ALBERT

Description: Because fossil fuel derived CO2 is the only source of atmospheric CO2 that is devoid of 14C, atmospheric measurements of Δ14CO2 can be used to constrain fossil fuel emissions at local and regional scales. However, at the continental scale, atmospheric transport and other sources of variability in Δ14CO2 may influence the fossil fuel detection capability. We present a set of Δ14CO2 observations from the train-based TROICA-8 expedition across Eurasia in March–April 2004. Local perturbations in Δ14CO2 are caused by easily identifiable sources from nuclear reactors and localized pollution events. The remaining data show an increase in Δ14CO2 from Western Russia (40° E) to Eastern Siberia (120° E), consistent with depletion in 14CO2 caused by fossil fuel CO2 emissions in heavily populated Europe, and gradual dispersion of the fossil fuel plume across Northern Asia. Other tracer gas species which may be correlated with fossil fuel CO2 emissions, including carbon monoxide, sulphur hexafluoride, and perchloroethylene, were also measured and the results compared with the Δ14CO2 measurements. The sulphur hexafluoride longitudinal gradient is not significant relative to the measurement uncertainty. Carbon monoxide and perchloroethylene show large-scale trends of enriched values in Western Russia and decreasing values in Eastern Siberia, consistent with fossil fuel emissions, but exhibit significant spatial variability, especially near their primary sources in Western Russia. The clean air Δ14CO2 observations are compared with simulated spatial gradients from the TM5 atmospheric transport model. We show that the change in Δ14CO2 across the TROICA transect is due almost entirely to emissions of fossil fuel CO2, but that the magnitude of this Δ14CO2 gradient is relatively insensitive to modest uncertainties in the fossil fuel flux. In contrast, the Δ14CO2 gradient is strongly sensitive to the modeled representation of vertical mixing, suggesting that Δ14CO2 may be a useful tracer for training mixing in atmospheric transport models.

Description: Tunable diode laser absorption spectrometry (TDLAS) is gaining in popularity for measuring the mole fraction [CO2] and stable isotopic composition (δ13C) of carbon dioxide (CO2) in air in studies of biosphere-atmosphere gas exchange. Here we present a detailed examination of the performance of a commercially-available TDLAS located in a high-altitude subalpine coniferous forest (the Niwot Ridge AmeriFlux site), providing the first multi-year analysis of TDLAS instrument performance for measuring CO2 isotopes in the field. Air was sampled from five to nine vertical locations in and above the forest canopy every ten minutes for 2.4 years. A variety of methods were used to assess instrument performance. Measurement of two compressed air cylinders that were in place over the entire study establish the long-term field precision of 0.2 μmol mol−1 for [CO2] and 0.35‰ for δ13C, but after fixing several problems the isotope precision improved to 0.2‰ (over the last several months). The TDLAS provided detail on variability of δ13C of atmospheric CO2 that was not represented in weekly flask samples, as well as information regarding the influence of large-scale (regional) seasonal cycle and local forest processes on [CO2] and δ13C of CO2. There were also clear growing season and winter differences in the relative contributions of photosynthesis and respiration on the [CO2] and δ13C of forest air.

Description: Particle size distribution from biomass combustion is an important parameter as it affects air quality, climate modelling and health effects. To date, particle size distributions reported from prior studies vary not only due to difference in fuels but also difference in experimental conditions. This study aims to report characteristics of particle size distributions in well controlled repeatable lab scale biomass fires for southwestern United States fuels with focus on chaparral. The combustion laboratory at the United States Department of Agriculture-Forest Service's Fire Science Laboratory (USDA-FSL), Missoula, MT provided a repeatable combustion and dilution environment ideal for measurements. For a variety of fuels tested the major mode of particle size distribution was in the range of 29 to 52 nm, which is attributable to dilution of the fresh smoke. Comparing mass size distribution from FMPS and APS measurement 51–68% of particle mass was attributable to the particles ranging from 0.5 to 10 μm for PM10. Geometric mean diameter rapidly increased during flaming and gradually decreased during mixed and smoldering phase combustion. Most fuels produced a unimodal distribution during flaming phase and strong biomodal distribution during smoldering phase. The mode of combustion (flaming, mixed and smoldering) could be better distinguished using the slopes in MCE (Modified Combustion Efficiency) vs. geometric mean diameter than only using MCE values.

