COS-derived GPP relationships with temperature and light help explain high-latitude atmospheric CO2 seasonal cycle amplification.

In the Arctic and Boreal region (ABR) where warming is especially pronounced, the increase of gross primary production (GPP) has been suggested as an important driver for the increase of the atmospheric CO2 seasonal cycle amplitude (SCA). However, the role of GPP relative to changes in ecosystem respiration (ER) remains unclear, largely due to our inability to quantify these gross fluxes on regional scales. Here, we use atmospheric carbonyl sulfide (COS) measurements to provide observation-based estimates of GPP over the North American ABR. Our annual GPP estimate is 3.6 (2.4 to 5.5) PgC · y-1 between 2009 and 2013, the uncertainty of which is smaller than the range of GPP estimated from terrestrial ecosystem models (1.5 to 9.8 PgC · y-1). Our COS-derived monthly GPP shows significant correlations in space and time with satellite-based GPP proxies, solar-induced chlorophyll fluorescence, and near-infrared reflectance of vegetation. Furthermore, the derived monthly GPP displays two different linear relationships with soil temperature in spring versus autumn, whereas the relationship between monthly ER and soil temperature is best described by a single quadratic relationship throughout the year. In spring to midsummer, when GPP is most strongly correlated with soil temperature, our results suggest the warming-induced increases of GPP likely exceeded the increases of ER over the past four decades. In autumn, however, increases of ER were likely greater than GPP due to light limitations on GPP, thereby enhancing autumn net carbon emissions. Both effects have likely contributed to the atmospheric CO2 SCA amplification observed in the ABR.

Siberian and temperate ecosystems shape Northern Hemisphere atmospheric CO2 seasonal amplification.

The amplitude of the atmospheric CO2 seasonal cycle has increased by 30 to 50% in the Northern Hemisphere (NH) since the 1960s, suggesting widespread ecological changes in the northern extratropics. However, substantial uncertainty remains in the continental and regional drivers of this prominent amplitude increase. Here we present a quantitative regional attribution of CO2 seasonal amplification over the past 4 decades, using a tagged atmospheric transport model prescribed with observationally constrained fluxes. We find that seasonal flux changes in Siberian and temperate ecosystems together shape the observed amplitude increases in the NH. At the surface of northern high latitudes, enhanced seasonal carbon exchange in Siberia is the dominant contributor (followed by temperate ecosystems). Arctic-boreal North America shows much smaller changes in flux seasonality and has only localized impacts. These continental contrasts, based on an atmospheric approach, corroborate heterogeneous vegetation greening and browning trends from field and remote-sensing observations, providing independent evidence for regionally divergent ecological responses and carbon dynamics to global change drivers. Over surface midlatitudes and throughout the midtroposphere, increased seasonal carbon exchange in temperate ecosystems is the dominant contributor to CO2 amplification, albeit with considerable contributions from Siberia. Representing the mechanisms that control the high-latitude asymmetry in flux amplification found in this study should be an important goal for mechanistic land surface models moving forward.

Estimating US fossil fuel CO2 emissions from measurements of 14C in atmospheric CO2.

We report national scale estimates of CO2 emissions from fossil-fuel combustion and cement production in the United States based directly on atmospheric observations, using a dual-tracer inverse modeling framework and CO2 and [Formula: see text] measurements obtained primarily from the North American portion of the National Oceanic and Atmospheric Administration's Global Greenhouse Gas Reference Network. The derived US national total for 2010 is 1,653 ± 30 TgC yr-1 with an uncertainty ([Formula: see text]) that takes into account random errors associated with atmospheric transport, atmospheric measurements, and specified prior CO2 and 14C fluxes. The atmosphere-derived estimate is significantly larger ([Formula: see text]) than US national emissions for 2010 from three global inventories widely used for CO2 accounting, even after adjustments for emissions that might be sensed by the atmospheric network, but which are not included in inventory totals. It is also larger ([Formula: see text]) than a similarly adjusted total from the US Environmental Protection Agency (EPA), but overlaps EPA's reported upper 95% confidence limit. In contrast, the atmosphere-derived estimate is within [Formula: see text] of the adjusted 2010 annual total and nine of 12 adjusted monthly totals aggregated from the latest version of the high-resolution, US-specific "Vulcan" emission data product. Derived emissions appear to be robust to a range of assumed prior emissions and other parameters of the inversion framework. While we cannot rule out a possible bias from assumed prior Net Ecosystem Exchange over North America, we show that this can be overcome with additional [Formula: see text] measurements. These results indicate the strong potential for quantification of US emissions and their multiyear trends from atmospheric observations.

