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A reliable and precise in situ CO2 and CO analysis system has been developed and deployed at eight sites in the NOAA Earth System Research Laboratory's (ESRL) Global Greenhouse Gas Reference Network. The network uses very tall (> 300 m) television and radio transmitter towers that provide a convenient platform for mid-boundary-layer trace-gas sampling. Each analyzer has three sample inlets for profile sampling, and a complete vertical profile is obtained every 15 min. The instrument suite at one site has been augmented with a cavity ring-down spectrometer for measuring CO2 and CH4. The long-term stability of the systems in the field is typically better than 0.1 ppm for CO2, 6 ppb for CO, and 0.5 ppb for CH4, as determined from repeated standard gas measurements. The instrumentation is fully automated and includes sensors for measuring a variety of status parameters, such as temperatures, pressures, and flow rates, that are inputs for automated alerts and quality control algorithms. Detailed and time-dependent uncertainty estimates have been constructed for all of the gases, and the uncertainty framework could be readily adapted to other species or analysis systems. The design emphasizes use of off-the-shelf parts and modularity to facilitate network operations and ease of maintenance. The systems report high-quality data with > 93% uptime. Recurrent problems and limitations of the current system are discussed along with general recommendations for high-accuracy trace-gas monitoring. The network is a key component of the North American Carbon Program and a useful model for future research-grade operational greenhouse gas monitoring efforts.
The fast development of solar radiation and energy applications, such as photovoltaic and solar thermodynamic systems, has increased the need for solar radiation measurement and monitoring, for not only the global but also the diffuse and direct components. End users look for the best compromise between getting close to state-of-the-art measurements and keeping low capital, maintenance and operating costs. Among the existing commercial options, SPN1 is a relatively low cost solar radiometer that estimates global and diffuse solar irradiances from seven thermopile sensors under a shading mask and without moving parts.
This work presents a comprehensive study of SPN1 accuracy and sources of uncertainty, drawing on laboratory experiments, numerical modelling and comparison studies between measurements from this sensor and state-of-the art instruments for six diverse sites. Several clues are provided for improving the SPN1 accuracy and agreement with state-of-the art measurements.
We estimate the CO2 flux over Tropical Asia in 2009, 2010, and 2011 using Greenhouse Gases Observing Satellite (GOSAT) total column CO2(XCO2) and in situ measurements of CO2. Compared to flux estimates from assimilating surface measurements of CO2, GOSAT XCO2 estimates a more dynamic seasonal cycle and a large source in March–May 2010. The more dynamic seasonal cycle is consistent with earlier work by Patra et al. (2011), and the enhanced 2010 source is supported by independent upper air CO2 measurements from the Comprehensive Observation Network for Trace gases by Airliner (CONTRAIL) project. Using Infrared Atmospheric Sounding Interferometer (IASI) measurements of total column CO (XCO), we show that biomass burning CO2 can explain neither the dynamic seasonal cycle nor the 2010 source. We conclude that both features must come from the terrestrial biosphere. In particular, the 2010 source points to biosphere response to above-average temperatures that year.
Understanding the processes that control the terrestrial exchange of carbon is critical for assessing atmospheric CO2 budgets. Carbonyl sulfide (COS) is taken up by vegetation during photosynthesis following a pathway that mirrors CO2 but has a small or nonexistent emission component, providing a possible tracer for gross primary production. Field measurements of COS and CO2 mixing ratios were made in forest, senescent grassland, and riparian ecosystems using a laser absorption spectrometer installed in a mobile trailer. Measurements of leaf fluxes with a branch-bag gas-exchange system were made across species from 10 genera of trees, and soil fluxes were measured with a flow-through chamber. These data show (1) the existence of a narrow normalized daytime uptake ratio of COS to CO2 across vascular plant species of 1.7, providing critical information for the application of COS to estimate photosynthetic CO2 fluxes and (2) a temperature-dependent normalized uptake ratio of COS to CO2 from soils. Significant nighttime uptake of COS was observed in broad-leafed species and revealed active stomatal opening prior to sunrise. Continuous high-resolution joint measurements of COS and CO2 concentrations in the boundary layer are used here alongside the flux measurements to partition the influence that leaf and soil fluxes and entrainment of air from above have on the surface carbon budget. The results provide a number of critical constraints on the processes that control surface COS exchange, which can be used to diagnose the robustness of global models that are beginning to use COS to constrain terrestrial carbon exchange.
Fossil fuel combustion has increased atmospheric CO2 by ≈ 115 µmol mol−1 since 1750 and decreased its carbon isotope composition (δ13C) by 1.7–2‰ (the 13C Suess effect). Because carbon is stored in the terrestrial biosphere for decades and longer, the δ13C of CO2 released by terrestrial ecosystems is expected to differ from the δ13C of CO2 assimilated by land plants during photosynthesis. This isotopic difference between land-atmosphere respiration (δR) and photosynthetic assimilation (δA) fluxes gives rise to the 13C land disequilibrium (D). Contemporary understanding suggests that over annual and longer time scales, D is determined primarily by the Suess effect, and thus, D is generally positive (δR > δA). A 7 year record of biosphere-atmosphere carbon exchange was used to evaluate the seasonality of δA and δR, and the 13C land disequilibrium, in a subalpine conifer forest. A novel isotopic mixing model was employed to determine the δ13C of net land-atmosphere exchange during day and night and combined with tower-based flux observations to assess δA and δR. The disequilibrium varied seasonally and when flux-weighted was opposite in sign than expected from the Suess effect (D = −0.75 ± 0.21‰ or −0.88 ± 0.10‰ depending on method). Seasonality in D appeared to be driven by photosynthetic discrimination (Δcanopy) responding to environmental factors. Possible explanations for negative D include (1) changes in Δcanopy over decades as CO2 and temperature have risen, and/or (2) post-photosynthetic fractionation processes leading to sequestration of isotopically enriched carbon in long-lived pools like wood and soil.
Natural gas (NG) is a potential “bridge fuel” during transition to a decarbonized energy system: It emits less carbon dioxide during combustion than other fossil fuels and can be used in many industries. However, because of the high global warming potential of methane (CH4, the major component of NG), climate benefits from NG use depend on system leakage rates. Some recent estimates of leakage have challenged the benefits of switching from coal to NG, a large near-term greenhouse gas (GHG) reduction opportunity (1–3). Also, global atmospheric CH4 concentrations are on the rise, with the causes still poorly understood (4).
To improve understanding of leakage rates for policy-makers, investors, and other decision-makers, we review 20 years of technical literature on NG emissions in the United States and Canada [see supplementary materials (SM) for details]. We find (i) measurements at all scales show that official inventories consistently underestimate actual CH4 emissions, with the NG and oil sectors as important contributors; (ii) many independent experiments suggest that a small number of “superemitters” could be responsible for a large fraction of leakage; (iii) recent regional atmospheric studies with very high emissions rates are unlikely to be representative of typical NG system leakage rates; and (iv) assessments using 100-year impact indicators show system-wide leakage is unlikely to be large enough to negate climate benefits of coal-to-NG substitution.
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.
No abstract available.
Urban environments are the primary contributors to global anthropogenic carbon emissions. Because much of the growth in CO2 emissions will originate from cities, there is a need to develop, assess, and improve measurement and modeling strategies for quantifying and monitoring greenhouse gas emissions from large urban centers. In this study the uncertainties in an aircraft-based mass balance approach for quantifying carbon dioxide and methane emissions from an urban environment, focusing on Indianapolis, IN, USA, are described. The relatively level terrain of Indianapolis facilitated the application of mean wind fields in the mass balance approach. We investigate the uncertainties in our aircraft-based mass balance approach by (1) assessing the sensitivity of the measured flux to important measurement and analysis parameters including wind speed, background CO2 and CH4, boundary layer depth, and interpolation technique, and (2) determining the flux at two or more downwind distances from a point or area source (with relatively large source strengths such as solid waste facilities and a power generating station) in rapid succession, assuming that the emission flux is constant. When we quantify the precision in the approach by comparing the estimated emissions derived from measurements at two or more downwind distances from an area or point source, we find that the minimum and maximum repeatability were 12 and 52%, with an average of 31%. We suggest that improvements in the experimental design can be achieved by careful determination of the background concentration, monitoring the evolution of the boundary layer through the measurement period, and increasing the number of downwind horizontal transect measurements at multiple altitudes within the boundary layer.
The amended and adjusted Montreal Protocol continues to be successful at reducing emissions and atmo- spheric abundances of most controlled ozone-depleting substances (ODSs).
The identification and quantification of methane emissions from natural gas production has become increasingly important owing to the increase in the natural gas component of the energy sector. An instrumented aircraft platform was used to identify large sources of methane and quantify emission rates in southwestern PA in June 2012. A large regional flux, 2.0–14 g CH4 s−1 km−2, was quantified for a ∼2,800-km2 area, which did not differ statistically from a bottom-up inventory, 2.3–4.6 g CH4 s−1 km−2. Large emissions averaging 34 g CH4/s per well were observed from seven well pads determined to be in the drilling phase, 2 to 3 orders of magnitude greater than US Environmental Protection Agency estimates for this operational phase. The emissions from these well pads, representing ∼1% of the total number of wells, account for 4–30% of the observed regional flux. More work is needed to determine all of the sources of methane emissions from natural gas production, to ascertain why these emissions occur and to evaluate their climate and atmospheric chemistry impacts.
We determined methane (CH4) emissions from Alaska using airborne measurements from the Carbon Arctic Reservoirs Vulnerability Experiment (CARVE). Atmospheric sampling was conducted between May and September 2012 and analyzed using a customized version of the polar weather research and forecast model linked to a Lagrangian particle dispersion model (stochastic time-inverted Lagrangian transport model). We estimated growing season CH4 fluxes of 8 ± 2 mg CH4⋅m−2⋅d−1 averaged over all of Alaska, corresponding to fluxes from wetlands of
T he 2013 American Meteorological Society (AMS) Symposium on Education continued its tradition of bringing together educators, researchers, professionals, and students to share innovations in education and increase the understanding of the role of educational activities and practices to benefit all ages of learners. The 2-day symposium included 32 oral presentations and 56 posters (available at online at https://ams.confex.com/ams/93Annual /webprogram/22EDUCATION.html).
The implementation and accuracy of a low-rate (~1 Hz) horizontal wind measurement system is described for a fixed-wing aircraft without modification to the airframe. The system is based on a global positioning system (GPS) compass that provides aircraft heading and a ground-referenced velocity, which, when subtracted from the standard true airspeed, provides estimates of the horizontal wind velocity. A series of tests was performed flying “L”-shaped patterns above the boundary layer, where the winds were assumed to be horizontally homogeneous over the area bounded by the flight (approximately 25 km2). Four headings were flown at each altitude at a constant airspeed. Scaling corrections for both heading and airspeed were found by minimizing the variance in the 1-s wind measurements; an upper limit to the error was then computed by calculating the variance of the corrected wind measurements on each of the four headings. A typical uncertainty found in this manner tends to be less than 0.2 m s−1. The measurement system described herein is inexpensive and relatively easy to implement on single-engine aircraft.
Tropospheric ozone plays a major role in Earth’s atmospheric chemistry processes and also acts as an air pollutant and greenhouse gas. Due to its short lifetime, and dependence on sunlight and precursor emissions from natural and anthropogenic sources, tropospheric ozone’s abundance is highly variable in space and time on seasonal, interannual and decadal time-scales. Recent, and sometimes rapid, changes in observed ozone mixing ratios and ozone precursor emissions inspired us to produce this up-to-date overview of tropospheric ozone’s global distribution and trends. Much of the text is a synthesis of in situ and remotely sensed ozone observations reported in the peer-reviewed literature, but we also include some new and extended analyses using well-known and referenced datasets to draw connections between ozone trends and distributions in different regions of the world. In addition, we provide a brief evaluation of the accuracy of rural or remote surface ozone trends calculated by three state-of-the-science chemistry-climate models, the tools used by scientists to fill the gaps in our knowledge of global tropospheric ozone distribution and trends.
Satellite retrievals of methane weighted atmospheric columns are assimilated within a Bayesian inversion system to infer the global and regional methane emissions and sinks for the period August 2009 to July 2010. Inversions are independently computed from three different space-borne observing systems and one surface observing system under several hypotheses for prior-flux and observation errors. Posterior methane emissions are compared and evaluated against surface mole fraction observations via a chemistry-transport model. Apart from SCIAMACHY (SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY), the simulations agree fairly well with the surface mole fractions. The most consistent configurations of this study using TANSO-FTS (Thermal And Near infrared Sensor for carbon Observation – Fourier Transform Spectrometer), IASI (Infrared Atmospheric Sounding Interferometer) or surface measurements induce posterior methane global emissions of, respectively, 565 ± 21 Tg yr−1, 549 ± 36 Tg yr−1 and 538 ± 15 Tg yr−1 over the one-year period August 2009–July 2010. This consistency between the satellite retrievals (apart from SCIAMACHY) and independent surface measurements is promising for future improvement of CH4 emission estimates by atmospheric inversions.
The Measurements of Pollution in the Troposphere (MOPITT) Version 6 (V6) product for carbon monoxide (CO) incorporates several enhancements which will benefit many users of MOPITT data. V6 algorithm improvements are described in detail, and V6 validation results are presented. First, a geolocation bias related to the orientation of the MOPITT instrument relative to the TERRA platform was characterized and eliminated. Second, the variable a priori for CO concentrations for V6 is based on simulations performed with the chemical transport model Community Atmosphere Model with Chemistry (CAM-chem) for the years 2000–2009 instead of the model-derived climatology for 1997–2004 used for V5. Third, meteorological fields required for V6 retrieval processing are extracted from the MERRA (Modern-Era Retrospective Analysis For Research And Applications) reanalysis. Finally, a significant latitude-dependent retrieval bias in the upper troposphere in Version 5 products has been substantially reduced.
In this study, methods of convective/stratiform precipitation classification and surface rain-rate estimation based on the Atmospheric Radiation Measurement Program (ARM) cloud radar measurements were developed and evaluated. Simultaneous and collocated observations of the Ka-band ARM zenith radar (KAZR), two scanning precipitation radars [NCAR S-band/Ka-band Dual Polarization, Dual Wavelength Doppler Radar (S-PolKa) and Texas A&M University Shared Mobile Atmospheric Research and Teaching Radar (SMART-R)], and surface precipitation during the Dynamics of the Madden–Julian Oscillation/ARM MJO Investigation Experiment (DYNAMO/AMIE) field campaign were used. The motivation of this study is to apply the unique long-term ARM cloud radar observations without accompanying precipitation radars to the study of cloud life cycle and precipitation features under different weather and climate regimes. The resulting convective/stratiform classification from KAZR was evaluated against precipitation radars. Precipitation occurrence and classified convective/stratiform rain fractions from KAZR compared favorably to the collocated SMART-R and S-PolKa observations. Both KAZR and S-PolKa radars observed about 5% precipitation occurrence. The convective (stratiform) precipitation fraction is about 18% (82%). Collocated disdrometer observations of two days showed an increased number concentration of small and large raindrops in convective rain relative to dominant small raindrops in stratiform rain. The composite distributions of KAZR reflectivity and Doppler velocity also showed distinct structures for convective and stratiform rain. These evidences indicate that the method produces physically consistent results for the two types of rain. A new KAZR-based, two-parameter [the gradient of accumulative radar reflectivity Ze (GAZ) below 1 km and near-surface Ze] rain-rate estimation procedure was developed for both convective and stratiform rain. This estimate was compared with the exponential Z–R (reflectivity–rain rate) relation. The relative difference between the estimated and surface-measured rainfall rates showed that the two-parameter relation can improve rainfall estimation relative to the Z–R relation.
The GCOS (Global Climate Observing System) Reference Upper-Air Network (GRUAN) data processing for the Vaisala RS92 radiosonde was developed to meet the criteria for reference measurements. These criteria stipulate the collection of metadata, the use of well-documented correction algorithms, and estimates of the measurement uncertainty. An important and novel aspect of the GRUAN processing is that the uncertainty estimates are vertically resolved. This paper describes the algorithms that are applied in version 2 of the GRUAN processing to correct for systematic errors in radiosonde measurements of pressure, temperature, humidity, and wind, as well as how the uncertainties related to these error sources are derived. Currently, the RS92 is launched on a regular basis at 13 out of 15 GRUAN sites. An additional GRUAN requirement for performing reference measurements with the RS92 is that the manufacturer-prescribed procedure for the radiosonde's preparation, i.e. heated reconditioning of the sensors and recalibration during ground check, is followed. In the GRUAN processing however, the recalibration of the humidity sensors that is applied during ground check is removed. For the dominant error source, solar radiation, laboratory experiments were performed to investigate and model its effect on the RS92's temperature and humidity measurements. GRUAN uncertainty estimates are 0.15 K for night-time temperature measurements and approximately 0.6 K at 25 km during daytime. The other uncertainty estimates are up to 6% relative humidity for humidity, 10–50 m for geopotential height, 0.6 hPa for pressure, 0.4–1 m s−1 for wind speed, and 1° for wind direction. Daytime temperature profiles for GRUAN and Vaisala processing are comparable and consistent within the estimated uncertainty. GRUAN daytime humidity profiles are up to 15% moister than Vaisala processed profiles, of which two-thirds is due to the radiation dry bias correction and one-third is due to an additional calibration correction. Redundant measurements with frost point hygrometers (CFH and NOAA FPH) show that GRUAN-processed RS92 humidity profiles and frost point data agree within 15% in the troposphere. No systematic biases occur, apart from a 5% dry bias for GRUAN data around −40 °C at night.
