occurs under mild conditions (35 °C and 50 psi CO/H2), and Z-olefins afford excellent enantioselectivities (up to 93% ee).
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.
Resolving the discrepancies between NEE estimates based upon (1) ground studies and (2) atmospheric inversion results, demands increasingly sophisticated techniques. In this paper we present a ...high-resolution inversion based upon a regional meteorology model (RAMS) and an underlying biosphere (SiB3) model, both running on an identical 40 km grid over most of North America. Current operational systems like CarbonTracker as well as many previous global inversions including the Transcom suite of inversions have utilized inversion regions formed by collapsing biome-similar grid cells into larger aggregated regions. An extreme example of this might be where corrections to NEE imposed on forested regions on the east coast of the United States might be the same as that imposed on forests on the west coast of the United States while, in reality, there likely exist subtle differences in the two areas, both natural and anthropogenic. Our current inversion framework utilizes a combination of previously employed inversion techniques while allowing carbon flux corrections to be biome independent. Temporally and spatially high-resolution results utilizing biome-independent corrections provide insight into carbon dynamics in North America. In particular, we analyze hourly CO2 mixing ratio data from a sparse network of eight towers in North America for 2004. A prior estimate of carbon fluxes due to Gross Primary Productivity (GPP) and Ecosystem Respiration (ER) is constructed from the SiB3 biosphere model on a 40 km grid. A combination of transport from the RAMS and the Parameterized Chemical Transport Model (PCTM) models is used to forge a connection between upwind biosphere fluxes and downwind observed CO2 mixing ratio data. A Kalman filter procedure is used to estimate weekly corrections to biosphere fluxes based upon observed CO2. RMSE-weighted annual NEE estimates, over an ensemble of potential inversion parameter sets, show a mean estimate 0.57 Pg/yr sink in North America. We perform the inversion with two independently derived boundary inflow conditions and calculate jackknife-based statistics to test the robustness of the model results. We then compare final results to estimates obtained from the CarbonTracker inversion system and at the Southern Great Plains flux site. Results are promising, showing the ability to correct carbon fluxes from the biosphere models over annual and seasonal time scales, as well as over the different GPP and ER components. Additionally, the correlation of an estimated sink of carbon in the South Central United States with regional anomalously high precipitation in an area of managed agricultural and forest lands provides interesting hypotheses for future work.
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