Description: Atmospheric radiocarbon (14C) represents an important observational constraint on emissions of fossil-fuel derived carbon into the atmosphere due to the absence of 14C in fossil fuel reservoirs. The high sensitivity and precision that accelerator mass spectrometry (AMS) affords in atmospheric 14C analysis has greatly increased the potential for using such measurements to evaluate bottom-up emissions inventories of fossil fuel CO2 (CO2ff), as well as those for other co-emitted species. Here we use observations of 14CO2 and a series of primary hydrocarbons and combustion tracers from discrete air samples collected between June 2009 and September 2010 at the National Oceanic and Atmospheric Administration Boulder Atmospheric Observatory (BAO; Lat: 40.050° N, Lon: 105.004° W) to derive emission ratios of each species with respect to CO2ff. The BAO tower is situated at the boundary of the Denver metropolitan area to the south and a large industrial and agricultural region to the north and east, making it an ideal location to study the contrasting mix of emissions from the activities in each region. The species considered in this analysis are carbon monoxide (CO), methane (CH4), acetylene (C2H2), benzene (C6H6), and C3–C5 alkanes. We estimate emissions for a subset of these species by using the Vulcan high resolution CO2ff emission data product as a reference. We find that CO is overestimated in the 2008 National Emissions Inventory (NEI08) by a factor of ~2. A close evaluation of the inventory suggests that the ratio of CO emitted per unit fuel burned from on-road gasoline vehicles is likely over-estimated by a factor of 2.5. Using a wind-directional analysis of the data, we find enhanced concentrations of CH4, relative to CO2ff, in air influenced by emissions to the north and east of the BAO tower when compared to air influenced by emissions in the Denver metro region to the south. Along with enhanced CH4, the strongest enhancements of the C3–C5 alkanes are also found in the north and east wind sector, suggesting that both the alkane and CH4 enhancements are sourced from oil and gas fields located to the northeast, though it was not possible to rule out the contribution of non oil and gas CH4 sources.

Description: 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.

Description: Because fossil fuel derived CO2 is the only source of atmospheric CO2 that is devoid of 14C, atmospheric measurements of Δ14CO2 can be used to constrain fossil fuel emission estimates at local and regional scales. However, at the continental scale, uncertainties in atmospheric transport and other sources of variability in Δ14CO2 may influence the fossil fuel detection capability. We present a set of Δ14CO2 observations from the train-based TROICA-8 expedition across Eurasia in March–April 2004. Local perturbations in Δ14CO2 are caused by easily identifiable sources from nuclear reactors and localized pollution events. The remaining data show an increase in Δ14CO2 from Western Russia (40° E) to Eastern Siberia (120° E), consistent with depletion in 14CO2 caused by fossil fuel CO2 emissions in heavily populated Europe, and gradual dispersion of the fossil fuel plume across Northern Asia. Other trace gas species which may be correlated with fossil fuel CO2 emissions, including carbon monoxide, sulphur hexafluoride, and perchloroethylene, were also measured and the results compared with the Δ14CO2 measurements. The sulphur hexafluoride longitudinal gradient is not significant relative to the measurement uncertainty. Carbon monoxide and perchloroethylene show large-scale trends of enriched values in Western Russia and decreasing values in Eastern Siberia, consistent with fossil fuel emissions, but exhibit significant spatial variability, especially near their primary sources in Western Russia. The clean air Δ14CO2 observations are compared with simulated spatial gradients from the TM5 atmospheric transport model. We show that the change in Δ14CO2 across the TROICA transect is due almost entirely to emissions of fossil fuel CO2, but that the magnitude of this Δ14CO2 gradient is relatively insensitive to modest uncertainties in the fossil fuel flux. In contrast, the Δ14CO2 gradient is more sensitive to the modeled representation of vertical mixing, suggesting that Δ14CO2 may be a useful tracer for training mixing in atmospheric transport models.