Carbon dioxide (CO2) is the dominant long-lived greenhouse gas (LLGHG) contributing to climate forcing; since 1750 its radiative forcing has increased by 1.88 W m-2 or ~65% of the increased forcing by all LLGHGs (see http://www.esrl.noaa.gov/gmd/aggi/aggi.html). When systematic CO2 measurements began at
Mauna Loa, Hawaii, (MLO) in 1958, the annual mean mole fraction was ~315 parts per million (ppm). In May 2013 daily-averaged CO2 at MLO exceeded 400 ppm for the first time (see http://www.esrl.noaa.gov/gmd/ccgg/trends/index.html). This 27% increase is mainly due to a fourfold rise in anthropogenic CO2 emissions from fossil fuel combustion and cement production. The CO2 growth rate has correspondingly increased from 0.7 ppm yr-1 in the early 1960s to 2.1 ppm yr-1 during the last decade. About half of the CO2 emitted remains in the atmosphere; the rest is taken up by the oceans and terrestrial biosphere. The annual atmospheric increase varies considerably from year to year, ranging from 0.7 ± 0.1 to 2.8 ± 0.1 ppm yr-1 since 1990. This is explained largely by variations in natural fluxes influenced by the phase of ENSO (Bastos et al. 2013). In 2013 the globally averaged CO2 mole fraction at Earth’s surface was 395.3 ± 0.1 ppm (Fig. 2.32a), an increase of 2.8 ± 0.1 ppm over the 2012 mean.
The NOAA/ESRL/GMD CCGG cooperative air sampling network effort began in 1967 at Niwot Ridge, Colorado. Today, the network is an international effort which includes regular discrete samples from the NOAA ESRL/GMD baseline observatories, cooperative fixed sites, and commercial ships. Air samples are collected approximately weekly from a globally distributed network of sites. Samples are analyzed for CO2, CH4, CO, H2, N2O, and SF6; and by INSTAAR for the stable isotopes of CO2 and CH4 and for many volatile organic compounds (voc) such as ethane (C2H6), ethylene (C2H4) and propane (C3H8). Measurement data are used to identify long-term trends, seasonal variability, and spatial distribution of carbon cycle gases.
Atmospheric transport model errors are a major contributor to uncertainty in CO2 inverse flux estimates. Our study compares CO2 mole fraction observations from the North American Carbon Program Mid-Continental Intensive (MCI) field campaign and modeled mole fractions from two atmospheric transport models: the global Transport Model 5 from NOAA's CarbonTracker system and the mesoscale Weather Research and Forecasting model. Both models are coupled to identical CO2 fluxes and lateral boundary conditions from CarbonTracker (CT2009 release). Statistical analyses were performed for two periods of 2007 using observed daily daytime average mole fractions of CO2 to test the ability of these models to reproduce the observations and to infer possible causes of the discrepancies. TM5-CT2009 overestimates midsummer planetary boundary layer CO2 for sites in the U.S. corn belt by 10 ppm. Weather Research and Forecasting (WRF)-CT2009 estimates diverge from the observations with similar magnitudes, but the signs of the differences vary from site to site. The modeled mole fractions are highly correlated with the observed seasonal cycle (r ≥ 0.7) but less correlated in the growing season, where weather-related changes in CO2 dominate the observed variability. Spatial correlations in residuals from TM5-CT2009 are higher than WRF-CT2009 perhaps due to TM5's coarse horizontal resolution and shallow vertical mixing. Vertical mixing appears to have influenced CO2 residuals from both models. TM5-CT2009 has relatively weak vertical mixing near the surface limiting the connection between local CO2 surface fluxes and boundary layer. WRF-CT2009 has stronger vertical mixing that may increase the connections between local surface fluxes and the boundary layer.
Atmospheric carbon dioxide (CO2) mole fractions were continuously measured from January 2009 to December 2011 at four atmospheric observatories in China using cavity ring-down spectroscopy instruments. The stations are Lin'an (LAN), Longfengshan (LFS), Shangdianzi (SDZ), and Waliguan (WLG), which are regional (LAN, LFS, SDZ) or global (WLG) measurement stations of the World Meteorological Organization's Global Atmosphere Watch program (WMO/GAW). LAN is located near the megacity of Shanghai, in China's economically most developed region. LFS is in a forest and rice production area, close to the city of Harbin in northeastern China. SDZ is located 150 km northeast of Beijing. WLG, hosting the longest record of measured CO2 mole fractions in China, is a high-altitude site in northwestern China recording background CO2 concentration. The CO2 growth rates are 3.7 ± 1.2 ppm yr−1 for LAN, 2.7 ± 0.8 ppm yr−1 for LFS, 3.5 ± 1.6 ppm yr−1 for SDZ, and 2.2 ± 0.8 ppm yr−1 (1σ) for WLG during the period of 2009 to 2011. The highest annual mean CO2 mole fraction of 404.2 ± 3.9 ppm was observed at LAN in 2011. A comprehensive analysis of CO2 variations, their diurnal and seasonal cycles as well as the analysis of the influence of local sources on the CO2 mole fractions allows a characterization of the sampling sites and of the key processes driving the CO2 mole fractions. These data form a basis to improve our understanding of atmospheric CO2 variations in China and the underlying fluxes using atmospheric inversion models.
Trifluoromethane (CHF3, HFC-23) is one of the hydrofluorocarbons (HFCs) regulated under the Kyoto Protocol with a global warming potential (GWP) of 14 800 (100-year). China’s past, present, and future HFC-23 emissions are of considerable interest to researchers and policymakers involved in climate change. In this study, we compiled a comprehensive historical inventory (1980–2012) and a projection (2013–2050) of HFC-23 production, abatements, and emissions in China. Results show that HFC-23 production in China increased from 0.08 ± 0.05 Gg/yr in 1980 to 15.4 ± 2.1 Gg/yr (228 ± 31 Tg/yr CO2-eq) in 2012, while actual HFC-23 emissions reached a peak of 10.5 ± 1.8 Gg/yr (155 ± 27 Tg/y CO2-eq) in 2006, and decreased to a minimum of 7.3 ± 1.3 Gg/yr (108 ± 19 Tg/yr CO2-eq) in 2008 and 2009. Under the examined business-as-usual (BAU) scenario, the cumulative emissions of HFC-23 in China over the period 2013–2050 are projected to be 609 Gg (9015 Tg CO2-eq which approximates China’s 2012 CO2 emissions). Currently, China’s annual HFC-23 emissions are much higher than those from the developed countries, while it is estimated that by year 2027, China’s historic contribution to the global atmospheric burden of HFC-23 will have surpassed that of the developed nations under the BAU scenario.
This article investigates the annual cycle observed in the Antarctic baseline aerosol scattering coefficient, total particle number concentration, and particle number size distribution (PNSD), as measured at Troll Atmospheric Observatory. Mie theory shows that the annual cycles in microphysical and optical aerosol properties have a common cause. By comparison with observations at other Antarctic stations, it is shown that the annual cycle is not a local phenomenon, but common to central Antarctic baseline air masses. Observations of ground-level ozone at Troll as well as backward plume calculations for the air masses arriving at Troll demonstrate that the baseline air masses originate from the free troposphere and lower stratosphere region, and descend over the central Antarctic continent. The Antarctic summer PNSD is dominated by particles with diameters <100 nm recently formed from the gas-phase despite the absence of external sources of condensible gases. The total particle volume in Antarctic baseline aerosol is linearly correlated with the integral insolation the aerosol received on its transport pathway, and the photooxidative production of particle volume is mostly limited by photooxidative capacity, not availability of aerosol precursor gases. The photooxidative particle volume formation rate in central Antarctic baseline air is quantified to 207 ± 4 μm3/(MJ m). Further research is proposed to investigate the applicability of this number to other atmospheric reservoirs, and to use the observed annual cycle in Antarctic baseline aerosol properties as a benchmark for the representation of natural atmospheric aerosol processes in climate models.
NOAA, through the Joint Polar Satellite System (JPSS) program, in partnership with the National Aeronautical and Space Administration, launched the Suomi National Polar-orbiting Partnership (S-NPP) satellite, a risk reduction and data continuity mission, on 28 October 2011. The JPSS program is executing the S-NPP Calibration and Validation program to ensure that the data products comply with the requirements of the sponsoring agencies. The Ozone Mapping and Profiler Suite (OMPS) consists of two telescopes feeding three detectors measuring solar radiance scattered by the Earth's atmosphere directly and solar irradiance by using diffusers. The measurements are used to generate estimates of total column ozone and vertical ozone profiles for use in near-real-time applications and extension of ozone climate data records. The calibration and validation efforts are progressing well, and both Level 1 (Sensor Data Records) and Level 2 (Ozone Environmental Data Records) have advanced to release at Provisional Maturity. This paper provides information on the product performance over the first 22 months of the mission. The products are evaluated through the use of internal consistency analysis techniques and comparisons to other satellite instrument and ground-based products. The initial performance finds total ozone showing negative bias of 2 to 4% with respect to correlative products and ozone profiles often within ±5% in the middle and upper stratosphere of current operational products. Potential improvements in the measurements and algorithms are identified. These will be implemented in coming months to reduce the differences further.
We use the GEOS-Chem global 3-D atmospheric chemistry transport model to interpret XCH4:XCO2 column ratios retrieved from the Japanese Greenhouse Gases Observing Satellite (GOSAT). The advantage of these data over CO2 and CH4 columns retrieved independently using a full physics optimal estimation algorithm is that they are less prone to scattering-related regional biases. We show that the model is able to reproduce observed global and regional spatial (mean bias =0.7%) and temporal variations (global r2=0.92) of this ratio with a model bias < 2.5%. We also show that these variations are driven by emissions of CO2 and CH4 that are typically 6 months out of phase, which may reduce the sensitivity of the ratio to changes in either gas. To simultaneously estimate fluxes of CO2 and CH4 we use a maximum likelihood estimation approach. We use two approaches to resolve independent flux estimates of these two gases using GOSAT observations of XCH4:XCO2: (1) the a priori error covariance between CO2 and CH4 describing common source from biomass burning; and (2) also fitting independent surface atmospheric measurements of CH4 and CO2 mole fraction that provide additional constraints, improving the effectiveness of the observed GOSAT ratio to constrain flux estimates. We demonstrate the impact of these two approaches using numerical experiments. A posteriori flux estimates inferred using only the GOSAT ratios and taking advantage of the error covariance due to biomass burning are not consistent with the true fluxes in our experiments, as the inversion system cannot judge which species' fluxes to adjust. This reflects the weak dependence of XCH4:XCO2 on biomass burning. We find that adding the surface data effectively provides an "anchor" to the inversion that dramatically improves the ability of the GOSAT ratios to infer both CH4 and CO2 fluxes. We show that the regional flux estimates inferred from GOSAT XCH4:XCO2 ratios together with the surface mole fraction data during 2010 are typically consistent with or better than the corresponding values inferred from fitting XCH4 or the full-physics XCO2 data products, as judged by a posteriori uncertainties. We show that the fluxes inferred from the ratio measurements perform best over regions where there is a large seasonal cycle such as Tropical South America, for which we report a small but significant annual source of CO2 compared to a small annual sink inferred from the XCO2 data. We argue that given that the ratio measurements are less compromised by systematic error than the full physics data products, the resulting a~posteriori estimates and uncertainties provide a more faithful description of the truth. Based on our analysis we also argue that by using the ratios we may be reaching the current limits on the precision of these observed space-based data.
In situ measurements of [OH], [HO2] (square brackets denote species concentrations), and other chemical species were made in the tropical upper troposphere (TUT). [OH] showed a robust correlation with solar zenith angle. Beyond this dependence, however, [OH] did not correlate to its primary source, the product of [O3] and [H2O] ([O3]•[H2O]), or its sink [NOy]. This suggests that [OH] is heavily buffered in the TUT. One important exception to this result is found in regions with very low [O3], [NO], and [NOy]. Under these conditions, [OH] is highly suppressed, pointing to the critical role of NO in sustaining OH in the TUT and the possibility of low [OH] over the western Pacific warm pool due to strong marine convections bringing NO-poor air to the TUT. In contrast to [OH], [HOx] ([OH] + [HO2]) correlated reasonably well with [O3]•[H2O]/[NOy], suggesting that [O3]•[H2O] and [NOy] are the significant source and sink, respectively, of [HOx].
Feedbacks between land carbon pools and climate provide one of the largest sources of uncertainty in our predictions of global climate1, 2. Estimates of the sensitivity of the terrestrial carbon budget to climate anomalies in the tropics and the identification of the mechanisms responsible for feedback effects remain uncertain3, 4. The Amazon basin stores a vast amount of carbon5, and has experienced increasingly higher temperatures and more frequent floods and droughts over the past two decades6. Here we report seasonal and annual carbon balances across the Amazon basin, based on carbon dioxide and carbon monoxide measurements for the anomalously dry and wet years 2010 and 2011, respectively. We find that the Amazon basin lost 0.48 ± 0.18 petagrams of carbon per year (Pg C yr−1) during the dry year but was carbon neutral (0.06 ± 0.1 Pg C yr−1) during the wet year. Taking into account carbon losses from fire by using carbon monoxide measurements, we derived the basin net biome exchange (that is, the carbon flux between the non-burned forest and the atmosphere) revealing that during the dry year, vegetation was carbon neutral. During the wet year, vegetation was a net carbon sink of 0.25 ± 0.14 Pg C yr−1, which is roughly consistent with the mean long-term intact-forest biomass sink of 0.39 ± 0.10 Pg C yr−1 previously estimated from forest censuses7. Observations from Amazonian forest plots suggest the suppression of photosynthesis during drought as the primary cause for the 2010 sink neutralization. Overall, our results suggest that moisture has an important role in determining the Amazonian carbon balance. If the recent trend of increasing precipitation extremes persists6, the Amazon may become an increasing carbon source as a result of both emissions from fires and the suppression of net biome exchange by drought.
Regional convection-permitting model simulations of cloud populations observed during the 2011 Atmospheric Radiation Measurement (ARM) Madden-Julian Oscillation Investigation Experiment/Dynamics of the Madden-Julian Oscillation Experiment (AMIE/DYNAMO) field campaign are evaluated against ground-based radar and ship-based observations. Sensitivity of model simulated reflectivity, surface rain rate, and cold pool statistics to variations of raindrop breakup/self-collection parameters in four state-of-the-art two-moment bulk microphysics schemes in the Weather Research and Forecasting (WRF) model is examined. The model simulations generally overestimate reflectivity from large and deep convective cells, and underestimate stratiform rain and the frequency of cold pools. In the sensitivity experiments, introduction of more aggressive raindrop breakup or decreasing the self-collection efficiency increases the cold pool occurrence frequency in all of the simulations, and slightly reduces the reflectivity and precipitation statistics bias in some schemes but has little effect on the overall mean surface precipitation. Both the radar observations and model simulations of cloud populations show an approximate power law relationship between convective echo-top height and equivalent convective cell radius.
The International Halocarbons in Air Comparison Experiment (IHALACE) was conducted to document relationships between calibration scales among various laboratories that measure atmospheric greenhouse and ozone depleting gases. This study included trace gases such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs), as well as nitrous oxide, methane, sulfur hexafluoride, very short-lived halocompounds, and carbonyl sulfide. Many of these gases are present in the unpolluted atmosphere at pmol mol−1 (parts per trillion) or nmol mol−1 (parts per billion) levels. Six stainless steel cylinders containing natural and modified natural air samples were circulated among 19 laboratories. Results from this experiment reveal relatively good agreement (within a few percent) among commonly used calibration scales. Scale relationships for some gases, such as CFC-12 and CCl4, were found to be consistent with those derived from estimates of global mean mole fractions, while others, such as halon-1211 and CH3Br, revealed discrepancies. The transfer of calibration scales among laboratories was problematic in many cases, meaning that measurements tied to a particular scale may not, in fact, be compatible. Large scale transfer errors were observed for CH3CCl3 (10–100%) and CCl4 (2–30%), while much smaller scale transfer errors (< 1%) were observed for halon-1211, HCFC-22, and HCFC-142b. These results reveal substantial improvements in calibration over previous comparisons. However, there is room for improvement in communication and coordination of calibration activities with respect to the measurement of halogenated and related trace gases.