Hydrocarbon Tracers Suggest Methane Emissions from Fossil Sources Occur Predominately Before Gas Processing and That Petroleum Plays Are a Significant Source.

We use global airborne observations of propane (C3H8) and ethane (C2H6) from the Atmospheric Tomography (ATom) and HIAPER Pole-to-Pole Observations (HIPPO), as well as U.S.-based aircraft and tower observations by NOAA and from the NCAR FRAPPE campaign as tracers for emissions from oil and gas operations. To simulate global mole fraction fields for these gases, we update the default emissions' configuration of C3H8 used by the global chemical transport model, GEOS-Chem v13.0.0, using a scaled C2H6 spatial proxy. With the updated emissions, simulations of both C3H8 and C2H6 using GEOS-Chem are in reasonable agreement with ATom and HIPPO observations, though the updated emission fields underestimate C3H8 accumulation in the arctic wintertime, pointing to additional sources of this gas in the high latitudes (e.g., Europe). Using a Bayesian hierarchical model, we estimate global emissions of C2H6 and C3H8 from fossil fuel production in 2016-2018 to be 13.3 ± 0.7 (95% CI) and 14.7 ± 0.8 (95% CI) Tg/year, respectively. We calculate bottom-up hydrocarbon emission ratios using basin composition measurements weighted by gas production and find their magnitude is higher than expected and is similar to ratios informed by our revised alkane emissions. This suggests that emissions are dominated by pre-processing activities in oil-producing basins.

Upward revision of global fossil fuel methane emissions based on isotope database.

Methane has the second-largest global radiative forcing impact of anthropogenic greenhouse gases after carbon dioxide, but our understanding of the global atmospheric methane budget is incomplete. The global fossil fuel industry (production and usage of natural gas, oil and coal) is thought to contribute 15 to 22 per cent of methane emissions to the total atmospheric methane budget. However, questions remain regarding methane emission trends as a result of fossil fuel industrial activity and the contribution to total methane emissions of sources from the fossil fuel industry and from natural geological seepage, which are often co-located. Here we re-evaluate the global methane budget and the contribution of the fossil fuel industry to methane emissions based on long-term global methane and methane carbon isotope records. We compile the largest isotopic methane source signature database so far, including fossil fuel, microbial and biomass-burning methane emission sources. We find that total fossil fuel methane emissions (fossil fuel industry plus natural geological seepage) are not increasing over time, but are 60 to 110 per cent greater than current estimates owing to large revisions in isotope source signatures. We show that this is consistent with the observed global latitudinal methane gradient. After accounting for natural geological methane seepage, we find that methane emissions from natural gas, oil and coal production and their usage are 20 to 60 per cent greater than inventories. Our findings imply a greater potential for the fossil fuel industry to mitigate anthropogenic climate forcing, but we also find that methane emissions from natural gas as a fraction of production have declined from approximately 8 per cent to approximately 2 per cent over the past three decades.

Carbon dioxide sources from Alaska driven by increasing early winter respiration from Arctic tundra.

High-latitude ecosystems have the capacity to release large amounts of carbon dioxide (CO2) to the atmosphere in response to increasing temperatures, representing a potentially significant positive feedback within the climate system. Here, we combine aircraft and tower observations of atmospheric CO2 with remote sensing data and meteorological products to derive temporally and spatially resolved year-round CO2 fluxes across Alaska during 2012-2014. We find that tundra ecosystems were a net source of CO2 to the atmosphere annually, with especially high rates of respiration during early winter (October through December). Long-term records at Barrow, AK, suggest that CO2 emission rates from North Slope tundra have increased during the October through December period by 73% ± 11% since 1975, and are correlated with rising summer temperatures. Together, these results imply increasing early winter respiration and net annual emission of CO2 in Alaska, in response to climate warming. Our results provide evidence that the decadal-scale increase in the amplitude of the CO2 seasonal cycle may be linked with increasing biogenic emissions in the Arctic, following the growing season. Early winter respiration was not well simulated by the Earth System Models used to forecast future carbon fluxes in recent climate assessments. Therefore, these assessments may underestimate the carbon release from Arctic soils in response to a warming climate.