Description: Direct quantification of fossil fuel CO2 (CO2ff) in atmospheric samples can be used to examine several carbon cycle and air quality questions. We collected in situ CO2, CO, and CH4 measurements and flask samples in the boundary layer and free troposphere over Sacramento, California, USA, during two aircraft flights over and downwind of this urban area during spring of 2009. The flask samples were analyzed for Δ14CO2 and CO2 to determine the recently added CO2ff mole fraction. A suite of greenhouse and other trace gases, including hydrocarbons and halocarbons, were measured in the same samples. Strong correlations were observed between CO2ff and numerous trace gases associated with urban emissions. From these correlations we estimate emission ratios between CO2ff and these species, and compare these with bottom-up inventory-derived estimates. Recent county level inventory estimates for carbon monoxide (CO) and benzene from the California Air Resources Board CEPAM database are in good agreement with our measured emission ratios, whereas older emissions inventories appear to overestimate emissions of these gases by a factor of two. For most other trace species, there are substantial differences (200–500%) between our measured emission ratios and those derived from available emission inventories. For the first flight, we combine in situ CO measurements with the measured CO:CO2ff emission ratio of 14 ± 2 ppbCO/ppmCO2 to derive an estimate of CO2ff mole fraction throughout this flight, and also estimate the biospheric CO2 mixing ratio (CO2bio) from the difference of total and fossil CO2. The resulting CO2bio varies dramatically from up to 8 ± 2 ppm in the urban plume to −6 ± 1 ppm in the surrounding boundary layer air. Finally, we use the in situ estimates of CO2ff mole fraction to infer total fossil fuel CO2 emissions from the Sacramento region, using a mass balance approach. The resulting emissions are uncertain to within a factor of two due to uncertainties in wind speed and boundary layer height. Nevertheless, this first attempt to estimate urban-scale CO2ff from atmospheric radiocarbon measurements shows that CO2ff can be used to verify and improve emission inventories for many poorly known anthropogenic species, separate biospheric CO2, and indicates the potential to constrain CO2ff emissions if transport uncertainties are reduced.

Description: Over the last 5 decades monitoring systems have been developed to detect changes in the accumulation of C in the atmosphere, ocean, and land; however, our ability to detect changes in the behavior of the global C cycle is still hindered by measurement and estimate errors. Here we present a rigorous and flexible framework for assessing the temporal and spatial components of estimate error and their impact on uncertainty in net C uptake by the biosphere. We present a novel approach for incorporating temporally correlated random error into the error structure of emission estimates. Based on this approach, we conclude that the 2 σ error of the atmospheric growth rate has decreased from 1.2 Pg C yr−1 in the 1960s to 0.3 Pg C yr−1 in the 2000s, leading to a ~20% reduction in the over-all uncertainty of net global C uptake by the biosphere. While fossil fuel emissions have increased by a factor of 4 over the last 5 decades, 2 σ errors in fossil fuel emissions due to national reporting errors and differences in energy reporting practices have increased from 0.3 Pg C yr−1 in the 1960s to almost 1.0 Pg C yr−1 during the 2000s. At the same time land use emissions have declined slightly over the last 5 decades, but their relative errors remain high. Notably, errors associated with fossil fuel emissions have come to dominate uncertainty in the global C budget and are now comparable to the total emissions from land use, thus efforts to reduce errors in fossil fuel emissions are necessary. Given all the major sources of error in the global C budget that we could identify, we are 93% confident that C uptake has increased and 97% confident that C uptake by the terrestrial biosphere has increased over the last 5 decades. Although the persistence of future C sinks remains unknown and some ecosystem services may be compromised by this continued C uptake (e.g. ocean acidification), it is clear that arguably the greatest ecosystem service currently provided by the biosphere is the continued removal of approximately half of atmospheric CO2 emissions from the atmosphere.

Description: Recent studies have demonstrated direct methane emission from plant foliage under aerobic conditions, particularly under high ultraviolet (UV) irradiance. We examined the potential importance of this phenomenon in a high-elevation conifer forest using micrometeorological techniques. Vertical profiles of methane and carbon dioxide in forest air were monitored every 2 h for 6 weeks in summer 2007. Day to day variability in above-canopy CH4 was high, with observed values in the range 1790 to 1910 nmol mol−1. High CH4 was correlated with high carbon monoxide and related to wind direction, consistent with pollutant transport from an urban area by a well-studied mountain-plain wind system. Soils were moderately dry during the study. Vertical gradients of CH4 were small but detectable day and night, both near the ground and within the vegetation canopy. Gradients near the ground were consistent with the forest soil being a net CH4 sink. Using scalar similarity with CO2, the magnitude of the summer soil CH4 sink was estimated at ~1.7 mg CH4 m−2 h−1, which is similar to other temperate forest upland soils. The high-elevation forest was naturally exposed to high UV irradiance under clear sky conditions, with observed peak UVB irradiance 〉2 W m−2. Gradients and means of CO2 within the canopy under daytime conditions showed net uptake of CO2 due to photosynthetic drawdown as expected. No evidence was found for a significant foliar CH4 source in the vegetation canopy, even under high UV conditions. While the possibility of a weak foliar source cannot be excluded given the observed soil sink, overall this subalpine forest was a net sink for atmospheric methane during the growing season.