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  • 1
    In: Proceedings of the National Academy of Sciences, Proceedings of the National Academy of Sciences, Vol. 118, No. 5 ( 2021-02-02)
    Abstract: Global and regional atmospheric measurements and modeling can play key roles in discovering and quantifying unexpected nascent emissions of environmentally important substances. We focus here on three hydrochlorofluorocarbons (HCFCs) that are restricted by the Montreal Protocol because of their roles in stratospheric ozone depletion. Based on measurements of archived air samples and on in situ measurements at stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, we report global abundances, trends, and regional enhancements for HCFC-132b ( C H 2 C l C C l F 2 ), which is newly discovered in the atmosphere, and updated results for HCFC-133a ( C H 2 C l C F 3 ) and HCFC-31 ( C H 2 ClF). No purposeful end-use is known for any of these compounds. We find that HCFC-132b appeared in the atmosphere 20 y ago and that its global emissions increased to 1.1 Gg ⋅ y −1 by 2019. Regional top-down emission estimates for East Asia, based on high-frequency measurements for 2016–2019, account for ∼ 95% of the global HCFC-132b emissions and for ∼ 80% of the global HCFC-133a emissions of 2.3 Gg ⋅ y −1 during this period. Global emissions of HCFC-31 for the same period are 0.71 Gg ⋅ y −1 . Small European emissions of HCFC-132b and HCFC-133a, found in southeastern France, ceased in early 2017 when a fluorocarbon production facility in that area closed. Although unreported emissive end-uses cannot be ruled out, all three compounds are most likely emitted as intermediate by-products in chemical production pathways. Identification of harmful emissions to the atmosphere at an early stage can guide the effective development of global and regional environmental policy.
    Type of Medium: Online Resource
    ISSN: 0027-8424 , 1091-6490
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    Language: English
    Publisher: Proceedings of the National Academy of Sciences
    Publication Date: 2021
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  • 2
    In: Earth System Science Data, Copernicus GmbH, Vol. 12, No. 3 ( 2020-07-15), p. 1561-1623
    Abstract: Abstract. Understanding and quantifying the global methane (CH4) budget is important for assessing realistic pathways to mitigate climate change. Atmospheric emissions and concentrations of CH4 continue to increase, making CH4 the second most important human-influenced greenhouse gas in terms of climate forcing, after carbon dioxide (CO2). The relative importance of CH4 compared to CO2 depends on its shorter atmospheric lifetime, stronger warming potential, and variations in atmospheric growth rate over the past decade, the causes of which are still debated. Two major challenges in reducing uncertainties in the atmospheric growth rate arise from the variety of geographically overlapping CH4 sources and from the destruction of CH4 by short-lived hydroxyl radicals (OH). To address these challenges, we have established a consortium of multidisciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate new research aimed at improving and regularly updating the global methane budget. Following Saunois et al. (2016), we present here the second version of the living review paper dedicated to the decadal methane budget, integrating results of top-down studies (atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up estimates (including process-based models for estimating land surface emissions and atmospheric chemistry, inventories of anthropogenic emissions, and data-driven extrapolations). For the 2008–2017 decade, global methane emissions are estimated by atmospheric inversions (a top-down approach) to be 576 Tg CH4 yr−1 (range 550–594, corresponding to the minimum and maximum estimates of the model ensemble). Of this total, 359 Tg CH4 yr−1 or ∼ 60 % is attributed to anthropogenic sources, that is emissions caused by direct human activity (i.e. anthropogenic emissions; range 336–376 Tg CH4 yr−1 or 50 %–65 %). The mean annual total emission for the new decade (2008–2017) is 29 Tg CH4 yr−1 larger than our estimate for the previous decade (2000–2009), and 24 Tg CH4 yr−1 larger than the one reported in the previous budget for 2003–2012 (Saunois et al., 2016). Since 2012, global CH4 emissions have been tracking the warmest scenarios assessed by the Intergovernmental Panel on Climate Change. Bottom-up methods suggest almost 30 % larger global emissions (737 Tg CH4 yr−1, range 594–881) than top-down inversion methods. Indeed, bottom-up estimates for natural sources such as natural wetlands, other