Continued emissions of carbon tetrachloride from the United States nearly two decades after its phaseout for dispersive uses.

National-scale emissions of carbon tetrachloride (CCl4) are derived based on inverse modeling of atmospheric observations at multiple sites across the United States from the National Oceanic and Atmospheric Administration's flask air sampling network. We estimate an annual average US emission of 4.0 (2.0-6.5) Gg CCl4 y(-1) during 2008-2012, which is almost two orders of magnitude larger than reported to the US Environmental Protection Agency (EPA) Toxics Release Inventory (TRI) (mean of 0.06 Gg y(-1)) but only 8% (3-22%) of global CCl4 emissions during these years. Emissive regions identified by the observations and consistently shown in all inversion results include the Gulf Coast states, the San Francisco Bay Area in California, and the Denver area in Colorado. Both the observation-derived emissions and the US EPA TRI identified Texas and Louisiana as the largest contributors, accounting for one- to two-thirds of the US national total CCl4 emission during 2008-2012. These results are qualitatively consistent with multiple aircraft and ship surveys conducted in earlier years, which suggested significant enhancements in atmospheric mole fractions measured near Houston and surrounding areas. Furthermore, the emission distribution derived for CCl4 throughout the United States is more consistent with the distribution of industrial activities included in the TRI than with the distribution of other potential CCl4 sources such as uncapped landfills or activities related to population density (e.g., use of chlorine-containing bleach).

Tropical nighttime warming as a dominant driver of variability in the terrestrial carbon sink.

The terrestrial biosphere is currently a strong carbon (C) sink but may switch to a source in the 21st century as climate-driven losses exceed CO2-driven C gains, thereby accelerating global warming. Although it has long been recognized that tropical climate plays a critical role in regulating interannual climate variability, the causal link between changes in temperature and precipitation and terrestrial processes remains uncertain. Here, we combine atmospheric mass balance, remote sensing-modeled datasets of vegetation C uptake, and climate datasets to characterize the temporal variability of the terrestrial C sink and determine the dominant climate drivers of this variability. We show that the interannual variability of global land C sink has grown by 50-100% over the past 50 y. We further find that interannual land C sink variability is most strongly linked to tropical nighttime warming, likely through respiration. This apparent sensitivity of respiration to nighttime temperatures, which are projected to increase faster than global average temperatures, suggests that C stored in tropical forests may be vulnerable to future warming.

Improved Mechanistic Understanding of Natural Gas Methane Emissions from Spatially Resolved Aircraft Measurements.

Divergence in recent oil and gas related methane emission estimates between aircraft studies (basin total for a midday window) and emissions inventories (annualized regional and national statistics) indicate the need for better understanding the experimental design, including temporal and spatial alignment and interpretation of results. Our aircraft-based methane emission estimates in a major U.S. shale gas basin resolved from west to east show (i) similar spatial distributions for 2 days, (ii) strong spatial correlations with reported NG production (R2 = 0.75) and active gas well pad count (R2 = 0.81), and (iii) 2× higher emissions in the western half (normalized by gas production) despite relatively homogeneous dry gas and well characteristics. Operator reported hourly activity data show that midday episodic emissions from manual liquid unloadings (a routine operation in this basin and elsewhere) could explain ∼1/3 of the total emissions detected midday by the aircraft and ∼2/3 of the west-east difference in emissions. The 22% emission difference between both days further emphasizes that episodic sources can substantially impact midday methane emissions and that aircraft may detect daily peak emissions rather than daily averages that are generally employed in emissions inventories. While the aircraft approach is valid, quantitative, and independent, our study sheds new light on the interpretation of previous basin scale aircraft studies, and provides an improved mechanistic understanding of oil and gas related methane emissions.

Development of a Northern Continental Air Standard Reference Material.

