Jocelyn Turnbull

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.

A new high precision 14CO2 time series for North American continental air

We develop a high precision Δ 14 CO 2 measurement capability in 2-5 L samples of whole air for implementation within existing greenhouse gas flask sampling networks. The long-term repeatability of the measurement is 1.8%o (1-sigma), as determined from repeated analyses of quality control standards and replicate extraction and measurement of authentic field samples. In a parallel effort, we have begun a Δ 14 CO 2 measurement series from NOAA/ESRLs (formerly NOAA/CMDL) surface flask sampling site at Niwot Ridge, Colorado, USA (40.05°N, 105.58°W, 3475 masl) in order to monitor the isotopic composition of carbon dioxide in relatively clean air over the North American continent. Δ 14 CO 2 at Niwot Ridge decreased by 5.7‰/yr from 2004 to 2006, with a seasonal amplitude of 3-5%o. A comparison with measurements from the free troposphere above New England, USA (41°N, 72°W) indicates that the Δ 14 CO 2 series at the two sites are statistically similar at timescales longer than a few days to weeks (i.e., those of synoptic scale variations in transport), suggesting that the Niwot Ridge measurements can be used as a proxy for North American free tropospheric air in future carbon cycle studies.

Toward quantification and source sector identification of fossil fuel CO2 emissions from an urban area: Results from the INFLUX experiment

The Indianapolis Flux Experiment (INFLUX) aims to develop and assess methods for quantifying urban greenhouse gas emissions. Here we use CO2, 14CO2, and CO measurements from tall towers around Indianapolis, USA, to determine urban total CO2, the fossil fuel derived CO2 component (CO2ff), and CO enhancements relative to background measurements. When a local background directly upwind of the urban area is used, the wintertime total CO2 enhancement over Indianapolis can be entirely explained by urban CO2ff emissions. Conversely, when a continental background is used, CO2ff enhancements are larger and account for only half the total CO2 enhancement, effectively representing the combined CO2ff enhancement from Indianapolis and the wider region. In summer, we find that diurnal variability in both background CO2 mole fraction and covarying vertical mixing makes it difficult to use a simple upwind-downwind difference for a reliable determination of total CO2 urban enhancement. We use characteristic CO2ff source sector CO:CO2ff emission ratios to examine the contribution of the CO2ff source sectors to total CO2ff emissions. This method is strongly sensitive to the mobile sector, which produces most CO. We show that the inventory-based emission product (“bottom up”) and atmospheric observations (“top down”) can be directly compared throughout the diurnal cycle using this ratio method. For Indianapolis, the top-down observations are consistent with the bottom-up Hestia data product emission sector patterns for most of the diurnal cycle but disagree during the nighttime hours. Further examination of both the top-down and bottom-up assumptions is needed to assess the exact cause of the discrepancy.

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.

Allocation of Terrestrial Carbon Sources Using 14CO2: Methods, Measurement, and Modeling

The radiocarbon content of whole air provides a theoretically ideal and now observationally proven tracer for recently added fossil-fuel-derived CO2 in the atmosphere (Cff). Over large industrialized land areas, determination of Cff also constrains the change in CO2 due to uptake and release by the terrestrial biosphere. Here, we review the development of a CO2 measurement program and its implementation within the US portion of the NOAA Global Monitoring Division’s air sampling network. The CO2 measurement repeatability is evaluated based on surveillance cylinders of whole air and equates to a Cff detection limit of 0.9 ppm from measurement uncertainties alone. We also attempt to quantify additional sources of uncertainty arising from non-fossil terms in the atmospheric CO2 budget and from uncertainties in the composition of “background” air against which Cff enhancements occur. As an example of how we apply the measurements, we present estimates of the boundary layer enhancements of Cff and Cbio using observations obtained from vertical airborne sampling profiles off of the northeastern US. We also present an updated time series of measurements from NOAA GMD’s Niwot Ridge site at 3475 m asl in Colorado in order to characterize recent CO2 variability in the well-mixed free troposphere.

Global Network Measurements of Atmospheric Trace Gas Isotopes

The Earth’s atmosphere is critical to life on Earth and human activities have been altering its composition since at least the industrial revolution. The global climate change during the twenty-first century will very likely be larger than that observed during the twentieth century. Atmospheric monitoring programs provide critical observations with long-term direct measurements of greenhouse gases and their isotopes that help constrain our understanding of that global climate change by driving models that improve our knowledge of biosphere/ocean processes at the heart of the climate system. In this chapter we highlight the importance of global atmospheric monitoring, explore several global measurement programs, and outline the critical elements necessary to operate these observational networks. We revisit the criteria necessary for intercomparison and linking of atmospheric isotopic data sets from the global measurement community, and present some recent data products and results for isotopic models that shed important light on sources and sinks of greenhouse gases.

