Atmospheric CO2 and 14CO2 observations at the northern foot of the Qinling Mountains in China: Temporal characteristics and source quantification.

A two-year (March 2021 to February 2023) continuous atmospheric CO2 and a one-year regular atmospheric 14CO2 measurement records were measured at the northern foot of the Qinling Mountains in Xi'an, China, aiming to study the temporal characteristics of atmospheric CO2 and the contributions from the sources of fossil fuel CO2 (CO2ff) and biological CO2 (CO2bio) fluxes. The two-year mean CO2 mole fraction was 442.2 ± 16.3 ppm, with a yearly increase of 4.7 ppm (i.e., 1.1 %) during the two-year observations. Seasonal CO2 mole fractions were the highest in winter (452.1 ± 17.7 ppm) and the lowest in summer (433.5 ± 13.3 ppm), with the monthly CO2 levels peaking in January and troughing in June. Diurnal CO2 levels peaked at dawn (05:00-07:00) in spring, summer and autumn, and at 10:00 in winter. 14C analysis revealed that the excess CO2 (CO2ex, atmospheric CO2 minus background CO2) at this site was mainly from CO2ff emissions (67.0 ± 26.8 %), and CO2ff mole fractions were the highest in winter (20.6 ± 17.7 ppm). Local CO enhancement above the background mole fraction (ΔCO) was significantly (r = 0.74, p < 0.05) positively correlated with CO2ff in a one-year measurement, and ΔCO:CO2ff showed a ratio of 23 ± 6 ppb/ppm during summer and winter sampling days, much lower than previous measurements and suggesting an improvement in combustion efficiency over the last decade. CO2bio mole fractions also peaked in winter (14.2 ± 9.6 ppm), apparently due to biomass combustion and the lower and more stable wintertime atmospheric boundary layer. The negative CO2bio values in summer indicated that terrestrial vegetation of the Qinling Mountains had the potential to uptake atmospheric CO2 during the corresponding sampling days. This site is most sensitive to local emissions from Xi'an and to short distance transportation from the southern Qinling Mountains through the valleys.

Urban flask measurements of CO2ff and CO to identify emission sources at different site types in Auckland, New Zealand.

As part of the CarbonWatch-NZ research programme, air samples were collected at 28 sites around Auckland, New Zealand, to determine the atmospheric ratio (RCO) of excess (local enhancement over background) carbon monoxide to fossil CO2 (CO2ff). Sites were categorized into seven types (background, forest, industrial, suburban, urban, downwind and motorway) to observe RCO around Auckland. Motorway flasks observed RCO of 14 ± 1 ppb ppm-1 and were used to evaluate traffic RCO. The similarity between suburban (14 ± 1 ppb ppm-1) and traffic RCO suggests that traffic dominates suburban CO2ff emissions during daytime hours, the period of flask collection. The lower urban RCO (11 ± 1 ppb ppm-1) suggests that urban CO2ff emissions are comprised of more than just traffic, with contributions from residential, commercial and industrial sources, all with a lower RCO than traffic. Finally, the downwind sites were believed to best represent RCO for Auckland City overall (11 ± 1 ppb ppm-1). We demonstrate that the initial discrepancy between the downwind RCO and Auckland's estimated daytime inventory RCO (15 ppb ppm-1) can be attributed to an overestimation in inventory traffic CO emissions. After revision based on our observed motorway RCO, the revised inventory RCO (12 ppb ppm-1) is consistent with our observations. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

Making the case for an International Decade of Radiocarbon.