The National Institute of Standards and Technology (NIST) recently began to develop standard mixtures of greenhouse gases as part of a broad program mandated by the 2009 United States Congress to support research in climate change. To this end, NIST developed suites of gravimetrically assigned primary standard mixtures (PSMs) comprising carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) in a dry-natural air balance at ambient mole fraction levels. In parallel, the National Oceanic and Atmospheric Administration (NOAA) in Boulder, Colorado, charged 30 aluminum gas cylinders with northern hemisphere air at Niwot Ridge, Colorado. These mixtures, which constitute NIST Standard Reference Material (SRM) 1720 Northern Continental Air, were certified by NIST for ambient mole fractions of CO2, CH4, and N2O relative to NIST PSMs. NOAA-assigned values are also provided as information in support of the World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) Program for CO2, CH4, and N2O, since NOAA serves as the WMO Central Calibration Laboratory (CCL) for CO2, CH4, and N2O. Relative expanded uncertainties at the 95% confidence interval are <±0.06% of the certified values for CO2 and N2O and <0.2% for CH4, which represents the smallest relative uncertainties specified to date for a gaseous SRM produced by NIST. Agreement between the NOAA (WMO/GAW) and NIST values based on their respective calibration standards suites is within 0.05%, 0.13%, and 0.06% for CO2, CH4, and N2O, respectively. This collaborative development effort also represents the first of its kind for a gaseous SRM developed by NIST.

Aircraft-Based Estimate of Total Methane Emissions from the Barnett Shale Region.

We present estimates of regional methane (CH4) emissions from oil and natural gas operations in the Barnett Shale, Texas, using airborne atmospheric measurements. Using a mass balance approach on eight different flight days in March and October 2013, the total CH4 emissions for the region are estimated to be 76 ± 13 × 10(3) kg hr(-1) (equivalent to 0.66 ± 0.11 Tg CH4 yr(-1); 95% confidence interval (CI)). We estimate that 60 ± 11 × 10(3) kg CH4 hr(-1) (95% CI) are emitted by natural gas and oil operations, including production, processing, and distribution in the urban areas of Dallas and Fort Worth. This estimate agrees with the U.S. Environmental Protection Agency (EPA) estimate for nationwide CH4 emissions from the natural gas sector when scaled by natural gas production, but it is higher than emissions reported by the EDGAR inventory or by industry to EPA's Greenhouse Gas Reporting Program. This study is the first to show consistency between mass balance results on so many different days and in two different seasons, enabling better quantification of the related uncertainty. The Barnett is one of the largest production basins in the United States, with 8% of total U.S. natural gas production, and thus, our results represent a crucial step toward determining the greenhouse gas footprint of U.S. onshore natural gas production.

Regional US carbon sinks from three-dimensional atmospheric CO2 sampling.

Studies diverge substantially on the actual magnitude of the North American carbon budget. This is due to the lack of appropriate data and also stems from the difficulty to properly model all the details of the flux distribution and transport inside the region of interest. To sidestep these difficulties, we use here a simple budgeting approach to estimate land-atmosphere fluxes across North America by balancing the inflow and outflow of CO(2) from the troposphere. We base our study on the unique sampling strategy of atmospheric CO(2) vertical profiles over North America from the National Oceanic and Atmospheric Administration/Earth System Research Laboratory aircraft network, from which we infer the three-dimensional CO(2) distribution over the continent. We find a moderate sink of 0.5 ± 0.4 PgC y(-1) for the period 2004-2006 for the coterminous United States, in good agreement with the forest-inventory-based estimate of the first North American State of the Carbon Cycle Report, and averaged climate conditions. We find that the highest uptake occurs in the Midwest and in the Southeast. This partitioning agrees with independent estimates of crop uptake in the Midwest, which proves to be a significant part of the US atmospheric sink, and of secondary forest regrowth in the Southeast. Provided that vertical profile measurements are continued, our study offers an independent means to link regional carbon uptake to climate drivers.

Microcollection of gases in a capillary tube: preservation of spatial and temporal resolution.