inland water systems, and geological sources are higher than top-down estimates. The atmospheric constraints on the top-down budget suggest that at least some of these bottom-up emissions are overestimated. The latitudinal distribution of atmospheric observation-based emissions indicates a predominance of tropical emissions (∼ 65 % of the global budget, 〈 30∘ N) compared to mid-latitudes (∼ 30 %, 30–60∘ N) and high northern latitudes (∼ 4 %, 60–90∘ N). The most important source of uncertainty in the methane budget is attributable to natural emissions, especially those from wetlands and other inland waters. Some of our global source estimates are smaller than those in previously published budgets (Saunois et al., 2016; Kirschke et al., 2013). In particular wetland emissions are about 35 Tg CH4 yr−1 lower due to improved partition wetlands and other inland waters. Emissions from geological sources and wild animals are also found to be smaller by 7 Tg CH4 yr−1 by 8 Tg CH4 yr−1, respectively. However, the overall discrepancy between bottom-up and top-down estimates has been reduced by only 5 % compared to Saunois et al. (2016), due to a higher estimate of emissions from inland waters, highlighting the need for more detailed research on emissions factors. Priorities for improving the methane budget include (i) a global, high-resolution map of water-saturated soils and inundated areas emitting methane based on a robust classification of different types of emitting habitats; (ii) further development of process-based models for inland-water emissions; (iii) intensification of methane observations at local scales (e.g., FLUXNET-CH4 measurements) and urban-scale monitoring to constrain bottom-up land surface models, and at regional scales (surface networks and satellites) to constrain atmospheric inversions; (iv) improvements of transport models and the representation of photochemical sinks in top-down inversions; and (v) development of a 3D variational inversion system using isotopic and/or co-emitted species such as ethane to improve source partitioning. The data presented here can be downloaded from https://doi.org/10.18160/GCP-CH4-2019 (Saunois et al., 2020) and from the Global Carbon Project.
    Type of Medium: Online Resource
    ISSN: 1866-3516
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
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  • 3
    In: Nature Geoscience, Springer Science and Business Media LLC, Vol. 16, No. 6 ( 2023-06), p. 546-546
    Type of Medium: Online Resource
    ISSN: 1752-0894 , 1752-0908
    Language: English
    Publisher: Springer Science and Business Media LLC
    Publication Date: 2023
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  • 4
    In: Nature Geoscience, Springer Science and Business Media LLC, Vol. 16, No. 4 ( 2023-04), p. 309-313
    Type of Medium: Online Resource
    ISSN: 1752-0894 , 1752-0908
    Language: English
    Publisher: Springer Science and Business Media LLC
    Publication Date: 2023
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  • 5
    In: Journal of Geophysical Research: Atmospheres, American Geophysical Union (AGU), Vol. 126, No. 1 ( 2021-01-16)
    Abstract: First study to measure a comprehensive set of ozone‐depleting substances in air entering the stratosphere above the Asian summer monsoon Higher than expected mixing ratios found for many compounds, particularly chlorinated very short‐lived substances Regional estimate but the extra equivalent chlorine could significantly enhance the chlorine and bromine loading of the entire stratosphere
    Type of Medium: Online Resource
    ISSN: 2169-897X , 2169-8996
    Language: English
    Publisher: American Geophysical Union (AGU)
    Publication Date: 2021
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  • 6
    Online Resource
    Online Resource
    American Geophysical Union (AGU) ; 2023
    In:  Journal of Geophysical Research: Atmospheres Vol. 128, No. 12 ( 2023-06-27)
    In: Journal of Geophysical Research: Atmospheres, American Geophysical Union (AGU), Vol. 128, No. 12 ( 2023-06-27)
    Abstract: A three‐phased growth of atmospheric N 2 O over the last century, where the growth rate started increasing significantly after 1965 CE While δ 15 N bulk & δ 18 O values have shown a decreasing trend over the last century, a long‐term trend in δ 15 N SP values has not been observed Continental regions have been the hot spot of anthropogenic emissions over the last four decades
    Type of Medium: Online Resource
    ISSN: 2169-897X , 2169-8996
    Language: English
    Publisher: American Geophysical Union (AGU)
    Publication Date: 2023
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  • 7