In addition to direct radiative forcing, long-lived gases containing chlorine and bromine also influence radiative forcing indirectly through destruction of stratospheric ozone. The atmospheric burdens of many of the most potent ozone-depleting gases have been declining in response to production and consumption restrictions imposed by the Montreal Protocol on Substances that Deplete the Ozone Layer and its Amendments (Figs. 2.32d, 2.33). Surface mole fractions of methyl chloroform (CH3CCl3), which has a relatively short lifetime of five years, have declined 95% from peak values in the early 1990s (Fig. 2.33). Gases with longer lifetimes (Table 2.7) are declining more slowly.
Executive Summary. The evidence of climate change from observations of the atmosphere and surface has grown significantly during recent years. At the same time new improved ways of characterizing and quantifying uncertainty have highlighted the challenges that remain for developing long-term global and regional climate quality data records. Currently, the observations of the atmosphere and surface indicate the following changes:. Atmospheric Composition. It is certain that atmospheric burdens of the well-mixed greenhouse gases (GHGs) targeted by the Kyoto Protocol increased from 2005 to 2011. The atmospheric abundance of carbon dioxide (CO2) was 390.5 ppm (390.3 to 390.7) in 2011; this is 40% greater than in 1750. Atmospheric nitrous oxide (N2O) was 324.2 ppb (324.0 to 324.4) in 2011 and has increased by 20% since 1750. Average annual increases in CO2 and N2O from 2005 to 2011 are comparable to those observed from 1996 to 2005. Atmospheric methane (CH4) was 1803.2 ppb (1801.2 to 1805.2) in 2011; this is 150% greater than before 1750. CH4 began increasing in 2007 after remaining nearly constant from 1999 to 2006. Hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), and sulphur hexafluoride (SF6) all continue to increase relatively rapidly, but their contributions to radiative forcing are less than 1% of the total by well-mixed GHGs.
Stratospheric water vapour is a powerful greenhouse gas. The longest available record from balloon observations over Boulder, Colorado, USA shows increases in stratospheric water vapour concentrations that cannot be fully explained by observed changes in the main drivers, tropical tropopause temperatures and methane. Satellite observations could help resolve the issue, but constructing a reliable long-term data record from individual short satellite records is challenging. Here we present an approach to merge satellite data sets with the help of a chemistry–climate model nudged to observed meteorology. We use the models’ water vapour as a transfer function between data sets that overcomes issues arising from instrument drift and short overlap periods. In the lower stratosphere, our water vapour record extends back to 1988 and water vapour concentrations largely follow tropical tropopause temperatures. Lower and mid-stratospheric long-term trends are negative, and the trends from Boulder are shown not to be globally representative. In the upper stratosphere, our record extends back to 1986 and shows positive long-term trends. The altitudinal differences in the trends are explained by methane oxidation together with a strengthened lower-stratospheric and a weakened upper-stratospheric circulation inferred by this analysis. Our results call into question previous estimates of surface radiative forcing based on presumed global long-term increases in water vapour concentrations in the lower stratosphere.
The short-chain non-methane hydrocarbons (NMHC) are mostly emitted into the atmosphere by anthropogenic processes. Recent studies have pointed out a tight linkage between the atmospheric mole fractions of the NMHC ethane and the atmospheric growth rate of methane. Consequently, atmospheric NMHC are valuable indicators for tracking changes in anthropogenic emissions, photochemical ozone production, and greenhouse gases. This study investigates the 1950–2010 Northern Hemisphere atmospheric C2–C5 NMHC ethane, propane, i-butane, n-butane, i-pentane, and n-pentane by (a) reconstructing atmospheric mole fractions of these trace gases using firn air extracted from three boreholes in 2008 and 2009 at the North Greenland Eemian Ice Drilling (NEEM) site and applying state-of-the-art models of trace gas transport in firn, and by (b) considering eight years of ambient NMHC monitoring data from five Arctic sites within the NOAA Global Monitoring Division (GMD) Cooperative Air Sampling Network. Results indicate that these NMHC increased by ~40–120% after 1950, peaked around 1980 (with the exception of ethane, which peaked approximately 10 yr earlier), and have since dramatically decreased to be now back close to 1950 levels. The earlier peak time of ethane vs. the C3–C5 NMHC suggests that different processes and emissions mitigation measures contributed to the decline in these NMHC. The 60 yr record also illustrates notable increases in the ratios of the isomeric iso-/n-butane and iso-/n-pentane ratios. Comparison of the reconstructed NMHC histories with 1950–2000 volatile organic compounds (VOC) emissions data and with other recently published ethane trend analyses from ambient air Pacific transect data showed (a) better agreement with North America and Western Europe emissions than with total Northern Hemisphere emissions data, and (b) better agreement with other Greenland firn air data NMHC history reconstructions than with the Pacific region trends. These analyses emphasize that for NMHC, having atmospheric lifetimes on the order of < 2 months, the Greenland firn air records are primarily a representation of Western Europe and North America emission histories.
Chlorofluorocarbons (CFCs) play a key role in stratospheric ozone loss and are strong infrared absorbers that contribute to global warming. The stratospheric lifetimes of CFCs are a measure of their stratospheric loss rates that are needed to determine global warming and ozone depletion potentials. We applied the tracer–tracer correlation approach to zonal mean climatologies from satellite measurements and model data to assess the lifetimes of CFCl3 (CFC-11) and CF2Cl2 (CFC-12). We present estimates of the CFC-11/CFC-12 lifetime ratio and the absolute lifetime of CFC-12, based on a reference lifetime of 52 years for CFC-11. We analyzed climatologies from three satellite missions, the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), the HIgh Resolution Dynamics Limb Sounder (HIRDLS), and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). We found a CFC-11/CFC-12 lifetime ratio of 0.47±0.08 and a CFC-12 lifetime of 112(96–133) years for ACE-FTS, a ratio of 0.46±0.07 and a lifetime of 113(97–134) years for HIRDLS, and a ratio of 0.46±0.08 and a lifetime of 114(98–136) years for MIPAS. The error-weighted, combined CFC-11/CFC-12 lifetime ratio is 0.46±0.04 and the CFC-12 lifetime estimate is 113(103–124) years. These results agree with the recent Stratosphere-troposphere Processes And their Role in Climate (SPARC) reassessment, which recommends lifetimes of 52(43–67) years and 102(88–122) years, respectively. Having smaller uncertainties than the results from other recent studies, our estimates can help to better constrain CFC-11 and CFC-12 lifetime recommendations in future scientific studies and assessments. Furthermore, the satellite observations were used to validate first simulation results from a new coupled model system, which integrates a Lagrangian chemistry transport model into a climate model. For the coupled model we found a CFC-11/CFC-12 lifetime ratio of 0.48±0.07 and a CFC-12 lifetime of 110(95–129) years, based on a 10-year perpetual run. Closely reproducing the satellite observations, the new model system will likely become a useful tool to assess the impact of advective transport, mixing, and photochemistry as well as climatological variability on the stratospheric lifetimes of long-lived tracers.
This study investigates the use of total column CH4 (XCH4) retrievals from the SCIAMACHY satellite instrument for quantifying large-scale emissions of methane. A unique data set from SCIAMACHY is available spanning almost a decade of measurements, covering a period when the global CH4 growth rate showed a marked transition from stable to increasing mixing ratios. The TM5 4DVAR inverse modelling system has been used to infer CH4 emissions from a combination of satellite and surface measurements for the period 2003-2010. In contrast to earlier inverse modelling studies, the SCIAMACHY retrievals have been corrected for systematic errors using the TCCON network of ground-based Fourier transform spectrometers. The aim is to further investigate the role of bias correction of satellite data in inversions. Methods for bias correction are discussed, and the sensitivity of the optimized emissions to alternative bias correction functions is quantified. It is found that the use of SCIAMACHY retrievals in TM5 4DVAR increases the estimated inter-annual variability of large-scale fluxes by 22% compared with the use of only surface observations. The difference in global methane emissions between 2-year periods before and after July 2006 is estimated at 27-35 Tg yr(-1). The use of SCIAMACHY retrievals causes a shift in the emissions from the extra-tropics to the tropics of 50 +/- 25 Tg yr(-1). The large uncertainty in this value arises from the uncertainty in the bias correction functions. Using measurements from the HIPPO and BARCA aircraft campaigns, we show that systematic errors in the SCIAMACHY measurements are a main factor limiting the performance of the inversions. To further constrain tropical emissions of methane using current and future satellite missions, extended validation capabilities in the tropics are of critical importance.
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Anomalies in tropical lower stratospheric water vapor were strongly negative (dry) at the start of 2013. Observations by the Aura Microwave Limb Sounder (MLS) during January 2013 depict tropical anomalies as large as −1.0 ppmv (−30%) at 82 hPa (Fig. 2.41a). By July, the dry tropical anomalies had weakened but had also spread out globally in the lower stratosphere (Fig. 2.41b). In general, the dry anomalies in July 2013 were stronger and more globally pervasive than in July 2012 (see figure 2.37 in Hurst and Rosenlof 2013). However, in January 2013 there were contrasting positive (wet) anomalies over the high latitudes of each hemisphere. The Arctic anomalies may be related to the strong sudden stratospheric warming event in
January 2013 (see section 2b3) accompanied by enhanced downwelling of older, wetter air into the lower stratosphere. Wet anomalies over the high southern latitudes are attributed to relatively weak dehydration within the smaller and warmer Antarctic vortex in 2012 that had split into two parts by early November (Long and Christy 2013; Newman et al. 2013).
Differences between stratospheric water vapor measurements by NOAA frost point hygrometers (FPHs) and the Aura Microwave Limb Sounder (MLS) are evaluated for the period August 2004 through December 2012 at Boulder, Colorado, Hilo, Hawaii, and Lauder, New Zealand. Two groups of MLS profiles coincident with the FPH soundings at each site are identified using unique sets of spatiotemporal criteria. Before evaluating the differences between coincident FPH and MLS profiles, each FPH profile is convolved with the MLS averaging kernels for eight pressure levels from 100 to 26 hPa (~16 to 25 km) to reduce its vertical resolution to that of the MLS water vapor retrievals. The mean FPH − MLS differences at every pressure level (100 to 26 hPa) are well within the combined measurement uncertainties of the two instruments. However, the mean differences at 100 and 83 hPa are statistically significant and negative, ranging from −0.46 ± 0.22 ppmv (−10.3 ± 4.8%) to −0.10 ± 0.05 ppmv (−2.2 ± 1.2%). Mean differences at the six pressure levels from 68 to 26 hPa are on average 0.8% (0.04 ppmv), and only a few are statistically significant. The FPH − MLS differences at each site are examined for temporal trends using weighted linear regression analyses. The vast majority of trends determined here are not statistically significant, and most are smaller than the minimum trends detectable in this analysis. Except at 100 and 83 hPa, the average agreement between MLS retrievals and FPH measurements of stratospheric water vapor is better than 1%.
Unconventional oil and natural gas extraction enabled by horizontal drilling and hydraulic fracturing (fracking) is driving an economic boom, with consequences described from “revolutionary” to “disastrous.” Reality lies somewhere in between. Unconventional energy generates income and, done well, can reduce air pollution and even water use compared with other fossil fuels. Alternatively, it could slow the adoption of renewables and, done poorly, release toxic chemicals into water and air. Primary threats to water resources include surface spills, wastewater disposal, and drinking-water contamination through poor well integrity. An increase in volatile organic compounds and air toxics locally are potential health threats, but the switch from coal to natural gas for electricity generation will reduce sulfur, nitrogen, mercury, and particulate air pollution. Data gaps are particularly evident for human health studies, for the question of whether natural gas will displace coal compared with renewables, and for decadal-scale legacy issues of well leakage and plugging and abandonment practices. Critical topics for future research include data for (a) estimated ultimate recovery (EUR) of unconventional hydrocarbons, (b) the potential for further reductions of water requirements and chemical toxicity, (c) whether unconventional resource development alters the frequency of well integrity failures, (d) potential contamination of surface and ground waters from drilling and spills, (e) factors that could cause wastewater injection to generate large earthquakes, and (f) the consequences of greenhouse gases and air pollution on ecosystems and human health.
Surface water partial pressure of CO2 (pCO2) variations in Drake Passage are examined using decade-long underway shipboard measurements. North of the Polar Front (PF), the observed pCO2 shows a seasonal cycle that peaks annually in August and dissolved inorganic carbon (DIC)–forced variations are significant. Just south of the PF, pCO2 shows a small seasonal cycle that peaks annually in February, reflecting the opposing effects of changes in SST and DIC in the surface waters. At the PF, the wintertime pCO2 is nearly in equilibrium with the atmosphere, leading to a small sea-to-air CO2 flux.
These observations are used to evaluate eight available Coupled Model Intercomparison Project, phase 5 (CMIP5), Earth system models (ESMs). Six ESMs reproduce the observed annual-mean pCO2 values averaged over the Drake Passage region. However, the model amplitude of the pCO2 seasonal cycle exceeds the observed amplitude of the pCO2 seasonal cycle because of the model biases in SST and surface DIC. North of the PF, deep winter mixed layers play a larger role in pCO2 variations in the models than they do in observations. Four ESMs show elevated wintertime pCO2 near the PF, causing a significant sea-to-air CO2 flux. Wintertime winds in these models are generally stronger than the satellite-derived winds. This not only magnifies the sea-to-air CO2 flux but also upwells DIC-rich water to the surface and drives strong equatorward Ekman currents. These strong model currents likely advect the upwelled DIC farther equatorward, as strong stratification in the models precludes subduction below the mixed layer.
We propose here a novel approach for retrieving in parallel the effective density and real refractive index of weakly absorbing aerosol from optical and size distribution measurements. Here we define “weakly absorbing” as aerosol single-scattering albedos that exceed 0.95 at 0.5 μm. The required optical measurements are the scattering coefficient and the hemispheric backscatter fraction, obtained in this work from an integrating nephelometer. The required size spectra come from mobility and aerodynamic particle size spectrometers commonly referred to as a scanning mobility particle sizer and an aerodynamic particle sizer. The performance of this approach is first evaluated using a sensitivity study with synthetically generated but measurement related inputs. The sensitivity study reveals that the proposed approach is robust to random noise; additionally the uncertainties of the retrieval are almost linearly proportional to the measurement errors, and these uncertainties are smaller for the real refractive index than for the effective density. Next, actual measurements are used to evaluate our approach. These measurements include the optical, microphysical, and chemical properties of weakly absorbing aerosol which are representative of a variety of coastal summertime conditions observed during the Two-Column Aerosol Project (TCAP; http://campaign.arm.gov/tcap/). The evaluation includes calculating the root mean square error (RMSE) between the aerosol characteristics retrieved by our approach, and the same quantities calculated using the conventional volume mixing rule for chemical constituents. For dry conditions (defined in this work as relative humidity less than 55 %) and sub-micron particles, a very good (RMSE3 %) and reasonable (RMSE28 %) agreement is obtained for the retrieved real refractive index (1.49±0.02) and effective density (1.68±0.21), respectively. Our approach permits discrimination between the retrieved aerosol characteristics of sub-micron and sub-10-micron particles. The evaluation results also reveal that the retrieved density and refractive index tend to decrease with an increase of the relative humidity.
We present here a simple retrieval of the areal-averaged spectral surface albedo using only ground-based measurements of atmospheric transmission under fully overcast conditions. Our retrieval is based on a one-line equation. The feasibility of our retrieval for routine determinations of albedo is demonstrated for different landscapes with various degrees of heterogeneity using three sets of measurements: (1) spectral atmospheric transmission from the Multi-Filter Rotating Shadowband Radiometer (MFRSR) at five wavelengths (415, 500, 615, 673, and 870 nm); (2) tower-based measurements of local surface albedo at the same wavelengths; and (3) areal-averaged surface albedo at four wavelengths (470, 560, 670 and 860 nm) from collocated and coincident Moderate Resolution Imaging Spectroradiometer (MODIS) observations. These integrated datasets cover both temporally long (2008–2013) and short (April–May 2010) periods at the Atmospheric Radiation Measurement (ARM) Southern Great Plains site and the National
Oceanic and Atmospheric Administration (NOAA) Table Mountain site, respectively. The calculated root mean square error (RMSE), defined here as the root mean squared difference between the MODIS-derived surface albedo and the retrieved areal-averaged albedo, is quite small (RMSE ≤ 0.015) and comparable with that obtained previously by other investigators for the shortwave broadband albedo. Good agreement between tower-based measurements of daily-averaged surface albedo for completely overcast and non-overcast conditions is also demonstrated.
The response of the carbon cycle in prognostic Earth system models (ESMs) contributes significant uncertainty to projections of global climate change. Quantifying contributions of known drivers of interannual variability in the growth rate of atmospheric carbon dioxide (CO2) is important for improving the representation of terrestrial ecosystem processes in these ESMs. Several recent studies have identified the temperature dependence of tropical net ecosystem exchange (NEE) as a primary driver of this variability by analyzing a single, globally averaged time series of CO2 anomalies. Here we examined how the temporal evolution of CO2 in different latitude bands may be used to separate contributions from temperature stress, drought stress, and fire emissions to CO2 variability. We developed atmospheric CO2 patterns from each of these mechanisms during 1997–2011 using an atmospheric transport model. NEE responses to temperature, NEE responses to drought, and fire emissions all contributed significantly to CO2 variability in each latitude band, suggesting that no single mechanism was the dominant driver. We found that the sum of drought and fire contributions to CO2 variability exceeded direct NEE responses to temperature in both the Northern and Southern Hemispheres. Additional sensitivity tests revealed that these contributions are masked by temporal and spatial smoothing of CO2 observations. Accounting for fires, the sensitivity of tropical NEE to temperature stress decreased by 25% to 2.9 ± 0.4 Pg C yr−1 K−1. These results underscore the need for accurate attribution of the drivers of CO2 variability prior to using contemporary observations to constrain long-term ESM responses.