Researchers at the National Oceanic and Atmospheric Administration (NOAA) have recently developed and reported a novel air collection device for measuring vertical profiles of trace gases in the atmosphere, which has been applied to carbon dioxide and methane so far. The device consists of a long stainless steel tube that is prefilled with calibrated gas and allowed to ascend on a weather balloon. During ascent, the device is evacuated as it equilibrates with the decreasing atmospheric pressure. During descent, the tube is filled with atmospheric gas in an ordered manner. The diffusion rate inside the tube is slow enough that the collected gas remains ordered. Here is reported a miniaturization of the device described above, in which the stainless steel tube is replaced with Hydroguard fused silica tubing (0.53 mm × 30 m) and two lightweight valves having a total mass of less than 28 g. This micro-AirCore device was deployed on the SwRI-developed unmanned SkyWisp glider. Profiling of carbon dioxide in the atmosphere proceeded via mass spectrometric detection. A laboratory-based validation system was used for evaluating the micro-AirCore function, including accuracy and precision, for carbon dioxide. The diffusion profiles of carbon dioxide, argon, oxygen, and methane were also investigated. Overall, the micro-AirCore demonstrated an accuracy error of 2% ((12)CO(2)) and minimal diffusion over a period of 16 h (peak width increased by a factor of 1.6). Even after 63 h, mixing of the gases inside the tube was not complete. A triplet of micro-AirCores was deployed on the SkyWisp glider yielding a relative standard deviation of 0.08%, or 0.3 ppm, for CO(2). The profile collected resulted in observation of the boundary layer with elevated CO(2) levels, a region in the free troposphere with relatively constant CO(2) mole fraction, and a gradual decrease in CO(2) above 10,000 m. This microdevice has broad applications extending beyond vertical profiling. Fitting the device with a metering device could enable horizontal collection of gases.

Strong Southern Ocean carbon uptake evident in airborne observations.

The Southern Ocean plays an important role in determining atmospheric carbon dioxide (CO2), yet estimates of air-sea CO2 flux for the region diverge widely. In this study, we constrained Southern Ocean air-sea CO2 exchange by relating fluxes to horizontal and vertical CO2 gradients in atmospheric transport models and applying atmospheric observations of these gradients to estimate fluxes. Aircraft-based measurements of the vertical atmospheric CO2 gradient provide robust flux constraints. We found an annual mean flux of ­0.53 ± 0.23 petagrams of carbon per year (net uptake) south of 45°S during the period 2009­2018. This is consistent with the mean of atmospheric inversion estimates and surface-ocean partial pressure of CO2 (Pco2)­based products, but our data indicate stronger annual mean uptake than suggested by recent interpretations of profiling float observations.

An atmospheric perspective on North American carbon dioxide exchange: CarbonTracker.

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.

Estimating the short-time rate of change in the trend of the Keeling curve.

What exactly is the short-time rate of change (growth rate) in the trend of [Formula: see text] data such as the Keeling curve? The answer to this question will obviously depend very much on the duration in time over which the trend has been defined, as well as the smoothing technique that has been used. As an estimate of the short-time rate of change we propose to employ a very simple and robust definition of the trend based on a centered 1-year sliding data window for averaging and a corresponding centered 1-year difference (2-year data window) to estimate its rate of change. In this paper, we show that this simple strategy applied to weekly data of the Keeling curve (1974-2020) gives an estimated rate of change which is perfectly consistent with a more sophisticated regression analysis technique based on Taylor and Fourier series expansions. From a statistical analysis of the regression model and by using the Cramér-Rao lower bound, it is demonstrated that the relative error in the estimated rate of change is less than 5 [Formula: see text]. As an illustration, the estimates are finally compared to some other publicly available data regarding anthropogenic [Formula: see text] emissions and natural phenomena such as the El Niño.

Enhanced North American carbon uptake associated with El Niño.

Long-term atmospheric CO2 mole fraction and δ13CO2 observations over North America document persistent responses to the El Niño-Southern Oscillation. We estimate these responses corresponded to 0.61 (0.45 to 0.79) PgC year-1 more North American carbon uptake during El Niño than during La Niña between 2007 and 2015, partially offsetting increases of net tropical biosphere-to-atmosphere carbon flux around El Niño. Anomalies in derived North American net ecosystem exchange (NEE) display strong but opposite correlations with surface air temperature between seasons, while their correlation with water availability was more constant throughout the year, such that water availability is the dominant control on annual NEE variability over North America. These results suggest that increased water availability and favorable temperature conditions (warmer spring and cooler summer) caused enhanced carbon uptake over North America near and during El Niño.