Radiocarbon (14C) is a critical tool for understanding the global carbon cycle. During the Anthropocene, two new processes influenced 14C in atmospheric, land and ocean carbon reservoirs. First, 14C-free carbon derived from fossil fuel burning has diluted 14C, at rates that have accelerated with time. Second, 'bomb' 14C produced by atmospheric nuclear weapon tests in the mid-twentieth century provided a global isotope tracer that is used to constrain rates of air-sea gas exchange, carbon turnover, large-scale atmospheric and ocean transport, and other key C cycle processes. As we write, the 14C/12C ratio of atmospheric CO2 is dropping below pre-industrial levels, and the rate of decline in the future will depend on global fossil fuel use and net exchange of bomb 14C between the atmosphere, ocean and land. This milestone coincides with a rapid increase in 14C measurement capacity worldwide. Leveraging future 14C measurements to understand processes and test models requires coordinated international effort-a 'decade of radiocarbon' with multiple goals: (i) filling observational gaps using archives, (ii) building and sustaining observation networks to increase measurement density across carbon reservoirs, (iii) developing databases, synthesis and modelling tools and (iv) establishing metrics for identifying and verifying changes in carbon sources and sinks. This article is part of the Theo Murphy meeting issue 'Radiocarbon in the Anthropocene'.

A multi-city urban atmospheric greenhouse gas measurement data synthesis.

Urban regions emit a large fraction of anthropogenic emissions of greenhouse gases (GHG) such as carbon dioxide (CO2) and methane (CH4) that contribute to modern-day climate change. As such, a growing number of urban policymakers and stakeholders are adopting emission reduction targets and implementing policies to reach those targets. Over the past two decades research teams have established urban GHG monitoring networks to determine how much, where, and why a particular city emits GHGs, and to track changes in emissions over time. Coordination among these efforts has been limited, restricting the scope of analyses and insights. Here we present a harmonized data set synthesizing urban GHG observations from cities with monitoring networks across North America that will facilitate cross-city analyses and address scientific questions that are difficult to address in isolation.

Dramatic Lockdown Fossil Fuel CO2 Decrease Detected by Citizen Science-Supported Atmospheric Radiocarbon Observations.

COVID-19 lockdowns resulted in dramatic changes to fossil fuel CO2 emissions around the world, most prominently in the transportation sector. Yet travel restrictions also hampered observational data collection, making it difficult to evaluate emission changes as they occurred. To overcome this, we used a novel citizen science campaign to detect emission changes during lockdown and engage youth in climate science. Citizen scientists collected grass samples from their garden or local park, from which we analyzed the radiocarbon content to infer the recently added atmospheric fossil fuel CO2 mole fraction at each sampling location. The local fossil fuel CO2 mole fractions during lockdown were compared with a "normal" nonlockdown period. Our results from 17 sites in five cities around New Zealand demonstrate dramatic reductions in traffic emissions of 75 ± 3% during the most severe lockdown restriction period. This is consistent with sparse local traffic count information and a much larger decrease in traffic emissions than reported in global aggregate estimates of emission changes. Our results demonstrate that despite nationally consistent rules on travel during lockdown, emission changes varied by location, with inner-city sites typically dominated by bus traffic showing smaller decreases in emissions than elsewhere.

Radiocarbon bomb-peak signal in tree-rings from the tropical Andes register low latitude atmospheric dynamics in the Southern Hemisphere.

South American tropical climate is strongly related to the tropical low-pressure belt associated with the South American monsoon system. Despite its central societal role as a modulating agent of rainfall in tropical South America, its long-term dynamical variability is still poorly understood. Here we combine a new (and world's highest) tree-ring 14C record from the Altiplano plateau in the central Andes with other 14C records from the Southern Hemisphere during the second half of the 20th century in order to elucidate the latitudinal gradients associated with the dissemination of the bomb 14C signal. Our tree-ring 14C record faithfully captured the bomb signal of the 1960's with an excellent match to atmospheric 14C measured in New Zealand but with significant differences with a recent record from Southeast Brazil located at almost equal latitude. These results imply that the spreading of the bomb signal throughout the Southern Hemisphere was a complex process that depended on atmospheric dynamics and surface topography generating reversals on the expected north-south gradient in certain years. We applied air-parcel modeling based on climate data to disentangle their different geographical provenances and their preformed (reservoir affected) radiocarbon content. We found that air parcel trajectories arriving at the Altiplano during the bomb period were sourced i) from the boundary layer in contact with the Pacific Ocean (41%), ii) from the upper troposphere (air above the boundary layer, with no contact with oceanic or continental carbon reservoirs) (38%) and iii) from the Amazon basin (21%). Based on these results we estimated the ∆14C endmember values for the different carbon reservoirs affecting our record which suggest that the Amazon basin biospheric 14C isoflux could have been reversed from negative to positive as early as the beginning of the 1970's. This would imply a much faster carbon turnover rate in the Amazon than previously modelled.