Near-surface ozone depletion events (ODEs) generally occur in the Arctic spring, and the frequency shows large interannual variations. We use surface ozone measurements at Barrow, Alert, and Zeppelinfjellet to analyze if their variations are due to climate variability. In years with frequent ODEs at Barrow and Alert, the western Pacific (WP) teleconnection pattern is usually in its negative phase, during which the Pacific jet is strengthened but the storm track originated over the western Pacific is weakened. Both factors tend to reduce the transport of ozone-rich air mass from midlatitudes to the Arctic, creating a favorable environment for the ODEs. The correlation of ODE frequencies at Zeppelinfjellet with WP indices is higher in the 2000s, reflecting stronger influence of the WP pattern in recent decade to cover ODEs in broader Arctic regions. We find that the WP pattern can be used to diagnose ODE changes and subsequent environmental impacts in the Arctic spring.
We present a description of the NASA Aura Tropospheric Emission Spectrometer (TES) carbonyl sulfide (OCS) retrieval algorithm for oceanic observations, along with evaluation of the biases and uncertainties using aircraft profiles from the HIPPO (HIAPER Pole-to-Pole Observations) campaign and data from the NOAA Mauna Loa site. In general, the OCS retrievals (1) have less than 1.0 degree of freedom for signals (DOFs), (2) are sensitive in the mid-troposphere with a peak sensitivity typically between 300 and 500 hPa, (3) but have much smaller systematic errors from temperature, CO2 and H2O calibrations relative to random errors from measurement noise. We estimate the monthly means from TES measurements averaged over multiple years so that random errors are reduced and useful information about OCS seasonal and latitudinal variability can be derived. With this averaging, TES OCS data are found to be consistent (within the calculated uncertainties) with NOAA ground observations and HIPPO aircraft measurements. TES OCS data also captures the seasonal and latitudinal variations observed by these in situ data.
We present the results of an extensive validation program of the most recent version of ozone vertical profiles retrieved with the IMK/IAA (Institute for Meteorology and Climate Research/Instituto de Astrofísica de Andalucía) MIPAS (Michelson Interferometer for Passive Atmospheric Sounding) research level 2 processor from version 5 spectral level 1 data. The time period covered corresponds to the reduced spectral resolution period of the MIPAS instrument, i.e., January 2005–April 2012. The comparison with satellite instruments includes all post-2005 satellite limb and occultation sensors that have measured the vertical profiles of tropospheric and stratospheric ozone: ACE-FTS, GOMOS, HALOE, HIRDLS, MLS, OSIRIS, POAM, SAGE II, SCIAMACHY, SMILES, and SMR. In addition, balloon-borne MkIV solar occultation measurements and ground-based Umkehr measurements have been included, as well as two nadir sensors: IASI and SBUV. For each reference data set, bias determination and precision assessment are performed. Better agreement with reference instruments than for the previous data version, V5R_O3_220 (Laeng et al., 2014), is found: the known high bias around the ozone vmr (volume mixing ratio) peak is significantly reduced and the vertical resolution at 35 km has been improved. The agreement with limb and solar occultation reference instruments that have a known small bias vs. ozonesondes is within 7% in the lower and middle stratosphere and 5% in the upper troposphere. Around the ozone vmr peak, the agreement with most of the satellite reference instruments is within 5%; this bias is as low as 3% for ACE-FTS, MLS, OSIRIS, POAM and SBUV.
We analyze background surface ozone (O3) concentrations as estimated by coupled GEOS-Chem/CAMx models for 23 monitoring sites across the US at high- and low-elevation, rural and urban locations during 2006. Specifically, we consider hourly contributions from global tropospheric O3entering North America, stratospheric O3 over North America, and natural O3 formed from continental biogenic, fire, and lightning sources according to CAMx source apportionment calculations. Unlike historical modeled background definitions that reflect the absence of anthropogenic emissions, we define "Emissions-Influenced Background" (EIB), which includes chemical interactions with anthropogenic emissions and thus reflects "current" background levels at the sites analyzed. We further define global background O3 (GBO3) as the sum of the global tropospheric and stratospheric components and find that higher modeled GBO3 occurs during the spring at sites across the US. At many of the sites during the spring, fall, and winter months higher GBO3 is associated with more frequent stratosphere-to-troposphere transport to the surface (STT-S) events according to independent three-dimensional trajectories based on global meteorological analyses. Patterns of higher spring EIB O3 are followed by lower values during the summer, due to heightened chemical interaction with anthropogenic sources, which are then followed by rising EIB O3 during the fall and winter months. For some high-elevation western US sites, this seasonal pattern is less discernible due to relatively small anthropogenic contributions and the high EIB O3 estimated throughout the year. EIB O3 at all high-elevation sites contributes a significant proportion to total O3 throughout the year and throughout the observed total O3 frequency distribution, while EIB O3 at most urban sites contributes a major portion to total O3 during non-summer months and to the mid-range concentrations (30-50 ppb) of the frequency distribution.
Accurate assessment of anthropogenic carbon dioxide (CO2) emissions and their redistribution among the atmosphere, ocean, and terrestrial biosphere is important to better understand the global carbon cycle, support the development of climate policies, and project future climate change. Here we describe data sets and a methodology to quantify all major components of the global carbon budget, including their uncertainties, based on the combination of a range of data, algorithms, statistics and model estimates and their interpretation by a broad scientific community. We discuss changes compared to previous estimates, consistency within and among components, alongside methodology and data limitations. CO2 emissions from fossil-fuel combustion and cement production (EFF) are based on energy statistics, while emissions from land-use change (ELUC), mainly deforestation, are based on combined evidence from land-cover change data, fire activity associated with deforestation, and models. The global atmospheric CO2 concentration is measured directly and its rate of growth (GATM) is computed from the annual changes in concentration. The mean ocean CO2 sink (SOCEAN) is based on observations from the 1990s, while the annual anomalies and trends are estimated with ocean models. The variability in SOCEAN is evaluated for the first time in this budget with data products based on surveys of ocean CO2 measurements. The global residual terrestrial CO2 sink (SLAND) is estimated by the difference of the other terms of the global carbon budget and compared to results of independent dynamic global vegetation models forced by observed climate, CO2 and land cover change (some including nitrogen–carbon interactions). All uncertainties are reported as ±1σ, reflecting the current capacity to characterise the annual estimates of each component of the global carbon budget. For the last decade available (2003–2012), EFF was 8.6 ± 0.4 GtC yr−1, ELUC 0.9 ± 0.5 GtC yr−1, GATM 4.3 ± 0.1 GtC yr−1, SOCEAN 2.5 ± 0.5 GtC yr−1, and SLAND 2.8 ± 0.8 GtC yr−1. For year 2012 alone, EFF grew to 9.7 ± 0.5 GtC yr−1, 2.2% above 2011, reflecting a continued growing trend in these emissions, GATM was 5.1 ± 0.2 GtC yr−1, SOCEAN was 2.9 ± 0.5 GtC yr−1, and assuming an ELUC of 1.0 ± 0.5 GtC yr−1 (based on the 2001–2010 average), SLAND was 2.7 ± 0.9 GtC yr−1. GATM was high in 2012 compared to the 2003–2012 average, almost entirely reflecting the high EFF. The global atmospheric CO2 concentration reached 392.52 ± 0.10 ppm averaged over 2012. We estimate that EFF will increase by 2.1% (1.1–3.1%) to 9.9 ± 0.5 GtC in 2013, 61% above emissions in 1990, based on projections of world gross domestic product and recent changes in the carbon intensity of the economy. With this projection, cumulative emissions of CO2 will reach about 535 ± 55 GtC for 1870–2013, about 70% from EFF (390 ± 20 GtC) and 30% from ELUC (145 ± 50 GtC).
This paper also documents any changes in the methods and data sets used in this new carbon budget from previous budgets (Le Quéré et al., 2013). All observations presented here can be downloaded from the Carbon Dioxide Information Analysis Center (doi:10.3334/CDIAC/GCP_2013_V2.3).
Natural gas production is associated with emissions of several trace gases, some of them classified as air toxics. While volatile organic compounds (VOCs) have received much attention, hydrogen sulfide (H2S) can also be of concern due to the known health impacts of exposure to this hazardous air pollutant. Here, we present quantitative, fast time-response measurements of H2S using protontransfer-reaction mass-spectrometry (PTR-MS) instruments. An ultra-light-weight PTR-MS (ULW-PTR-MS) in a mobile laboratory was operated for measurements of VOCs and H2S in a gas and oil field during the Uintah Basin Winter Ozone Study (UBWOS) 2012 campaign. Measurements of VOCs and H2S by a PTR-MS were also made at the Horse Pool ground site in the Uintah Basin during UBWOS 2013. The H2S measurement by PTR-MS is strongly humidity dependent because the proton affinity of H2S is only slightly higher than that of water. The H2S sensitivity of PTR-MS ranged between 0.6–1.4 ncps ppbv−1 during UBWOS 2013. We compare the humidity dependence determined in the laboratory with in-field calibrations and determine the H2S mixing ratios for the mobile and ground measurements. The PTR-MS measurements at Horse Pool are evaluated by comparison with simultaneous H2S measurements using a PTR time-offlight MS (PTR-ToF-MS) and a Picarro cavity ring down spectroscopy (CRDS) instrument for H2S /CH4. On average 0.6±0.3 ppbv H2S was present at Horse Pool during UBWOS 2013. The correlation between H2S and methane enhancements suggests that the source of H2S is associated
with oil and gas extraction in the basin. Significant H2S mixing ratios of up to 9 ppmv downwind of storage tanks were observed during the mobile measurements. This study suggests that H2S emissions associated with oil and gas production can lead to short-term high levels close to point sources, and elevated background levels away from those sources. In addition, our work has demonstrated that PTR-MS can make reliable measurements of H2S at levels below 1 ppbv.
Carbon tetrachloride (CCl4) is a major anthropogenic ozone-depleting substance and greenhouse gas and has been regulated under the Montreal Protocol. However, the near-zero 2007–2012 emissions estimate based on the UNEP reported production and feedstock usage cannot be reconciled with the observed slow decline of atmospheric concentrations and the inter-hemispheric gradient (IHG) for CCl4. Our 3-D model simulations suggest that the observed IHG (1.5 ± 0.2 ppt for 2000–2012) is primarily caused by ongoing current emissions, while ocean and soil losses and stratosphere-troposphere exchange together contribute a small negative gradient (~0 – −0.3 ppt). Using the observed CCl4 global trend and IHG, we deduce that the mean global emissions for the 2000–2012 period are 
Gg/yr (~30% of the peak 1980s emissions) and a corresponding total lifetime of 
years.
A potent greenhouse gas and biological irritant, tropospheric ozone is also the primary source of atmospheric hydroxyl radicals, which remove numerous hazardous trace gases from the atmosphere. Tropospheric ozone levels have increased in spring at remote sites in the mid-latitudes of the Northern Hemisphere over the past few decades; this increase has been attributed to a growth in Asian precursor emissions. In contrast, 40 years of continuous measurements at Mauna Loa Observatory in Hawaii reveal little change in tropospheric ozone levels during spring (March–April), but a rise in autumn (September–October). Here we examine the contribution of decadal shifts in atmospheric circulation patterns to decadal variability in tropospheric ozone levels at Mauna Loa using a suite of chemistry–climate model simulations. We show that the flow of ozone-rich air from Eurasia towards Hawaii during spring weakened in the 2000s as a result of La-Niña-like decadal cooling in the eastern equatorial Pacific Ocean. During autumn, in contrast, the flow of ozone-rich air from Eurasia to Hawaii strengthened in the mid-1990s onwards, coincident with the positive phase of the Pacific–North American pattern. We suggest that these shifts in atmospheric circulation patterns can reconcile observed trends in tropospheric ozone levels at Mauna Loa and the northern mid-latitudes in recent decades. We conclude that decadal variability in atmospheric circulation patterns needs to be considered when attributing observed changes in tropospheric ozone levels to human-induced trends in precursor emissions.
Using observational data from 2007 to 2010 at the Waliguan and Shangdianzi stations in China, atmospheric CO2, its δ13C composition, and their potential relationship with sources and sinks are studied. Results suggest that at Waliguan (WLG) station, both CO2 and δ13C possess long-term trends and seasonal cycles that correlate well with each other. CO2 and δ13C interannual variations indicate terrestrial ecosystem source-sink seasonal features in the midlatitude to high-latitude Northern Hemisphere. CO2 annual means vary from 384.0 ppm to 390.2 ppm and increase in an approximately linear manner with a mean annual growth rate of 2.1 ± 0.1 ppm. The δ13C annual means vary from −8.30‰ to −8.35‰ and decrease almost linearly with a mean annual rate of −0.02‰ ± 0.001‰. Under the given conditions of terrestrial biosphere and anthropogenic activities at Shangdianzi (SDZ) station, the CO2 annual means vary from 385.1 ppm to 390.6 ppm and approximately increase linearly with a mean annual growth rate of 1.8 ± 0.1 ppm. The peak-to-peak annual seasonal amplitude is 23.0 ppm. The δ13C annual means vary from −8.27‰ to −8.36‰ between 2009 and 2010. Mean values of −25.44‰ ± 0.72‰ and −21.70‰ ± 0.67‰ for the respective sources are obtained at WLG and SDZ. The estimated δs values are more negative in winter and spring than in summer and autumn at WLG. While because substantial C4 photosynthesis taking place in summer and biomass burning strongly contribute in winter, the estimated δs values at SDZ are unusually heavier throughout the year and more positive than those at WLG.
Methyl chloroform (MCF) is a man-made chlorinated solvent contributing to the destruction of stratospheric ozone and is controlled under the "Montreal Protocol on Substances that Deplete the Ozone Layer" and its amendments, which called for its phase-out in 1996 in developed countries and 2015 in developing countries. Long-term, high-frequency observations of MCF carried out at three European sites show a constant decline in the background mixing ratios of MCF. However, we observe persistent non-negligible mixing ratio enhancements of MCF in pollution episodes, suggesting unexpectedly high ongoing emissions in Europe. In order to identify the source regions and to give an estimate of the magnitude of such emissions, we have used a Bayesian inversion method and a point source analysis, based on high-frequency long-term observations at the three European sites.
The inversion identified southeastern France (SEF) as a region with enhanced MCF emissions. This estimate was confirmed by the point source analysis. We performed this analysis using an 11-year data set, from January 2002 to December 2012. Overall, emissions estimated for the European study domain decreased nearly exponentially from 1.1 Gg yr−1 in 2002 to 0.32 Gg yr−1 in 2012, of which the estimated emissions from the SEF region accounted for 0.49 Gg yr−1 in 2002 and 0.20 Gg yr−1 in 2012. The European estimates are a significant fraction of the total semi-hemisphere (30–90° N) emissions, contributing a minimum of 9.8% in 2004 and a maximum of 33.7% in 2011, of which on average 50% are from the SEF region. On the global scale, the SEF region is thus responsible for a minimum of 2.6% (in 2003) and a maximum of 10.3% (in 2009) of the global MCF emissions.
Many of the next generation of global climate models will include aerosol schemes which explicitly simulate the microphysical processes that determine the particle size distribution. These models enable aerosol optical properties and cloud condensation nuclei (CCN) concentrations to be determined by fundamental aerosol processes, which should lead to a more physically based simulation of aerosol direct and indirect radiative forcings. This study examines the global variation in particle size distribution simulated by 12 global aerosol microphysics models to quantify model diversity and to identify any common biases against observations. Evaluation against size distribution measurements from a new European network of aerosol supersites shows that the mean model agrees quite well with the observations at many sites on the annual mean, but there are some seasonal biases common to many sites. In particular, at many of these European sites, the accumulation mode number concentration is biased low during winter and Aitken mode concentrations tend to be overestimated in winter and underestimated in summer. At high northern latitudes, the models strongly underpredict Aitken and accumulation particle concentrations compared to the measurements, consistent with previous studies that have highlighted the poor performance of global aerosol models in the Arctic. In the marine boundary layer, the models capture the observed meridional variation in the size distribution, which is dominated by the Aitken mode at high latitudes, with an increasing concentration of accumulation particles with decreasing latitude. Considering vertical profiles, the models reproduce the observed peak in total particle concentrations in the upper troposphere due to new particle formation, although modelled peak concentrations tend to be biased high over Europe. Overall, the multi-model-mean data set simulates the global variation of the particle size distribution with a good degree of skill, suggesting that most of the individual global aerosol microphysics models are performing well, although the large model diversity indicates that some models are in poor agreement with the observations. Further work is required to better constrain size-resolved primary and secondary particle number sources, and an improved understanding of nucleation and growth (e.g. the role of nitrate and secondary organics) will improve the fidelity of simulated particle size distributions.