Sampling, storage, and analysis of C2-C7 non-methane hydrocarbons from the US National Oceanic and Atmospheric Administration Cooperative Air Sampling Network glass flasks.

An analytical technique was developed to analyze light non-methane hydrocarbons (NMHC), including ethane, propane, iso-butane, n-butane, iso-pentane, n-pentane, n-hexane, isoprene, benzene and toluene from whole air samples collected in 2.5l-glass flasks used by the National Oceanic and Atmospheric Administration, Earth System Research Laboratory, Global Monitoring Division (NOAA ESRL GMD, Boulder, CO, USA) Cooperative Air Sampling Network. This method relies on utilizing the remaining air in these flasks (which is at below-ambient pressure at this stage) after the completion of all routine greenhouse gas measurements from these samples. NMHC in sample aliquots extracted from the flasks were preconcentrated with a custom-made, cryogen-free inlet system and analyzed by gas chromatography (GC) with flame ionization detection (FID). C2-C7 NMHC, depending on their ambient air mixing ratios, could be measured with accuracy and repeatability errors of generally < or =10-20%. Larger deviations were found for ethene and propene. Hexane was systematically overestimated due to a chromatographic co-elution problem. Saturated NMHC showed less than 5% changes in their mixing ratios in glass flask samples that were stored for up to 1 year. In the same experiment ethene and propene increased at approximately 30% yr(-1). A series of blank experiments showed negligible contamination from the sampling process and from storage (<10 pptv yr(-1)) of samples in these glass flasks. Results from flask NMHC analyses were compared to in-situ NMHC measurements at the Global Atmospheric Watch station in Hohenpeissenberg, Germany. This 9-months side-by-side comparison showed good agreement between both methods. More than 94% of all data comparisons for C2-C5 alkanes, isoprene, benzene and toluene fell within the combined accuracy and precision objectives of the World Meteorological Organization Global Atmosphere Watch (WMO-GAW) for NMHC measurements.

Potential improvements aimed at high precision δ13C isotopic ratio determinations in CO2 mixtures using optical absorption spectrometry.

The manuscript explores some advantages and limitations of laser based optical spectroscopy, aimed at achieving robust, high-reproducibility 13C16O2 and 12C16O2 ratio determinations on the VPDB-CO2 δ13C scale by measuring the absorbance of line pairs of 13C16O2 and 12C16O2. In particular, the sensitivities of spectroscopic lines to both pressure (P) and temperature (T) are discussed. Based on the considerations and estimations presented, a level of reproducibility of the 13C16O2/12C16O2 ratio determinations may be achieved of about 10-6. Thus one may establish an optical spectroscopic measurement technique for robust, high-precision 13C16O2 and 12C16O2 ratio measurements aimed at very low uncertainty. (Notably, creating such an optical instrument and developing technical solutions is beyond the scope of this paper.) The total combined uncertainty will also include the uncertainty component(s) related to the accuracy of calibration on the VPDB-CO2 δ13C scale. Addressing high-accuracy calibrations is presently not straightforward - absolute numerical values of 13C/12C for the VPDB-CO2 scale are not well known. Traditional stable isotope mass-spectrometry uses calibrations vs CO2 evolved from the primary carbonate reference materials; which can hardly be used for calibrating commercial optical stable isotope analysers. In contrast to mass-spectrometry, the major advantage of the laser-based spectrometric technique detailed in this paper is its high robustness. Therefore one can introduce a new spectrometric δ13C characterisation method which, being once well-calibrated on the VPDB-CO2 scale, may not require any further (re-)calibrations. This can be used for characterisation of δ13C in CO2-in-air mixtures with high precision and also with high accuracy. If this technique can be realised with the estimated long-term reproducibility (order of 10-6), it could potentially serve as a more convenient Optical Transfer Standard (OTS), characterising large amounts of CO2 gas mixtures on the VPDB-CO2 δ13C scale without having to compare to carbonate-evolved CO2. Furthermore, if the OTS method proves to be successful, it might be considered for re-defining the VPDB-CO2 δ13C-scale as the ratio of selected CO2 spectroscopic absorbance lines measured at pre-defined T & P conditions. The approach can also be expanded to δ18O characterisation (using 16O12C18O and 16O12C16O absorbance lines) of CO2 gas mixtures and potentially to other isotope ratios of other gases.