Authenticating bioplastics using carbon and hydrogen stable isotopes - An alternative analytical approach.

RATIONALE: A combination of stable carbon (δ13 C) and hydrogen (δ2 H) isotope ratios and carbon content (% C) was evaluated as a rapid, low-cost analytical approach to authenticate bioplastics, complementing existing radiocarbon (14 C) and Fourier transform infrared (FTIR) analytical methods. METHODS: Petroleum- and bio-based precursor materials and in-market plastics were analysed and their δ13 C, δ2 H and % C values were used to establish isotope criteria to evaluate plastic claims, and the source and biocontent of the samples. 14 C was used to confirm the findings of the isotope approach and FTIR analysis was used to vertify the plastic type of the in-market plastics. RESULTS: Distinctive carbon and hydrogen stable isotope ratios were found for authentic bio-based and petroleum-based precursor plastics, and it was possible to classify in-market plastics according to their source materials (petroleum, C3, C4, and mixed sources). An estimation of C4 biocontent was possible from a C4-petroleum isotope mixing model using δ13 C which was well correlated (R2 = 0.98) to 14 C. It was not possible to establish a C3-petroleum isotope mixing model due to δ13 C isotopic overlap with petroleum plastics; however, the addition of δ2 H and % C was useful to evaluate if petroleum-bioplastic mixes contained C3 bioplastics, and PLS-DA modelling reliably clustered each plastic type. CONCLUSIONS: A combined dual stable isotope and carbon content approach was found to rapidly and accurately identify C3 and C4 bio-based products from their petroleum counterparts, and identify instances of petroleum and bio-based mixes frequently found in mislabelled bioplastics. Out of 37 in-market products labelled as bioplastic, 19 were found to contain varying amounts of petroleum-based plastic and did not meet their bio-based claims.

The influence of near-field fluxes on seasonal carbon dioxide enhancements: results from the Indianapolis Flux Experiment (INFLUX).

BACKGROUND: Networks of tower-based CO2 mole fraction sensors have been deployed by various groups in and around cities across the world to quantify anthropogenic CO2 emissions from metropolitan areas. A critical aspect in these approaches is the separation of atmospheric signatures from distant sources and sinks (i.e., the background) from local emissions and biogenic fluxes. We examined CO2 enhancements compared to forested and agricultural background towers in Indianapolis, Indiana, USA, as a function of season and compared them to modeled results, as a part of the Indianapolis Flux (INFLUX) project. RESULTS: At the INFLUX urban tower sites, daytime growing season enhancement on a monthly timescale was up to 4.3-6.5 ppm, 2.6 times as large as those in the dormant season, on average. The enhancement differed significantly depending on choice of background and time of year, being 2.8 ppm higher in June and 1.8 ppm lower in August using a forested background tower compared to an agricultural background tower. A prediction based on land cover and observed CO2 fluxes showed that differences in phenology and drawdown intensities drove measured differences in enhancements. Forward modelled CO2 enhancements using fossil fuel and biogenic fluxes indicated growing season model-data mismatch of 1.1 ± 1.7 ppm for the agricultural background and 2.1 ± 0.5 ppm for the forested background, corresponding to 25-29% of the modelled CO2 enhancements. The model-data total CO2 mismatch during the dormant season was low, - 0.1 ± 0.5 ppm. CONCLUSIONS: Because growing season biogenic fluxes at the background towers are large, the urban enhancements must be disentangled from the biogenic signal, and growing season increases in CO2 enhancement could be misinterpreted as increased anthropogenic fluxes if the background ecosystem CO2 drawdown is not considered. The magnitude and timing of enhancements depend on the land cover type and net fluxes surrounding each background tower, so a simple box model is not appropriate for interpretation of these data. Quantification of the seasonality and magnitude of the biological fluxes in the study region using high-resolution and detailed biogenic models is necessary for the interpretation of tower-based urban CO2 networks for cities with significant vegetation.