We have extensively evaluated the response of cloud base drizzle rate (Rcb; mm d−1) in warm clouds to liquid water path (LWP; g m−2) and to cloud condensation nuclei (CCN) number concentration (NCCN; cm−3), an aerosol proxy. This evaluation is based on a 19 month long data set of Doppler radar, lidar, microwave radiometers, and aerosol observing systems from the Atmospheric Radiation Measurement (ARM) Mobile Facility deployments at the Azores and in Germany. Assuming 0.55% supersaturation to calculate NCCN, we found a power law 
, indicating that Rcb decreases by a factor of 2–3 as NCCN increases from 200 to 1000 cm−3 for fixed LWP. Additionally, the precipitation susceptibility to NCCN ranges between 0.5 and 0.9, in agreement with values from simulations and aircraft measurements. Surprisingly, the susceptibility of the probability of precipitation from our analysis is much higher than that from CloudSat estimates but agrees well with simulations from a multiscale high-resolution aerosol-climate model. Although scale issues are not completely resolved in the intercomparisons, our results are encouraging, suggesting that it is possible for multiscale models to accurately simulate the response of LWP to aerosol perturbations.
Observation Package (ObsPack) is a framework designed to bring together atmospheric greenhouse gas observations from a variety of sampling platforms, prepare them with specific applications in mind, and package and distribute them in a self-consistent and well-documented product. Data products created using the ObsPack framework (called "ObsPack products") are intended to support carbon cycle modeling studies and represent a next generation of value-added greenhouse gas observation products modeled after the cooperative GLOBALVIEW products introduced in 1996. Depending on intended use, ObsPack products may include data in their original form reformatted using the ObsPack framework or may contain derived data consisting of averages, subsets, or smoothed representations of original data. All products include extensive ancillary information (metadata) intended to help ensure the data are used appropriately, their calibration and quality assurance history are clearly described, and that individuals responsible for the measurements (data providers or principal investigators (PIs)) are properly acknowledged for their work. ObsPack products are made freely available using a distribution strategy designed to improve communication between data providers and product users. The strategy includes a data usage policy that requires users to directly communicate with data providers and an automated e-mail notification system triggered when a product is accessed. ObsPack products will be assigned a unique digital object identifier (DOI) to ensure each product can be unambiguously identified in scientific literature. Here we describe the ObsPack framework and its potential role in supporting the evolving needs of both data providers and product users.
To the Editor
We share the excitement on the launch of OCO-2 and appreciate the editorial on the importance of observations of atmospheric carbon dioxide (Nature Geosci. 7, 549; 2014). However, we would like to point out that OCO-2 is essentially an exploratory mission to figure out the extent to which carbon dioxide can be precisely and accurately measured from space. If OCO-2's carbon dioxide measurements improve our understanding of the carbon cycle, this will be a bonus.
From experience with the Japanese GOSAT satellite, which has been in orbit for five years, we know already that there will be significant challenges in interpreting the data, despite the fact that OCO-2 is expected to have higher performance. It is by no means a forgone conclusion that “Carbon dioxide sources and sinks can now be measured from space at high resolution”.
For this to occur, the signals received by OCO-2 first need to be attributed unambiguously to variations in atmospheric CO2 concentrations (via a radiative transfer model), as opposed to variations caused, for example, by aerosols, thin clouds or other artefacts. The stringent requirement for in situ measurements is that they are free of bias to 0.1 ppm against a global ambient level of 400 ppm. Second, even if unbiased CO2 retrievals are obtained, translating atmospheric CO2 abundance to sources and sinks requires the intermediary of an excellent model of horizontal and vertical atmospheric motion — no mean feat.
Extensive validation of both OCO-2's CO2 retrievals and atmospheric transport models will be needed before calculations of sources and sinks are credible enough to contribute in the policy arena. This will require significant investment to supplement existing networks of well-calibrated in situ CO2 measurements from surface and airborne platforms, such as NOAA's Global Greenhouse Gas Reference Network (www.esrl.noaa.gov/gmd/ccgg/ggrn.php) or the Japanese CONTRAIL aircraft observation programme (www.cger.nies.go.jp/contrail/index.html).
OCO-2 and similar satellite missions represent ambitious and necessary experiments of how to determine carbon sources and sinks on the surface. Although the potential of satellite-based CO2 sensors is great, in the long run it will likely be a combination of remotely sensed and in situ CO2 measurements that will produce the trusted answers that society needs.
Wetlands comprise the single largest global source of atmospheric methane, but current flux estimates disagree in both magnitude and distribution at the continental scale. This study uses atmospheric methane observations over North America from 2007 to 2008 and a geostatistical inverse model to improve understanding of Canadian methane fluxes and associated biogeochemical models. The results bridge an existing gap between traditional top-down, inversion studies, which typically emphasize total emission budgets, and biogeochemical models, which usually emphasize environmental processes. The conclusions of this study are threefold. First, the most complete process-based methane models do not always describe available atmospheric methane observations better than simple models. In this study, a relatively simple model of wetland distribution, soil moisture, and soil temperature outperformed more complex model formulations. Second, we find that wetland methane fluxes have a broader spatial distribution across western Canada and into the northern U.S. than represented in existing flux models. Finally, we calculate total methane budgets for Canada and for the Hudson Bay Lowlands, a large wetland region (50–60°N, 75–96°W). Over these lowlands, we find total methane fluxes of 1.8±0.24 Tg C yr−1, a number in the midrange of previous estimates. Our total Canadian methane budget of 16.0±1.2 Tg C yr−1 is larger than existing inventories, primarily due to high anthropogenic emissions in Alberta. However, methane observations are sparse in western Canada, and additional measurements over Alberta will constrain anthropogenic sources in that province with greater confidence.
Analyses of stratospheric ozone data determined from Dobson–Umkehr measurements since 1977 at the Syowa (69.0° S, 39.6° E), Antarctica, station show a significant decrease in ozone at altitudes higher than that of the 4 hPa pressure level during the 1980s and 1990s. Ozone values over Syowa have remained low since 2001. The time series of upper stratospheric ozone from the homogenized NOAA SBUV (Solar Backscatter Ultraviolet Instrument)(/2) 8.6 overpass data (±4°, 24 h) are in qualitative agreement with those from the Syowa station data. Ozone recovery during the austral spring over the Syowa station appears to be slower than predicted by the equivalent effective stratospheric chlorine (EESC) curve. The long-term changes in the station's equivalent latitude (indicative of vortex size/position in winter and spring) are derived from MERRA (Modern Era Retrospective-analysis for Research and Applications) reanalyses at ~ 2 and ~ 50 hPa. These data are used to attribute some of the upper and middle stratospheric ozone changes to the changes in vortex position relative to the station's location. In addition, high correlation of the Southern Hemisphere annular mode (SAM) with polar upper stratospheric ozone during years of maximum solar activity points toward a strong relationship between the strength of the Brewer–Dobson circulation and the polar stratospheric ozone recovery. In the lower stratosphere, ozone recovery attributable to CFCs (chlorofluorocarbons) is still not definitive, whereas the recovery of the upper stratosphere is slower than predicted. Further research indicates that dynamical and other chemical changes in the atmosphere are delaying detection of recovery over this station.
NOAA halocarbon flasks have been collected at the CGBAPS since the early 1990s. A suite of halocarbons, hydrocarbons, and sulfur-containing gases have been measured in these flasks at NOAA/ESRL/GMD Boulder Laboratories (see Table 1). Results from Cape Grim provide a critical record for understanding how the atmospheric concentrations of trace gases are changing in the remote SH atmosphere (Figure 1). Samples are collected only under background conditions so this data record is predominantly free of local influences, which for some gases emitted from coastal or oceanic environments can be quite substantial at the CGBAPS. Results from this site are among the most consistent records obtained from any site where NOAA flask measurements of halocarbons are made owing to a number of factors: the highly capable observatory staff, the conditional sampling restrictions on collecting flasks employed at the site, and the nature of the site (low mixing ratio variability owing to the site being far removed from the largest sources of most anthropogenically-emitted gases).
A stratospheric trace gas measurement program using balloon-based sonde and AirCore sampler techniques is proposed as a way to monitor the strength of the stratospheric mean meridional or Brewer–Dobson circulation. Modeling work predicts a strengthening of the Brewer–Dobson circulation in response to increasing greenhouse gas concentrations; such a change will likely impact tropospheric climate. Because the strength of the Brewer–Dobson circulation is an unmeasureable quantity, trace gas measurements are used to infer characteristics of the circulation. At present, stratospheric trace gas measurements are sporadic in time and/or place, primarily associated with localized aircraft or balloon campaigns or relatively short-lived satellite instruments. This program would consist of regular trace gas profile measurements taken at multiple latitudes covering tropical, midlatitude, and polar regimes. The program would make use of the relatively low-cost AirCore and sonde techniques, allowing more frequent measurements given the significantly lower cost than with current techniques. The program will provide a means of monitoring changes in the strength and redistribution of the stratospheric circulation. The goals are to monitor the strength of the Brewer–Dobson circulation and to improve understanding of the reasons for stratospheric circulation changes, ultimately resulting in more realistic model predictions of climate change for the coming decades.
We present a new correction scheme for filter-based absorption photometers based on a constrained two-stream (CTS) radiative transfer model and experimental calibrations. The two-stream model was initialized using experimentally accessible optical parameters of the filter. Experimental calibrations were taken from the literature and from dedicated experiments for the present manuscript. Uncertainties in the model and calibration experiments are discussed and uncertainties for retrieval of absorption coefficients are derived. For single-scattering albedos lower than 0.8, the new CTS method and also other correction schemes suffer from the uncertainty in calibration experiments, with an uncertainty of about 20% in the absorption coefficient. For high single-scattering albedos, the CTS correction significantly reduces errors. At a single-scattering albedo of about 0.98 the error can be reduced to 30%, whereas errors using the Bond correction (Bond et al., 1999) are up to 100%. The correction scheme was tested using data from an independent experiment. The tests confirm the modeled performance of the correction scheme when comparing the CTS method to other established correction methods.
Recent observations reveal a seasonally occurring layer of aerosol located from 0° to 100°E, 20° to 45°N and extending vertically from about 13 km to 18 km; this has been termed the Asian tropopause aerosol layer (ATAL), and its existence is closely associated with the Asian summer monsoon circulation. Observational studies argue that the ATAL is a recent phenomenon, as the layer is not observed in the satellite record prior to 1998. This suggests that the ATAL may be of anthropogenic origin associated with a shift in the dominant regional emission of sulfur dioxide (SO2) to China and India in the late 1990s. Here we test the hypothesis that SO2emitted from Asia led to the formation of the ATAL using an aerosol microphysical model coupled to a global chemistry climate model. This is the first modeling study to specifically examine the ATAL and its possible origin. From our results, we conclude that the ATAL is most likely due to anthropogenic emissions, but its source cannot solely be attributed to emissions from Asia. Specifically, the results indicate that Chinese and Indian emissions contribute ∼30% of the sulfate aerosol extinction in the ATAL during volcanically quiescent periods. We also show that even small volcanic eruptions preclude our ability to make any conclusions about the existence of the ATAL before 1998 with observations alone.
NO ABSTRACT - FIRST PARAGRAPH
Roughly one-fifth of the increase in radiative forcing by human-linked greenhouse gases since 1750 is due to methane. The past three decades have seen prolonged periods of increasing atmospheric methane, but the growth rate slowed in the 1990s (1), and from 1999 to 2006, the methane burden (that is, the total amount of methane in the air) was nearly constant. Yet strong growth resumed in 2007. The reasons for these observed changes remain poorly understood because of limited knowledge of what controls the global methane budget (2).
During the winter of 2012–2013 atmospheric surface ozone mole fractions exceeded the US 8 h standard of 75 ppb on 39 days in the Uinta Basin of Utah. As part of the Uinta Basin Winter Ozone Study (UBWOS) aircraft flights were conducted throughout the basin with continuous measurements of ozone (O3), methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), nitrogen dioxide (NO2), and discrete whole air flask samples for determination of ∼50 trace gases including a number of non-methane hydrocarbons (NMHCs). During the course of seven flights conducted between 31 January and 7 February 2013, coinciding with strong, multi-day temperature inversions, O3 levels gradually built up in the shallow boundary layer from ∼45 ppb to ∼140 ppb. Near-surface CH4 mole fractions increased during the episode from near background levels of ∼2 ppm to over 10 ppm. Based on elevated levels of CH4 across the basin and high correlations of CH4 with NMHCs from the discrete air samples, O3 precursor NMHCs were also inferred to be elevated throughout the basin. Discrete plumes of high NO2 were observed in the gas production region of the basin suggesting that gas processing plants and compressor facilities were important point sources of reactive nitrogen oxides (NOx). Vertical profiles obtained during the flights showed that the high O3 mole fractions (as well as other elevated constituents) were confined to a shallow layer from near the ground to 300–400 m above ground level (m a.g.l.) capped by a strong temperature inversion. The highest mole fractions of the measured constituents during the study period were in an isothermal cold layer that varied from ∼300 m depth on 4 February to ∼150 m on 5 February. A gradient layer with declining mole fractions with altitude extended above the isothermal layer to ∼1900 m a.s.l. (300–400 m a.g.l.) indicative of some mixing of air out of the boundary layer. O3 mole fractions continued to increase within the basin as the high O3 episode developed over the course of a week. CH4 mole fractions, on the other hand, leveled off after several days. On several flights, the aircraft sampled the plume of a coal-fired power plant (located east of the main gas field) flowing above the inversion layer. These measurements ruled out the effluents of the power plant as a significant source of NOx for O3 production beneath the temperature inversion in the basin. The presence of elevated O3 precursors within the basin and the rapid daytime production of O3 in the atmosphere beneath the temperature inversion both indicated that O3 was being produced from precursors emitted within the basin beneath the temperature inversion. Although observations show that horizontal winds in the surface layer were relatively light during the high ozone event, they were sufficient to disperse precursors up to 80 km from primary sources in the main gas field in the southeast quadrant to the balance of the Uinta Basin.
Winter maximum daily 8-hour average (MDA8) ozone concentrations in the Upper Green River Basin, Wyoming (UGRBWY) and the Uintah Basin, Utah (UBUT) have frequently exceeded 100 ppb in January, February and March, in the past few years. Such levels are well above the U.S. air quality standard of 75 ppb. In these two remote basins in the Rockies, local ozone precursor emissions result from intense oil and gas extraction activities that release methane, volatile organic compounds (VOCs), and nitrogen oxides (NOx) to the atmosphere. These emissions become trapped beneath a stable and shallow (∼50–200 m) boundary layer maintained in low wind conditions. Wintertime surface ozone formation conditions are more likely in the
UBUT than in the UGRBWY as the topography of the UBUT is an enclosed basin whereas the UGRBWY is open on its southern perimeter thus allowing for more air turnover. With snow-covered ground, high ozone events regularly begin in mid-December and last into early March in the UBUT whereas they usually do not begin in earnest until about a month later in the UGRBWY and may persist until mid-March. Winters without snow cover and the accompanying cold pool meteorological conditions do not experience high ozone events in either basin. For nine years with ozone observations in the UGRBWY (2005–2013) and four in the UBUT (2010–2013), all years with adequate (≥6 inches) and persistent snow cover, experienced days with
ozone values ≥75 ppb except in 2012 in the UGRBWY when persistent high wind (>5 m/s) conditions were prevalent. Year to year differences in the occurrences of high ozone episodes appear to be driven primarily by differing meteorological conditions rather than by variations in ozone precursor levels.
Atmospheric CO were monitored at the Lulin Atmospheric Background Station (LABS) with an elevation of 2862 m AMSL from April 2006 to April 2011 by the in-situ non-dispersive infrared (NDIR) spectrometer and weekly flask sample collections via collaboration with NOAA/ESRL/GMD. In general very coherent results were observed between the two datasets, despite a slight difference between the two. A distinct seasonal pattern of CO was noticed at the LABS with a springtime maximum and a summertime minimum, which was predominately shaped by the long-range transport of biomass burning air masses from Southeast Asia and oceanic influences from the Pacific, respectively. Diurnal cycles were also observed at the LABS, with a maximum in late afternoon and a minimum in early morning. The daytime CO maximum was most likely caused by the up-slope transport of lower elevation air. After filtering out the possibly polluted data points from the entire dataset with a mathematic procedure, the mean background CO level at the LABS was assessed as 129.3 ± 46.6 ppb, compared to 149.0 ± 72.2 ppb prior to the filtering.
The cluster analysis of the backward trajectories revealed six possible source regions, which shows that air masses originating from the Westerly Wind Zone were dominated in spring and winter resulting in higher CO concentrations. As a contrast, the oceanic influences from the Pacific were found mostly in summer, contributing a lower seasonal CO concentration throughout a year.