Iconic CO2 Time Series at Risk

The steady rise in atmospheric long-lived greenhouse gas concentrations is the main driver of contemporary climate change. The Mauna Loa CO2 time series (1, 2), started by C. D. Keeling in 1958 and maintained today by the Scripps Institution of Oceanography and the Earth System Research Laboratory (ESRL) of NOAA, is iconic evidence of the effect of human-caused fossil fuel and land-use change emissions on the atmospheric increase of CO2. The continuity of such records depends critically on having stable funding, which is challenging to maintain in the context of 3- to 4-year research grant funding cycles (3), and is currently threatened by the financial crisis. The ESRL Global Monitoring Division maintains a network of about 100 surface and aircraft sites worldwide at which whole air samples are collected approximately every week for analysis of CO2, CH4, CO, halocarbons, and many other chemical species (4). This is complemented by high-frequency measurements at the Mauna Loa, Barrow, American Samoa, and South Pole observatories, and about 10 North American tall towers. The success of the NOAA program has inspired similar efforts in Europe (5), China (6), India (7), and Brazil (8), with the United Nations World Meteorological Organization providing guidance and precision requirements through the Global Atmosphere Watch program (9), but no funding. The data collected by NOAA and its worldwide partners have been used not only to demonstrate the unassailable rise of atmospheric greenhouse gas concentrations, but also to infer the magnitudes, locations, and times of surface-atmosphere exchange of those gases based on small concentration gradients between sites (10). Important findings from analysis of these records include the detection of a significant terrestrial carbon sink at northern mid-latitudes (11) and subsequent research aimed at identifying the mechanisms by which that sink must operate. Long-term, high-quality, atmospheric measurements are crucial for quantifying trends in greenhouse gas fluxes and attributing them to fossil fuel emissions, changes in land-use and management, or the response of natural land and ocean ecosystems to climate change and elevated CO2 concentrations. Greenhouse gas measurements along tall towers in the interior continents allow quantification of regional sources and sinks, which has a very high relevance for measuring the effectiveness of climate policy. NOAA ESRL provides measurements that are critical for the U.S. national security in that they provide independent verification and early warning of changing greenhouse gas emissions from countries involved in efforts to mitigate greenhouse gases. Dedicated carbon-observing satellites such as GOSAT and OCO-2 are needed to fill in the missing geographical information required for verification of carbon flux mitigation efforts. However, satellite retrievals do not yet provide sufficient information to deliver new constraints on surface fluxes, although quick progress is being made in this direction. In situ observations are crucial for anchoring space-borne measurements, for detecting potential biases of remote sensing techniques, and for providing continuity given the finite lifetime of satellites. Despite the growing importance of greenhouse gas observations to humanity, substantial budget cuts at NOAA have resulted in curtailment of our ability to observe and understand changes to the global carbon cycle. Already, a dozen surface flask-sampling sites have been removed from NOAAs operational network and aircraft profiling sites have been eliminated and reduced in frequency at the remaining NOAA sites. The planned growth in the tall tower program has stopped, and plans for closing some towers are being developed. The U.S. budget process in this election year, with the added risk of mandatory across-the-board cuts due to the 2011 Budget Control Act, foretells more bleak news for greenhouse gas monitoring at NOAA and could cause further retreat from the goal of recording ongoing changes in atmospheric composition. As scientists, we believe that preserving the continuity of these vital time series must remain a priority for U.S. carbon cycle research.

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

Significance The 1,000 largest power plants comprise 22% of total global fossil fuel CO2 emissions, making them an obvious target for regulating and reducing emissions. The success of existing and upcoming regulations and emission trading schemes requires reliable monitoring and verification of emissions, preferably using independent, objective evaluation to establish trust and transparency. However, such methodology has thus far been elusive, and emissions reporting currently relies solely on self-reported “bottom-up” inventory data. We demonstrate a method using time-integrated atmospheric observations and modeling to reliably quantify fossil fuel CO2 emissions from point sources to within 10%. This level of uncertainty is a marked improvement over current ∼20% uncertainties for individual power plants and allows independent evaluation of reported emissions. 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 (14CO2) 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 14CO2. 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-Precision Atmospheric 14 CO 2 Measurement at the Rafter Radiocarbon Laboratory

This article describes a new capability for high-precision 14 C measurement of CO2 from air at the Rafter Radiocarbon Laboratory, GNS Science, New Zealand. We evaluate the short-term within-wheel repeatability and long-term between-wheel repeatability from measurements of multiple aliquots of control materials sourced from whole air. Samples are typically measured to 650,000 14C counts, providing a nominal accelerator mass spectrometry (AMS) statistical uncer- tainty of 1.3‰. No additional uncertainty is required to explain the within-wheel variability. An additional uncertainty factor is needed to explain the long-term repeatability spanning multiple measurement wheels, bringing the overall repeatability to 1.8‰, comparable to other laboratories measuring air materials to high precision. This additional uncertainty factor appears to be due to variability in the measured 14 C content of OxI primary standard targets, likely from the combustion process. We observe an offset of 1.4‰ in our samples relative to those measured by the University of Colorado INSTAAR, comparable to interlaboratory offsets observed in recent intercomparison exercises. This article describes the high-precision atmospheric 14 CO 2 measurement capability at the Rafter Radiocarbon Laboratory at GNS Science, New Zealand. We discuss the two different methods we commonly use for CO 2 collection and subsequent extraction. We describe our recently upgraded graphitization system and detail our measurement protocols for samples requiring high precision. We use replicate measurements of CO 2 from a number of different control materials, all derived from whole air, to examine mean values and offsets between different standardization methods within our laboratory, as well as interlaboratory offsets based on an ongoing intercomparison with the University of Colorado INSTAAR. We then examine short-term within-wheel and long-term repeatability of our measurements, and the sources of uncertainty that contribute to these. METHODS CO 2 from air is collected either by in situ absorption of CO 2 into sodium hydroxide (NaOH) solution or by collection of whole air into flasks or pressurized cylinders. In addition, control materials, pri - mary standards, and process blanks are routinely analyzed. In this section, we describe the collection methods and protocols for extracting and purifying the CO 2 in the laboratory.