Policy-Relevant Assessment of Urban CO2 Emissions.

Global fossil fuel carbon dioxide (FFCO2) emissions will be dictated to a great degree by the trajectory of emissions from urban areas. Conventional methods to quantify urban FFCO2 emissions typically rely on self-reported economic/energy activity data transformed into emissions via standard emission factors. However, uncertainties in these traditional methods pose a roadblock to implementation of effective mitigation strategies, independently monitor long-term trends, and assess policy outcomes. Here, we demonstrate the applicability of the integration of a dense network of greenhouse gas sensors with a science-driven building and street-scale FFCO2 emissions estimation through the atmospheric CO2 inversion process. Whole-city FFCO2 emissions agree within 3% annually. Current self-reported inventory emissions for the city of Indianapolis are 35% lower than our optimal estimate, with significant differences across activity sectors. Differences remain, however, regarding the spatial distribution of sectoral FFCO2 emissions, underconstrained despite the inclusion of coemitted species information.

Synthesis of Urban CO2 Emission Estimates from Multiple Methods from the Indianapolis Flux Project (INFLUX).

Urban areas contribute approximately three-quarters of fossil fuel derived CO2 emissions, and many cities have enacted emissions mitigation plans. Evaluation of the effectiveness of mitigation efforts will require measurement of both the emission rate and its change over space and time. The relative performance of different emission estimation methods is a critical requirement to support mitigation efforts. Here we compare results of CO2 emissions estimation methods including an inventory-based method and two different top-down atmospheric measurement approaches implemented for the Indianapolis, Indiana, U.S.A. urban area in winter. By accounting for differences in spatial and temporal coverage, as well as trace gas species measured, we find agreement among the wintertime whole-city fossil fuel CO2 emission rate estimates to within 7%. This finding represents a major improvement over previous comparisons of urban-scale emissions, making urban CO2 flux estimates from this study consistent with local and global emission mitigation strategy needs. The complementary application of multiple scientifically driven emissions quantification methods enables and establishes this high level of confidence and demonstrates the strength of the joint implementation of rigorous inventory and atmospheric emissions monitoring approaches.

The Indianapolis Flux Experiment (INFLUX): A test-bed for developing urban greenhouse gas emission measurements.

The objective of the Indianapolis Flux Experiment (INFLUX) is to develop, evaluate and improve methods for measuring greenhouse gas (GHG) emissions from cities. INFLUX's scientific objectives are to quantify CO2 and CH4 emission rates at 1 km resolution with a 10% or better accuracy and precision, to determine whole-city emissions with similar skill, and to achieve high (weekly or finer) temporal resolution at both spatial resolutions. The experiment employs atmospheric GHG measurements from both towers and aircraft, atmospheric transport observations and models, and activity-based inventory products to quantify urban GHG emissions. Multiple, independent methods for estimating urban emissions are a central facet of our experimental design. INFLUX was initiated in 2010 and measurements and analyses are ongoing. To date we have quantified urban atmospheric GHG enhancements using aircraft and towers with measurements collected over multiple years, and have estimated whole-city CO2 and CH4 emissions using aircraft and tower GHG measurements, and inventory methods. Significant differences exist across methods; these differences have not yet been resolved; research to reduce uncertainties and reconcile these differences is underway. Sectorally- and spatially-resolved flux estimates, and detection of changes of fluxes over time, are also active research topics. Major challenges include developing methods for distinguishing anthropogenic from biogenic CO2 fluxes, improving our ability to interpret atmospheric GHG measurements close to urban GHG sources and across a broader range of atmospheric stability conditions, and quantifying uncertainties in inventory data products. INFLUX data and tools are intended to serve as an open resource and test bed for future investigations. Well-documented, public archival of data and methods is under development in support of this objective.

Independent evaluation of point source fossil fuel CO2 emissions to better than 10%.