Thirteen years of ozone soundings at the Antarctic Belgrano II station (78° S, 34.6° W) have been analysed to establish a climatology of stratospheric ozone and temperature over the area. The station is inside the polar vortex during the period of development of chemical ozone depletion. Weekly periodic profiles provide a suitable database for seasonal characterization of the evolution of stratospheric ozone, especially valuable during wintertime, when satellites and ground-based instruments based on solar radiation are not available. The work is focused on ozone loss rate variability (August–October) and its recovery (November–December) at different layers identified according to the severity of ozone loss. The time window selected for the calculations covers the phase of a quasi-linear ozone reduction, around day 220 (mid-August) to day 273 (end of September). Decrease of the total ozone column over Belgrano during spring is highly dependent on the meteorological conditions. Largest depletions (up to 59%) are reached in coldest years, while warm winters exhibit significantly lower ozone loss (20%). It has been found that about 11% of the total O3 loss, in the layer where maximum depletion occurs, takes place before sunlight has arrived, as a result of transport to Belgrano of air from a somewhat lower latitude, near the edge of the polar vortex, providing evidence of mixing inside the vortex. Spatial homogeneity of the vortex has been examined by comparing Belgrano results with those previously obtained for South Pole station (SPS) for the same altitude range and for 9 yr of overlapping data. Results show more than 25% higher ozone loss rate at SPS than at Belgrano. The behaviour can be explained taking into account (i) the transport to both stations of air from a somewhat lower latitude, near the edge of the polar vortex, where sunlight reappears sooner, resulting in earlier depletion of ozone, and (ii) the accumulated hours of sunlight, which become much greater at the South Pole after the spring equinox. According to the variability of the ozone hole recovery, a clear connection between the timing of the breakup of the vortex and the monthly ozone content was found. Minimum ozone concentration of 57 DU in the 12–24 km layer remained in November, when the vortex is more persistent, while in years when the final stratospheric warming took place "very early", mean integrated ozone rose by up to 160–180 DU.
The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere1, 2, 3. The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species such as nitrogen oxides and methane4, 5, 6. It remains poorly constrained, however, with a range of estimates from 0.85 to 1.4 (refs 4, 7,8,9,10). Here we determine the NH/SH ratio of OH with the help of methyl chloroform data (a proxy for OH concentrations) and an atmospheric transport model that accurately describes interhemispheric transport and modelled emissions. We find that for the years 2004–2011 the model predicts an annual mean NH–SH gradient of methyl chloroform that is a tight linear function of the modelled NH/SH ratio in annual mean OH. We estimate a NH/SH OH ratio of 0.97 ± 0.12 during this time period by optimizing global total emissions and mean OH abundance to fit methyl chloroform data from two surface-measurement networks and aircraft campaigns11, 12, 13. Our findings suggest that top-down emission estimates of reactive species such as nitrogen oxides in key emitting countries in the NH that are based on a NH/SH OH ratio larger than 1 may be overestimated.
Emissions of methane (CH4) from oil and natural gas (O&G) operations in the most densely drilled area of the Denver-Julesburg Basin in Weld County located in northeastern Colorado are estimated for 2 days in May 2012 using aircraft-based CH4 observations and planetary boundary layer height and ground-based wind profile measurements. Total top-down CH4 emission estimates are 25.8 ± 8.4 and 26.2 ± 10.7 t CH4/h for the 29 and 31 May flights, respectively. Using inventory data, we estimate the total emissions of CH4 from non-O&G gas-related sources at 7.1 ± 1.7 and 6.3 ± 1.0 t CH4/h for these 2 days. The difference in emissions is attributed to O&G sources in the study region, and their total emission is on average 19.3 ± 6.9 t/h, close to 3 times higher than an hourly emission estimate based on Environmental Protection Agency's Greenhouse Gas Reporting Program data for 2012. We derive top-down emissions estimates for propane, n-butane, i-pentane, n-pentane, and benzene from our total top-down CH4 emission estimate and the relative hydrocarbon abundances in aircraft-based discrete air samples. Emissions for these five nonmethane hydrocarbons alone total 25.4 ± 8.2 t/h. Assuming that these emissions are solely originating from O&G-related activities in the study region, our results show that the state inventory for total volatile organic compounds emitted by O&G activities is at least a factor of 2 too low for May 2012. Our top-down emission estimate of benzene emissions from O&G operations is 173 ± 64 kg/h, or 7 times larger than in the state inventory.
In this study we reexamine nearly four decades of in situ balloon-based stratospheric observations of SF6 and CO2 with an idealized model and reanalysis products. We use new techniques to account for the spatial and temporal inhomogeneity of the sparse balloon profiles and to calculate stratospheric mean ages of air more consistently from the observations with the idealized model. By doing so we are able to more clearly show and account for the variability of mean age of air throughout the bulk of the depth of the stratosphere. From an idealized model guided by the observations, we identify variability in the mean age due to the seasonal cycle of stratospheric transport, the quasi-biennial oscillation in tropical zonal winds, major volcanic eruptions, and linear trends that vary significantly with altitude. We calculate a negative mean age trend in the lowest 5 km of the stratosphere that agrees within uncertainties with a trend calculated from a set of chemistry climate model mean ages in this layer. The mean age trends reverse sign in the middle and upper stratosphere and are in agreement with a previous positive trend estimate using the same observational data set, although we have substantially reduced the uncertainty on the trend. Our analysis shows that a long time series of in situ profile measurements of trace gases such as SF6 and CO2 can be a unique and useful indicator of stratospheric circulation variability on a range of time scales and an important contributor to help validate the stratospheric portion of global chemistry climate models. However, with only SF6 and CO2 measurements, the competing effects on mean age between mean circulation and mixing (tropical entrainment) are not uniquely separable.
The primary ground-based instruments used to report total column ozone (TOC) are Brewer and Dobson spectrophotometers in separate networks. These instruments make measurements of the UV irradiances, and through a well-defined process, a TOC value is produced. Inherent to the algorithm is the use of a laboratory-determined cross-section data set. We used five ozone cross-section data sets: three data sets that are based on measurements of Bass and Paur; one derived from Daumont, Brion and Malicet (DBM); and a new set determined by Institute of Experimental Physics (IUP), University of Bremen. The three Bass and Paur (1985) sets are as follows: quadratic temperature coefficients from the IGACO (a glossary is provided in Appendix A) web page (IGQ4), the Brewer network operational calibration set (BOp), and the set used by Bernhard et al. (2005) in the reanalysis of the Dobson absorption coefficient values (B05). The ozone absorption coefficients for Brewer and Dobson instruments are then calculated using the normal Brewer operative method, which is essentially the same as that used for Dobson instruments.
Considering the standard TOC algorithm for the Brewer instruments and comparing to the Brewer standard operational calibration data set, using the slit functions for the individual instruments, we find the IUP data set changes the calculated TOC by −0.5%, the DBM data set changes the calculated TOC by −3.2%, and the IGQ4 data set at −45 °C changes the calculated TOC by +1.3%.
Considering the standard algorithm for the Dobson instruments, and comparing to results using the official 1992 ozone absorption coefficients values and the single set of slit functions defined for all Dobson instruments, the calculated TOC changes by +1%, with little variation depending on which data set is used.
We applied the changes to the European Dobson and Brewer reference instruments during the Izaña 2012 Absolute Calibration Campaign. With the application of a common Langley calibration and the IUP cross section, the differences between Brewer and Dobson data sets vanish, whereas using those of Bass and Paur and DBM produces differences of 1.5 and 2%, respectively. A study of the temperature dependence of these cross-section data sets is presented using the Arosa, Switzerland, total ozone record of 2003–2006, obtained from two Brewer-type instruments and one Dobson-type instrument, combined with the stratospheric ozone and temperature profiles from the Payerne soundings in the same period. The seasonal dependence of the differences between the results from the various instruments is greatly reduced with the application of temperature-dependent absorption coefficients, with the greatest reduction obtained using the IUP data set.
The growing awareness of climate change/global warming and continuing concerns regarding stratospheric ozone depletion will require future measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track and control the emissions of these species globally in the atmosphere, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. This report describes the results of a pilot study between National Metrology Institutes and atmospheric research laboratories for several of the more important halocarbons at atmospheric concentration levels. The comparison includes the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC 12), trichlorofluoromethane (CFC 11), and 1,1,2-trichlorotrifluoroethane (CFC 113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC 22) and 1-chloro-1,1-difluoroethane (HCFC 142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC 134a), all in a dried whole air sample. The objective of this key comparison is to compare the measurement capabilities of the participants for these halocarbons at trace atmospheric levels.
Studies of climate change increasingly recognize the diverse influences of hydrocarbons in the atmosphere, including roles in particulates and ozone formation. Measurements of key nonmethane hydrocarbons (NMHCs) suggest atmospheric mole fractions ranging from low picomoles per mol (ppt) to nanomoles per mol (ppb), depending on location and compound. To accurately establish mole fraction trends and to relate measurement records from many laboratories and researchers, it is essential to have accurate, stable, calibration standards. In February of 2008, the National Institute of Standards and Technology (NIST) developed and reported on picomoles per mol standards containing 18 nonmethane hydrocarbon compounds covering the mole fraction range of 60 picomoles per mol to 230 picomoles per mol. The stability of these gas mixtures was only characterized over a short time period (2 to 3 months). NIST recently prepared a suite of primary standard gas mixtures by gravimetric dilution to ascertain the stability of the 2008 picomoles per mol NMHC standards suite. The data from this recent chromatographic intercomparison of the 2008 to the 2011 suites confirm a much longer stability of almost 5 years for 15 of the 18 hydrocarbons; the double-bonded alkenes of propene, isobutene, and 1-pentene showed instability, in line with previous publications. The agreement between the gravimetric values from preparation and the analytical mole fractions determined from regression illustrate the internal consistency of the suite within ±2 pmol/mol. However, results for several of the compounds reflect stability problems for the three double-bonded hydrocarbons. An international intercomparison on one of the 2008 standards has also been completed. Participants included National Metrology Institutes, United States government laboratories, and academic laboratories. In general, results for this intercomparison agree to within about ±5% with the gravimetric mole fractions of the hydrocarbons.
Understanding the cooling effect of recent volcanoes is of particular interest in the context of the post-2000 slowing of the rate of global warming. Satellite observations of aerosol optical depth above 15 km have demonstrated that small-magnitude volcanic eruptions substantially perturb incoming solar radiation. Here we use lidar, Aerosol Robotic Network, and balloon-borne observations to provide evidence that currently available satellite databases neglect substantial amounts of volcanic aerosol between the tropopause and 15 km at middle to high latitudes and therefore underestimate total radiative forcing resulting from the recent eruptions. Incorporating these estimates into a simple climate model, we determine the global volcanic aerosol forcing since 2000 to be −0.19 ± 0.09 Wm−2. This translates into an estimated global cooling of 0.05 to 0.12°C. We conclude that recent volcanic events are responsible for more post-2000 cooling than is implied by satellite databases that neglect volcanic aerosol effects below 15 km.
Increasing our understanding of regional greenhouse gas transport, sources, and sinks requires accurate, precise, continuous measurements of small gas enhancements over long ranges. We demonstrate a coherent dual frequency-comb spectroscopy technique capable of achieving these goals. Spectra are acquired spanning 5990 to 6260 cm−1 (1600–1670 nm) covering ∼700 absorption features from CO2, CH4, H2O, HDO, and 13CO2, across a 2 km path. The spectra have sub-1-kHz frequency accuracy, no instrument lineshape, and a 0.0033 cm−1 point spacing. They are fit with different absorption models to yield dry-air mole fractions of greenhouse gases. These results are compared with a point sensor under well-mixed conditions to
evaluate the accuracy of models critical to global satellite-based trace gas monitoring. Under heterogeneous conditions, time-resolved data demonstrate tracking of small variations in mole fractions, with a precision <1 ppm for CO2 and <3 ppb for CH4 in 5 min. Portable systems could enable regional monitoring.
Atmospheric measurements show that emissions of hydrofluorocarbons (HFCs) and hydrochlorofluorocarbons are now the primary drivers of the positive growth in synthetic greenhouse gas (SGHG) radiative forcing. We infer recent SGHG emissions and examine the impact of future emissions scenarios, with a particular focus on proposals to reduce HFC use under the Montreal Protocol. If these proposals are implemented, overall SGHG radiative forcing could peak at around 355 mW m−2 in 2020, before declining by approximately 26% by 2050, despite continued growth of fully fluorinated greenhouse gas emissions. Compared to “no HFC policy” projections, this amounts to a reduction in radiative forcing of between 50 and 240 mW m−2 by 2050 or a cumulative emissions saving equivalent to 0.5 to 2.8 years of CO2 emissions at current levels. However, more complete reporting of global HFC emissions is required, as less than half of global emissions are currently accounted for.
Acquiring accurate measurements of water vapor at the low mixing ratios (< 10 ppm) encountered in the upper troposphere and lower stratosphere (UT/LS) has proven to be a significant analytical challenge evidenced by persistent disagreements between high-precision hygrometers. These disagreements have caused uncertainties in the description of the physical processes controlling dehydration of air in the tropical tropopause layer and entry of water into the stratosphere and have hindered validation of satellite water vapor retrievals. A 2011 airborne intercomparison of a large group of in situ hygrometers onboard the NASA WB-57F high-altitude research aircraft and balloons has provided an excellent opportunity to evaluate progress in the scientific community toward improved measurement agreement. In this work we intercompare the measurements from the Midlatitude Airborne Cirrus Properties Experiment (MACPEX) and discuss the quality of agreement. Differences between values reported by the instruments were reduced in comparison to some prior campaigns but were nonnegligible and on the order of 20% (0.8 ppm). Our analysis suggests that unrecognized errors in the quantification of instrumental background for some or all of the hygrometers are a likely cause. Until these errors are understood, differences at this level will continue to somewhat limit our understanding of cirrus microphysical processes and dehydration in the tropical tropopause layer.
The Palmer Long Term Ecological Research study region west of the Antarctic Peninsula is experiencing warming and changing seasonal sea ice dynamics. Abundance patterns of 3 species of pelagic secondary producers were analyzed for trends, cycles, range extensions or shifts in the location of highest density, and for changes in population dynamics over a 16 yr period (1993-2008). Species analyzed represented different hydrographic regimes and are known to have contrasting responses to seasonal sea ice dynamics: krill Euphausia superba, seasonal sea ice zone; tunicates Salpa thompsoni, warmer waters with minimal sea ice; and larval Antarctic silverfish Pleuragramma antarcticum, cold continental shelf waters. Cycles were observed in grid-wide abundance and recruitment for E. superba. Maximum grid-wide densities did not decrease, but the location of highest densities shifted southward 200 km, away from Adélie penguin rookeries at the northern end. A distinct change post-1999 was apparent in the frequency of occurrence and abundance of S. thompsoni. Mixtures of krill and salps became common, but neither peak densities nor the frequency of peak years for salps increased. As with Antarctic krill, highest salp densities shifted southward alongshore. Larval P. antarcticum were abundant in the northern coastal region in the early 1990s, but virtually disappeared in that region after 1999/2000. Possible mechanisms underlying these observations include the southerly movement of the sea ice edge during spring, changes in proximity of source populations (salps), and changes in transport pathways (larval P. antarcticum). Patterns are compared to those in the SW Atlantic.
No abstract available.
We present a comprehensive estimate of nitrous oxide (N2O) emissions using observations and models from 1995 to 2008. High-frequency records of tropospheric N2O are available from measurements at Cape Grim, Tasmania; Cape Matatula, American Samoa; Ragged Point, Barbados; Mace Head, Ireland; and at Trinidad Head, California using the Advanced Global Atmospheric Gases Experiment (AGAGE) instrumentation and calibrations. The Global Monitoring Division of the National Oceanic and Atmospheric Administration/Earth System Research Laboratory (NOAA/ESRL) has also collected discrete air samples in flasks and in situ measurements from remote sites across the globe and analyzed them for a suite of species including N2O. In addition to these major networks, we include in situ and aircraft measurements from the National Institute of Environmental Studies (NIES) and flask measurements from the Tohoku University and Commonwealth Scientific and Industrial Research Organization (CSIRO) networks. All measurements show increasing atmospheric mole fractions of N2O, with a varying growth rate of 0.1–0.7% per year, resulting in a 7.4% increase in the background atmospheric mole fraction between 1979 and 2011. Using existing emission inventories as well as bottom-up process modeling results, we first create globally gridded a priori N2O emissions over the 37 years since 1975. We then use the three-dimensional chemical transport model, Model for Ozone and Related Chemical Tracers version 4 (MOZART v4), and a Bayesian inverse method to estimate global as well as regional annual emissions for five source sectors from 13 regions in the world. This is the first time that all of these measurements from multiple networks have been combined to determine emissions. Our inversion indicates that global and regional N2O emissions have an increasing trend between 1995 and 2008. Despite large uncertainties, a significant increase is seen from the Asian agricultural sector in recent years, most likely due to an increase in the use of nitrogenous fertilizers, as has been suggested by previous studies.
We present an evaluation of aircraft observations of the carbon and greenhouse gases CO2, CH4, N2O, and CO using a direct-absorption pulsed quantum cascade laser spectrometer (QCLS) operated during the HIPPO and CalNex airborne experiments. The QCLS made continuous 1 Hz measurements with 1σ Allan precisions of 20, 0.5, 0.09, and 0.15 ppb for CO2, CH4, N2O, and CO, respectively, over > 500 flight hours on 79 research flights. The QCLS measurements are compared to two vacuum ultraviolet (VUV) CO instruments (CalNex and HIPPO), a cavity ring-down spectrometer (CRDS) measuring CO2 and CH4 (CalNex), two broadband non-dispersive infrared (NDIR) spectrometers measuring CO2 (HIPPO), two onboard gas chromatographs measuring a variety of chemical species including CH4, N2O, and CO (HIPPO), and various flask-based measurements of all four species. QCLS measurements are tied to NOAA and WMO standards using an in-flight calibration system, and mean differences when compared to NOAA CCG flask data over the 59 HIPPO research flights were 100, 1, 1, and 2 ppb for CO2, CH4, N2O, and CO, respectively. The details of the end-to-end calibration procedures and the data quality assurance and quality control (QA/QC) are presented. Specifically, we discuss our practices for the traceability of standards given uncertainties in calibration cylinders, isotopic and surface effects for the long-lived greenhouse gas tracers, interpolation techniques for in-flight calibrations, and the effects of instrument linearity on retrieved mole fractions.
Natural gas (NG)-related fugitive methane (CH4) emissions estimates from life cycle assessments (LCA) and local field measurements are highly uncertain. Globally distributed long-term atmospheric measurements and top-down modeling can help understand whether LCA and field studies are representative of the global industry average. Attributing sources, such as the NG industry, to global total top-down emissions estimates requires detailed and transparent global a priori bottom-up emissions inventories. Establishing an a priori bottom-up inventory as a tool for top-down modeling is the focus of this work, which extends existing fossil fuel (FF) inventories over the past three decades: (i) It includes ethane (C2H6) emissions, which is a convenient FF tracer gas given available global C2H6 observations. (ii) Fuel specific CH4 and C2H6 emissions uncertainties are quantified. (iii) NG CH4 and C2H6 emissions are estimated for different fugitive emissions rate (FER; % of dry production) scenarios as a basis for quantifying global average FER top-down. While our global oil and coal CH4 estimates coincide well with EDGAR v4.2 for most years, country-level emissions vary substantially, and coal emissions increase at a lower rate over the past decade. Global emissions grid maps are presented for use in top-down modeling.
The amount of methane emissions released by the natural gas (NG) industry is a critical and uncertain value for various industry and policy decisions, such as for determining the climate implications of using NG over coal. Previous studies have estimated fugitive emissions rates (FER)—the fraction of produced NG (mainly methane and ethane) escaped to the atmosphere—between 1 and 9%. Most of these studies rely on few and outdated measurements, and some may represent only temporal/regional NG industry snapshots. This study estimates NG industry representative FER using global atmospheric methane and ethane measurements over three decades, and literature ranges of (i) tracer gas atmospheric lifetimes, (ii) non-NG source estimates, and (iii) fossil fuel fugitive gas hydrocarbon compositions. The modeling suggests an upper bound global average FER of 5% during 2006–2011, and a most likely FER of 2–4% since 2000, trending downward. These results do not account for highly uncertain natural hydrocarbon seepage, which could lower the FER. Further emissions reductions by the NG industry may be needed to ensure climate benefits over coal during the next few decades.
A key question surrounding proposals for climate engineering by increasing Earth's reflection of sunlight is the feasibility of detecting engineered albedo increases from short-duration experiments or prolonged implementation of solar-radiation management. We show that satellite observations permit detection of large increases, but interannual variability overwhelms the maximum conceivable albedo increases for some schemes. Detection of an abrupt global average albedo increase <0.002 (comparable to a ~0.7 W m−2 reduction in radiative forcing) would be unlikely within a year, given a five-year prior record. A three-month experiment in the equatorial zone (5° N–5° S), a potential target for stratospheric aerosol injection, would need to cause an ~0.03 albedo increase, three times larger than that due to the Mount Pinatubo eruption, to be detected. Detection limits for three-month experiments in 1° (latitude and longitude) regions of the subtropical Pacific, possible targets for cloud brightening, are ~0.2, which is larger than might be expected from some model simulations.
An improved version of the vibrating wire sensor, used to measure supercooled cloud liquid water content, was developed by Anasphere Inc. and tested during early 2012. The sensor works on the principle that supercooled liquid will freeze to the vibrating wire and reduce the frequency at a known rate proportional to the liquid water content as the sensor rises through the cloud attached to a weather balloon and radiosonde. The disposable Anasphere sensor interfaces with an InterMet Systems iMet radiosonde. This updated sensor reduces the weight of the instrument while updating the technology when compared to the preceding balloon-borne sensor that was developed in the 1980's by Hill and Woffinden.
Balloon-borne test flights were performed from Boulder, Colorado during February and March of 2012. These flights provided comparisons to integrated liquid water and profiles of liquid water content derived from a collocated multichannel microwave radiometer, built and operated by Radiometrics Corporation. Inter-comparison data such as these are invaluable for calibration, verification and validation of remote-sensing instruments. The data gathered from this sensor are potentially important to detection of icing hazards to aircraft, validation of microphysical output from numerical models, and calibrating remote sensors measuring supercooled liquid water.
Airborne observations from four flights during the 2008 Indirect and Semi-Direct Aerosol Campaign (ISDAC) are used to examine some cloud-free optical, physical, and chemical properties of aerosol particles in the springtime Arctic troposphere. The number concentrations of particles larger than 0.12 µm (Na>120), important for light extinction and cloud droplet formation, ranged from 15 to 2260 cm−3, with the higher Na>120 cases dominated by measurements from two flights of long-range transported biomass burning (BB) aerosols. The two other flights examined here document a relatively clean aerosol and an Arctic Haze aerosol impacted by larger particles largely composed of dust. For observations from the cleaner case and the BB cases, the particle light scattering coefficients at low relative humidity (RH<20%) increased nonlinearly with increasing Na>120, driven mostly by an increase in mean sizes of particles with increasing Na>120 (BB cases). For those three cases, particle light absorption coefficients also increased nonlinearly with increasing Na>120 and linearly with increasing submicron particle volume concentration. In addition to black carbon, brown carbon was estimated to have increased light absorption coefficients by 27% (450 nm wavelength) and 14% (550 nm) in the BB cases. For the case with strong dust influence, the absorption relative to submicron particle volume was small compared with the other cases. There was a slight gradient of Passive Cavity Aerosol Spectrometer Probe (PCASP) mean volume diameter (MVD) towards smaller sizes with increasing height, which suggests more scavenging of the more elevated particles, consistent with a typically longer lifetime of particles higher in the atmosphere. However, in approximately 10% of the cases, the MVD increased (>0.4 µm) with increasing altitude, suggesting transport of larger fine particle mass (possibly coarse particle mass) at high levels over the Arctic. This may be because of transport of larger particles at higher elevations and relatively slow deposition to the surface.
Abstract
Aerosols, transported from distant source regions, influence the Arctic surface radiation budget. When deposited on snow and ice, carbonaceous particles can reduce the surface albedo, which accelerates melting, leading to a temperature-albedo feedback that amplifies Arctic warming. Black carbon (BC), in particular, has been implicated as a major warming agent at high latitudes. BC and co-emitted aerosols in the atmosphere, however, attenuate sunlight and radiatively cool the surface. Warming by soot deposition and cooling by atmospheric aerosols are referred to as “darkening” and “dimming” effects, respectively. In this study, climatologies of spectral aerosol optical depth AOD (2001–2011) and Equivalent BC (EBC) (1989–2011) from three Arctic observatories and from a number of aircraft campaigns are used to characterize Arctic aerosols. Since the 1980s, concentrations of BC in the Arctic have decreased by more than 50% at ground stations where in situ observations are made. AOD has increased slightly during the past decade, with variations attributed to changing emission inventories and source strengths of natural aerosols, including biomass smoke and volcanic aerosol, further influenced by deposition rates and airflow patterns.
Background CO2 mole fraction and seasonal variations, measured at Zhongshan station, Antarctica, for 2010 through 2013, exhibit the expected lowest mole fraction in March with a peak in November. Irrespective of wind direction, the mole fraction of CO2 distributes evenly after polluted air from station operations is removed from the data sets. The daily range of average CO2 mole fraction in all four seasons is small. The monthly mean CO2 mole fraction at Zhongshan station is similar to that of other stations in Antarctica, with seasonal CO2 amplitudes in the order of 384–392 µmol∙mol−1. The annual increase in recent years is about 2 µmol∙mol−1∙yr−1. There is no appreciable difference between CO2 mole fractions around the coast of Antarctica and in the interior, showing that CO2 observed in Antarctica has been fully mixed in the atmosphere as it moves from the north through the southern hemisphere.
We investigated differences in the five currently-available datasets of column-integrated CO2 concentrations (
) retrieved from spectral soundings collected by Greenhouse gases Observing SATellite (GOSAT) and assessed their impact on regional CO2 flux estimates. We did so by estimating the fluxes from each of the five 
datasets combined with surface-based CO2 data, using a single inversion system. The five 
datasets are available in raw and bias-corrected versions, and we found that the bias corrections diminish the range of the five coincident values by ~30% on average. The departures of the five individual inversion results (annual-mean regional fluxes based on 
-surface combined data) from the surface-data-only results were close to one another in some terrestrial regions where spatial coverage by each 
dataset was similar. The mean of the five annual global land uptakes was 1.7 ± 0.3 GtC yr−1, and they were all smaller than the value estimated from the surface-based data alone.
Climatological mean monthly distributions of pH in the total H+ scale, total CO2 concentration (TCO2), and the degree of CaCO3 saturation for the global surface ocean waters (excluding coastal areas) are calculated using a data set for pCO2, alkalinity and nutrient concentrations in surface waters (depths < 50 m), which is built upon the GLODAP, CARINA and LDEO databases. The mutual consistency among these measured parameters is demonstrated using the inorganic carbon chemistry model with the dissociation constants for carbonic acid by Lueker et al. (2000) and for boric acid by Dickson (1990). Linear potential alkalinity-salinity relationships are established for 24 regions of the global ocean. The mean monthly distributions of pH and carbon chemistry parameters for the reference year 2005 are computed using the climatological mean monthly pCO2 data adjusted to a reference year 2005 and the alkalinity estimated from the potential alkalinity-salinity relationships. The equatorial zone (4°N-4°S) of the Pacific is excluded from the analysis because of the large interannual changes associated with ENSO events. The pH thus calculated ranges from 7.9 to 8.2. Lower values are located in the upwelling regions in the tropical Pacific and in the Arabian and Bering Seas; higher values are found in the subpolar and polar waters during the spring-summer months of intense photosynthetic production. The vast areas of subtropical oceans have seasonally varying pH values ranging from 8.05 during warmer months to 8.15 during colder months. The warm tropical and subtropical waters are supersaturated by a factor of as much as 4.2 with respect to aragonite and 6.3 for calcite, whereas the cold subpolar and polar waters are supersaturated by 1.2 for aragonite and 2.0 for calcite because of the lower pH values resulting from greater TCO2 concentrations. In the western Arctic Ocean, aragonite undersaturation is observed. The time-series data from the Bermuda (BATS), Hawaii (HOT) and the Drake Passage show that pH has been declining at a mean rate of about -0.02 pH per decade, and that pCO2 has been increasing at about 19 μatm per decade tracking the atmospheric pCO2 increase rate. This suggests that the ocean acidification is caused primarily by the uptake of atmospheric CO2. The relative importance of the four environmental drivers (temperature, salinity, alkalinity and total CO2 concentration) controlling the seasonal variability of carbonate chemistry at these sites is quantitatively assessed. The ocean carbon chemistry is governed sensitively by the TA/TCO2 ratio, and the rate of change in TA is equally important for the future ocean environment as is the TCO2 in ocean waters increases in the future.
N2O surface fluxes were estimated for 1999 to 2009 using a time-dependent Bayesian inversion technique. Observations were drawn from 5 different networks, incorporating 59 surface sites and a number of ship-based measurement series. To avoid biases in the inverted fluxes, the data were adjusted to a common scale and scale offsets were included in the optimization problem. The fluxes were calculated at the same resolution as the transport model (3.75° longitude × 2.5° latitude) and at monthly time resolution. Over the 11-year period, the global total N2O source varied from 17.5 to 20.1 Tg a−1 N. Tropical and subtropical land regions were found to consistently have the highest N2O emissions, in particular in South Asia (20 ± 3% of global total), South America (13 ± 4%) and Africa (19 ± 3%), while emissions from temperate regions were smaller: Europe (6 ± 1%) and North America (7 ± 2%). A significant multi-annual trend in N2O emissions (0.045 Tg a−2 N) from South Asia was found and confirms inventory estimates of this trend. Considerable interannual variability in the global N2O source was observed (0.8 Tg a−1 N, 1 standard deviation, SD) and was largely driven by variability in tropical and subtropical soil fluxes, in particular in South America (0.3 Tg a−1 N, 1 SD) and Africa (0.3 Tg a−1 N, 1 SD). Notable variability was also found for N2O fluxes in the tropical and southern oceans (0.15 and 0.2 Tg a−1 N, 1 SD, respectively). Interannual variability in the N2O source shows some correlation with the El Niño–Southern Oscillation (ENSO), where El Niño conditions are associated with lower N2O fluxes from soils and from the ocean and vice versa for La Niña conditions.
This study examines N2O emission estimates from five different atmospheric inversion frameworks based on chemistry transport models (CTMs). The five frameworks differ in the choice of CTM, meteorological data, prior uncertainties and inversion method but use the same prior emissions and observation data set. The posterior modelled atmospheric N2O mole fractions are compared to observations to assess the performance of the inversions and to help diagnose problems in the modelled transport. Additionally, the mean emissions for 2006 to 2008 are compared in terms of the spatial distribution and seasonality. Overall, there is a good agreement among the inversions for the mean global total emission, which ranges from 16.1 to 18.7 TgN yr−1 and is consistent with previous estimates. Ocean emissions represent between 31 and 38% of the global total compared to widely varying previous estimates of 24 to 38%. Emissions from the northern mid- to high latitudes are likely to be more important, with a consistent shift in emissions from the tropics and subtropics to the mid- to high latitudes in the Northern Hemisphere; the emission ratio for 0–30° N to 30–90° N ranges from 1.5 to 1.9 compared with 2.9 to 3.0 in previous estimates. The largest discrepancies across inversions are seen for the regions of South and East Asia and for tropical and South America owing to the poor observational constraint for these areas and to considerable differences in the modelled transport, especially inter-hemispheric exchange rates and tropical convective mixing. Estimates of the seasonal cycle in N2O emissions are also sensitive to errors in modelled stratosphere-to-troposphere transport in the tropics and southern extratropics. Overall, the results show a convergence in the global and regional emissions compared to previous independent studies.
We present a comparison of chemistry-transport models (TransCom-N2O) to examine the importance of atmospheric transport and surface fluxes on the variability of N2O mixing ratios in the troposphere. Six different models and two model variants participated in the inter-comparison and simulations were made for the period 2006 to 2009. In addition to N2O, simulations of CFC-12 and SF6 were made by a subset of four of the models to provide information on the models' proficiency in stratosphere–troposphere exchange (STE) and meridional transport, respectively. The same prior emissions were used by all models to restrict differences among models to transport and chemistry alone. Four different N2O flux scenarios totalling between 14 and 17 TgN yr−1 (for 2005) globally were also compared. The modelled N2O mixing ratios were assessed against observations from in situ stations, discrete air sampling networks and aircraft. All models adequately captured the large-scale patterns of N2O and the vertical gradient from the troposphere to the stratosphere and most models also adequately captured the N2O tropospheric growth rate. However, all models underestimated the inter-hemispheric N2O gradient by at least 0.33 parts per billion (ppb), equivalent to 1.5 TgN, which, even after accounting for an overestimate of emissions in the Southern Ocean of circa 1.0 TgN, points to a likely underestimate of the Northern Hemisphere source by up to 0.5 TgN and/or an overestimate of STE in the Northern Hemisphere. Comparison with aircraft data reveal that the models overestimate the amplitude of the N2O seasonal cycle at Hawaii (21° N, 158° W) below circa 6000 m, suggesting an overestimate of the importance of stratosphere to troposphere transport in the lower troposphere at this latitude. In the Northern Hemisphere, most of the models that provided CFC-12 simulations captured the phase of the CFC-12, seasonal cycle, indicating a reasonable representation of the timing of STE. However, for N2O all models simulated a too early minimum by 2 to 3 months owing to errors in the seasonal cycle in the prior soil emissions, which was not adequately represented by the terrestrial biosphere model. In the Southern Hemisphere, most models failed to capture the N2O and CFC-12 seasonality at Cape Grim, Tasmania, and all failed at the South Pole, whereas for SF6, all models could capture the seasonality at all sites, suggesting that there are large errors in modelled vertical transport in high southern latitudes.