Independent estimates of fossil fuel CO2 (CO2ff) emissions are key to ensuring that emission reductions and regulations are effective and provide needed transparency and trust. Point source emissions are a key target because a small number of power plants represent a large portion of total global emissions. Currently, emission rates are known only from self-reported data. Atmospheric observations have the potential to meet the need for independent evaluation, but useful results from this method have been elusive, due to challenges in distinguishing CO2ff emissions from the large and varying CO2 background and in relating atmospheric observations to emission flux rates with high accuracy. Here we use time-integrated observations of the radiocarbon content of CO2 ((14)CO2) to quantify the recently added CO2ff mole fraction at surface sites surrounding a point source. We demonstrate that both fast-growing plant material (grass) and CO2 collected by absorption into sodium hydroxide solution provide excellent time-integrated records of atmospheric (14)CO2 These time-integrated samples allow us to evaluate emissions over a period of days to weeks with only a modest number of measurements. Applying the same time integration in an atmospheric transport model eliminates the need to resolve highly variable short-term turbulence. Together these techniques allow us to independently evaluate point source CO2ff emission rates from atmospheric observations with uncertainties of better than 10%. This uncertainty represents an improvement by a factor of 2 over current bottom-up inventory estimates and previous atmospheric observation estimates and allows reliable independent evaluation of emissions.

High-resolution atmospheric inversion of urban CO2 emissions during the dormant season of the Indianapolis Flux Experiment (INFLUX).

Based on a uniquely dense network of surface towers measuring continuously the atmospheric concentrations of greenhouse gases (GHGs), we developed the first comprehensive monitoring systems of CO2 emissions at high resolution over the city of Indianapolis. The urban inversion evaluated over the 2012-2013 dormant season showed a statistically significant increase of about 20% (from 4.5 to 5.7 MtC ± 0.23 MtC) compared to the Hestia CO2 emission estimate, a state-of-the-art building-level emission product. Spatial structures in prior emission errors, mostly undetermined, appeared to affect the spatial pattern in the inverse solution and the total carbon budget over the entire area by up to 15%, while the inverse solution remains fairly insensitive to the CO2 boundary inflow and to the different prior emissions (i.e., ODIAC). Preceding the surface emission optimization, we improved the atmospheric simulations using a meteorological data assimilation system also informing our Bayesian inversion system through updated observations error variances. Finally, we estimated the uncertainties associated with undetermined parameters using an ensemble of inversions. The total CO2 emissions based on the ensemble mean and quartiles (5.26-5.91 MtC) were statistically different compared to the prior total emissions (4.1 to 4.5 MtC). Considering the relatively small sensitivity to the different parameters, we conclude that atmospheric inversions are potentially able to constrain the carbon budget of the city, assuming sufficient data to measure the inflow of GHG over the city, but additional information on prior emission error structures are required to determine the spatial structures of urban emissions at high resolution.

Variable effects of nitrogen additions on the stability and turnover of soil carbon.

Soils contain the largest near-surface reservoir of terrestrial carbon and so knowledge of the factors controlling soil carbon storage and turnover is essential for understanding the changing global carbon cycle. The influence of climate on decomposition of soil carbon has been well documented, but there remains considerable uncertainty in the potential response of soil carbon dynamics to the rapid global increase in reactive nitrogen (coming largely from agricultural fertilizers and fossil fuel combustion). Here, using 14C, 13C and compound-specific analyses of soil carbon from long-term nitrogen fertilization plots, we show that nitrogen additions significantly accelerate decomposition of light soil carbon fractions (with decadal turnover times) while further stabilizing soil carbon compounds in heavier, mineral-associated fractions (with multidecadal to century lifetimes). Despite these changes in the dynamics of different soil pools, we observed no significant changes in bulk soil carbon, highlighting a limitation inherent to the still widely used single-pool approach to investigating soil carbon responses to changing environmental conditions. It remains to be seen if the effects observed here-caused by relatively high, short-term fertilizer additions-are similar to those arising from lower, long-term additions of nitrogen to natural ecosystems from atmospheric deposition, but our results suggest nonetheless that current models of terrestrial carbon cycling do not contain the mechanisms needed to capture the complex relationship between nitrogen availability and soil carbon storage.