Aerosol optical properties were measured by the DOE/ARM (US Department of Energy Atmospheric Radiation Measurements) Program Mobile Facility during the Two-Column Aerosol Project (TCAP) campaign deployed at Cape Cod, Massachusetts, for a 1-year period (from summer 2012 to summer 2013). Measured optical properties included aerosol light-absorption coefficient (σap) at low relative humidity (RH) and aerosol light-scattering coefficient (σsp) at low and at RH values varying from 30 to 85%, approximately. Calculated variables included the single scattering albedo (SSA), the scattering Ångström exponent (SAE) and the scattering enhancement factor (f(RH)). Over the period of measurement, f(RH = 80%) had a mean value of 1.9 ± 0.3 and 1.8 ± 0.4 in the PM10 and PM1 fractions, respectively. Higher f(RH = 80%) values were observed for wind directions from 0 to 180° (marine sector) together with high SSA and low SAE values. The wind sector from 225 to 315° was identified as an anthropogenically influenced sector, and it was characterized by smaller, darker and less hygroscopic aerosols. For the marine sector, f(RH = 80%) was 2.2 compared with a value of 1.8 obtained for the anthropogenically influenced sector. The air-mass backward trajectory analysis agreed well with the wind sector analysis. It shows low cluster to cluster variability except for air masses coming from the Atlantic Ocean that showed higher hygroscopicity. Knowledge of the effect of RH on aerosol optical properties is of great importance for climate forcing calculations and for comparison of in situ measurements with satellite and remote sensing retrievals. In this sense, predictive capability of f(RH) for use in climate models would be enhanced if other aerosol parameters could be used as proxies to estimate hygroscopic growth. Toward this goal, we propose an exponential equation that successfully estimates aerosol hygroscopicity as a function of SSA at Cape Cod. Further work is needed to determine if the equation obtained is valid in other environments.
We present spatial and temporal variations of methyl chloride (CH3Cl) in the upper troposphere (UT) observed mainly by the Civil Aircraft for Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) passenger aircraft for the years 2005–2011. The CH3Cl mixing ratio in the UT over Europe was higher than that observed at a European surface baseline station throughout the year, indicative of a persistent positive vertical gradient at Northern Hemisphere midlatitudes. A series of flights over Africa and South Asia show that CH3Cl mixing ratios increase toward tropical latitudes, and the observed UT CH3Cl level over these two regions and the Atlantic was higher than that measured at remote surface sites. Strong emissions of CH3Cl in the tropics combined with meridional air transport through the UT may explain such vertical and latitudinal gradients. Comparisons with carbon monoxide (CO) data indicate that noncombustion sources in the tropics dominantly contribute to forming the latitudinal gradient of CH3Cl in the UT. We also observed elevated mixing ratios of CH3Cl and CO in air influenced by biomass burning in South America and Africa, and the enhancement ratios derived for CH3Cl to CO in those regions agree with previous observations. In contrast, correlations indicate a high CH3Cl to CO ratio of 2.9 ± 0.5 ppt ppb−1 in the Asian summer monsoon anticyclone and domestic biofuel emissions in South Asia are inferred to be responsible. We estimated the CH3Cl emission in South Asia to be 134 ± 23 Gg Cl yr−1, which is higher than a previous estimate due to the higher CH3Cl to CO ratio observed in this study.
We present an enhanced version of the SiBCASA terrestrial biosphere model that is extended with (a) biomass burning emissions from the SiBCASA carbon pools using remotely sensed burned area from the Global Fire Emissions Database (GFED), (b) an isotopic discrimination scheme that calculates 13C signatures of photosynthesis and autotrophic respiration, and (c) a separate set of 13C pools to carry isotope ratios into heterotrophic respiration. We quantify in this study the terrestrial exchange of CO2 and 13CO2 as a function of environmental changes in humidity and biomass burning.
The implementation of biomass burning yields similar fluxes as CASA-GFED both in magnitude and spatial patterns. The implementation of isotope exchange gives a global mean discrimination value of 15.2‰, ranges between 4 and 20‰ depending on the photosynthetic pathway in the plant, and compares favorably (annually and seasonally) with other published values. Similarly, the isotopic disequilibrium is similar to other studies that include a small effect of biomass burning as it shortens the turnover of carbon. In comparison to measurements, a newly modified starch/sugar storage pool propagates the isotopic discrimination anomalies to respiration much better. In addition, the amplitude of the drought response by SiBCASA is lower than suggested by the measured isotope ratios. We show that a slight increase in the stomatal closure for large vapor pressure deficit would amplify the respired isotope ratio variability. Our study highlights the importance of isotope ratio observations of 13C to assess and improve biochemical models like SiBCASA, especially with regard to the allocation and turnover of carbon and the responses to drought.
Earth system models project that the tropical land carbon sink will decrease in size in response to an increase in warming and drought during this century, probably causing a positive climate feedback. But available data are too limited at present to test the predicted changes in the tropical carbon balance in response to climate change. Long-term atmospheric carbon dioxide data provide a global record that integrates the interannual variability of the global carbon balance. Multiple lines of evidence demonstrate that most of this variability originates in the terrestrial biosphere. In particular, the year-to-year variations in the atmospheric carbon dioxide growth rate (CGR) are thought to be the result of fluctuations in the carbon fluxes of tropical land areas. Recently, the response of CGR to tropical climate interannual variability was used to put a constraint on the sensitivity of tropical land carbon to climate change. Here we use the long-term CGR record from Mauna Loa and the South Pole to show that the sensitivity of CGR to tropical temperature interannual variability has increased by a factor of 1.9 ± 0.3 in the past five decades. We find that this sensitivity was greater when tropical land regions experienced drier conditions. This suggests that the sensitivity of CGR to interannual temperature variations is regulated by moisture conditions, even though the direct correlation between CGR and tropical precipitation is weak. We also find that present terrestrial carbon cycle models do not capture the observed enhancement in CGR sensitivity in the past five decades. More realistic model predictions of future carbon cycle and climate feedbacks require a better understanding of the processes driving the response of tropical ecosystems to drought and warming.
Emissions of volatile organic compounds (VOCs) associated with oil and natural gas production in the Uintah Basin, Utah were measured at a ground site in Horse Pool and from a NOAA mobile laboratory with PTR-MS instruments. The VOC compositions in the vicinity of individual gas and oil wells and other point sources such as evaporation ponds, compressor stations and injection wells are compared to the measurements at Horse Pool. High mixing ratios of aromatics, alkanes, cycloalkanes and methanol were observed for extended periods of time and for short-term spikes caused by local point sources. The mixing ratios during the time the mobile laboratory spent on the well pads were averaged. High mixing ratios were found close to all point sources, but gas well pads with collection and dehydration on the well pad were clearly associated with higher mixing ratios than other wells. The comparison of the VOC composition of the emissions from the oil and natural gas well pads showed that gas well pads without dehydration on the well pad compared well with the majority of the data at Horse Pool, and that oil well pads compared well with the rest of the ground site data. Oil well pads on average emit heavier compounds than gas well pads. The mobile laboratory measurements confirm the results from an emissions inventory: the main VOC source categories from individual point sources are dehydrators, oil and condensate tank flashing and pneumatic devices and pumps. Raw natural gas is emitted from the pneumatic devices and pumps and heavier VOC mixes from the tank flashings.
Ecosystems are important and dynamic components of the global carbon cycle, and terrestrial biospheric models (TBMs) are crucial tools in further understanding of how terrestrial carbon is stored and exchanged with the atmosphere across a variety of spatial and temporal scales.Improving TBM skills, and quantifying and reducing their estimation uncertainties, pose significant challenges. The Multi-scale Synthesis and Terrestrial Model Intercomparison Project (MsTMIP) is a formal multi-scale and multimodel intercomparison effort set up to tackle these challenges. The MsTMIP protocol prescribes standardized environmental driver data that are shared among model teams to facilitate model–model and model–observation comparisons.
This paper describes the global and North American environmental driver data sets prepared for the MsTMIP activity to both support their use in MsTMIP and make these data, along with the processes used in selecting/processing these data, accessible to a broader audience. Based on project needs and lessons learned from past model intercomparison activities, we compiled climate, atmospheric CO2 concentrations, nitrogen deposition, land use and land cover change (LULCC), C3 = C4 grasses fractions, major crops, phenology and soil data into a standard format for global (0.5 0.5 resolution)
and regional (North American: 0.25 0.25 resolution) simulations. In order to meet the needs of MsTMIP, improvements were made to several of the original environmental data sets, by improving the quality, and/or changing their spatial and temporal coverage, and resolution. The resulting
standardized model driver data sets are being used by over 20 different models participating in MsTMIP. The data are archived at the Oak Ridge National Laboratory Distributed Active Archive Center (ORNL DAAC, http://daac.ornl.gov) to provide long-term data management and distribution.
After several years strongly influenced by either La Niña or El Niño events, 2013 was the first full year without either of these phenomena present. Without
the typical large-scale dynamical teleconnections driven by variability within the El Niño-Southern Oscillation (ENSO), 2013 was dominated by patterns
of regional extremes of temperature and especially the hydrological cycle. Regional variations were particularly notable in the Northern Hemisphere extratropics
where anomalously meridional atmospheric circulation occurred throughout much of the year, leading to marked regionally coherent extremes of
heat/cold and dry/wet.
HCFC-22 (CHClF2) and HFC-134a (CH2FCF3) are two major gases currently used worldwide in domestic and commercial refrigeration and air conditioning. HCFC-22 contributes to stratospheric ozone depletion, and both species are potent greenhouse gases. In this work, we study in situ observations of HCFC-22 and HFC-134a taken from research aircraft over the Pacific Ocean in a 3-y span [HIaper-Pole-to-Pole Observations (HIPPO) 2009–2011] and combine these data with long-term ground observations from global surface sites [National Oceanic and Atmospheric Administration (NOAA) and Advanced Global Atmospheric Gases Experiment (AGAGE) networks]. We find the global annual emissions of HCFC-22 and HFC-134a have increased substantially over the past two decades. Emissions of HFC-134a are consistently higher compared with the United Nations Framework Convention on Climate Change (UNFCCC) inventory since 2000, by 60% more in recent years (2009–2012). Apart from these decadal emission constraints, we also quantify recent seasonal emission patterns showing that summertime emissions of HCFC-22 and HFC-134a are two to three times higher than wintertime emissions. This unforeseen large seasonal variation indicates that unaccounted mechanisms controlling refrigerant gas emissions are missing in the existing inventory estimates. Possible mechanisms enhancing refrigerant losses in summer are (i) higher vapor pressure in the sealed compartment of the system at summer high temperatures and (ii) more frequent use and service of refrigerators and air conditioners in summer months. Our results suggest that engineering (e.g., better temperature/vibration-resistant system sealing and new system design of more compact/efficient components) and regulatory (e.g., reinforcing system service regulations) steps to improve containment of these gases from working devices could effectively reduce their release to the atmosphere.
Methane is an important greenhouse gas and tropospheric ozone precursor. Simultaneous observation of ethane with methane can help identify specific methane source types. Aerodyne Ethane-Mini spectrometers, employing recently available mid-infrared distributed feedback tunable diode lasers (DFB-TDL), provide 1 s ethane measurements with sub-ppb precision. In this work, an Ethane-Mini spectrometer has been integrated into two mobile sampling platforms, a ground vehicle and a small airplane, and used to measure ethane/methane enhancement ratios downwind of methane sources. Methane emissions with precisely known sources are shown to have ethane/methane enhancement ratios that differ greatly depending on the source type. Large differences between biogenic and thermogenic sources are observed. Variation within thermogenic sources are detected and tabulated. Methane emitters are classified by their expected ethane content. Categories include the following: biogenic (<0.2%), dry gas (1–6%), wet gas (>6%), pipeline grade natural gas (<15%), and processed natural gas liquids (>30%). Regional scale observations in the Dallas/Fort Worth area of Texas show two distinct ethane/methane enhancement ratios bridged by a transitional region. These results demonstrate the usefulness of continuous and fast ethane measurements in experimental studies of methane emissions, particularly in the oil and natural gas sector.
In this paper we present an estimate of net ecosystem CO2 exchange over China for the years 2001–2010 using the CarbonTracker Data Assimilation System for CO2 (CTDAS). Additional Chinese and Asian CO2 observations are used in CTDAS to improve our estimate. We found that the combined terrestrial ecosystems in China absorbed about −0.33 Pg C yr−1 during 2001–2010. The uncertainty on Chinese terrestrial carbon exchange estimates as derived from a set of sensitivity experiments suggests a range of −0.29 to −0.64 Pg C yr−1. This total Chinese terrestrial CO2 sink is attributed to the three major biomes (forests, croplands, and grass/shrublands) with estimated CO2 fluxes of −0.12 Pg C yr−1 (range from −0.09 to −0.19 Pg C yr−1), −0.12 Pg C yr−1 (range from −0.09 to −0.26 Pg C yr−1), and −0.09 Pg C yr−1 (range from −0.09 to −0.17 Pg C yr−1), respectively. The peak-to-peak amplitude of interannual variability of the Chinese terrestrial ecosystem carbon flux is 0.21 Pg C yr−1 (~64% of mean annual average), with the smallest CO2 sink (−0.19 Pg C yr−1) in 2003 and the largest CO2 sink (−0.40 Pg C yr−1) in 2007. We stress that our estimate of terrestrial ecosystem CO2 uptake based on inverse modeling strongly depends on a limited number of atmospheric CO2 observations used. More observations in China specifically and in Asia in general are needed to improve the accuracy of terrestrial carbon budgeting for this region.
Current estimates of the terrestrial carbon fluxes in Asia show large uncertainties particularly in the boreal and mid-latitudes and in China. In this paper, we present an updated carbon flux estimate for Asia ("Asia" refers to lands as far west as the Urals and is divided into boreal Eurasia, temperate Eurasia and tropical Asia based on TransCom regions) by introducing aircraft CO2 measurements from the CONTRAIL (Comprehensive Observation Network for Trace gases by Airline) program into an inversion modeling system based on the CarbonTracker framework. We estimated the averaged annual total Asian terrestrial land CO2 sink was about −1.56 Pg C yr−1 over the period 2006–2010, which offsets about one-third of the fossil fuel emission from Asia (+4.15 Pg C yr−1). The uncertainty of the terrestrial uptake estimate was derived from a set of sensitivity tests and ranged from −1.07 to −1.80 Pg C yr−1, comparable to the formal Gaussian error of ±1.18 Pg C yr−1 (1-sigma). The largest sink was found in forests, predominantly in coniferous forests (−0.64 ± 0.70 Pg C yr−1) and mixed forests (−0.14 ± 0.27 Pg C yr−1); and the second and third large carbon sinks were found in grass/shrub lands and croplands, accounting for −0.44 ± 0.48 Pg C yr−1 and −0.20 ± 0.48 Pg C yr−1, respectively. The carbon fluxes per ecosystem type have large a priori Gaussian uncertainties, and the reduction of uncertainty based on assimilation of sparse observations over Asia is modest (8.7–25.5%) for most individual ecosystems. The ecosystem flux adjustments follow the detailed a priori spatial patterns by design, which further increases the reliance on the a priori biosphere exchange model. The peak-to-peak amplitude of inter-annual variability (IAV) was 0.57 Pg C yr−1 ranging from −1.71 Pg C yr−1 to −2.28 Pg C yr−1. The IAV analysis reveals that the Asian CO2 sink was sensitive to climate variations, with the lowest uptake in 2010 concurrent with a summer flood and autumn drought and the largest CO2 sink in 2009 owing to favorable temperature and plentiful precipitation conditions. We also found the inclusion of the CONTRAIL data in the inversion modeling system reduced the uncertainty by 11% over the whole Asian region, with a large reduction in the southeast of boreal Eurasia, southeast of temperate Eurasia and most tropical Asian areas.
This study seeks to quantify the roles of soybean and corn plants and the cropland ecosystem in the regional N2O budget of the Upper Midwest, USA. The N2O flux was measured at three scales (plant, the soil–plant ecosystem, and region) using newly designed steady-state flow-through plant chambers, a flux-gradient micrometeorological tower, and continuous tall-tower observatories. Results indicate that the following. (1) N2O fluxes from unfertilized soybean (0.03 ± 0.05 nmol m−2 s−1) and fertilized corn plants (−0.01 ± 0.04 nmol m−2 s−1) were about one magnitude lower than N2O emissions from the soil–plant ecosystem (0.26 nmol m−2 s−1 for soybean and 0.95 nmol m−2 s−1 for corn), confirming that cropland N2O emissions were mainly from the soil. (2) Fertilization increased the corn plant flux for a short period (about 20 days), and late-season fertilization dramatically increased the soybean plant emissions. (3) The direct N2O emission from cropland accounted for less than 20 % of the regional flux, suggesting a significant influence by other sources and indirect emissions, in the regional N2O budget.