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 22, No. 18 ( 2022-09-21), p. 12367-12386
    Abstract: Abstract. Molecular hydrogen, H2, is one of the most abundant trace gases in the atmosphere. The main known chemical source of H2 in the atmosphere is the photolysis of formaldehyde and glyoxal. Recent laboratory measurements and ground-state photochemistry calculations have shown other aldehydes photodissociate to yield H2 as well. This aldehyde photochemistry has not been previously accounted for in atmospheric H2 models. Here, we used two atmospheric models to test the implications of the previously unexplored aldehyde photochemistry on the H2 tropospheric budget. We used the AtChem box model implementing the nearly chemically explicit Master Chemical Mechanism at three sites selected to represent variable atmospheric environments: London, Cabo Verde and Borneo. We conducted five box model simulations per site using varying quantum yields for the photolysis of 16 aldehydes and compared the results against a baseline. The box model simulations showed that the photolysis of acetaldehyde, propanal, methylglyoxal, glycolaldehyde and methacrolein yields the highest chemical production of H2. We also used the GEOS-Chem 3-D atmospheric chemical transport model to test the impacts of the new photolytic H2 source on the global scale. A new H2 simulation capability was developed in GEOS-Chem and evaluated for 2015 and 2016. We then performed a sensitivity simulation in which the photolysis reactions of six aldehyde species were modified to include a 1 % yield of H2. We found an increase in the chemical production of H2 over tropical regions where high abundance of isoprene results in the secondary generation of methylglyoxal, glycolaldehyde and methacrolein, ultimately yielding H2. We calculated a final increase of 0.4 Tg yr−1 in the global chemical production budget, compared to a baseline production of ∼41 Tg yr−1. Ultimately, both models showed that H2 production from the newly discovered photolysis of aldehydes leads to only minor changes in the atmospheric mixing ratios of H2, at least for the aldehydes tested here when assuming a 1 % quantum yield across all wavelengths. Our results imply that the previously missing photochemical source is a less significant source of model uncertainty than other components of the H2 budget, including emissions and soil uptake.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2022
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  • 8
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 21, No. 2 ( 2021-01-29), p. 1245-1266
    Abstract: Abstract. We developed a high-resolution surface flux inversion system based on the global Eulerian–Lagrangian coupled tracer transport model composed of the National Institute for Environmental Studies (NIES) transport model (TM; collectively NIES-TM) and the FLEXible PARTicle dispersion model (FLEXPART). The inversion system is named NTFVAR (NIES-TM–FLEXPART-variational) as it applies a variational optimization to estimate surface fluxes. We tested the system by estimating optimized corrections to natural surface CO2 fluxes to achieve the best fit to atmospheric CO2 data collected by the global in situ network as a necessary step towards the capability of estimating anthropogenic CO2 emissions. We employed the Lagrangian particle dispersion model (LPDM) FLEXPART to calculate surface flux footprints of CO2 observations at a spatial resolution of 0.1∘×0.1∘. The LPDM is coupled with a global atmospheric tracer transport model (NIES-TM). Our inversion technique uses an adjoint of the coupled transport model in an iterative optimization procedure. The flux error covariance operator was implemented via implicit diffusion. Biweekly flux corrections to prior flux fields were estimated for the years 2010–2012 from in situ CO2 data included in the Observation Package (ObsPack) data set. High-resolution prior flux fields were prepared using the Open-Data Inventory for Anthropogenic Carbon dioxide (ODIAC) for fossil fuel combustion, the Global Fire Assimilation System (GFAS) for biomass burning, the Vegetation Integrative SImulator for Trace gases (VISIT) model for terrestrial biosphere exchange, and the Ocean Tracer Transport Model (OTTM) for oceanic exchange. The terrestrial biospheric flux field was constructed using a vegetation mosaic map and a separate simulation of CO2 fluxes at a daily time step by the VISIT model for each vegetation type. The prior flux uncertainty for the terrestrial biosphere was scaled proportionally to the monthly mean gross primary production (GPP) by the Moderate Resolution Imaging Spectroradiometer (MODIS) MOD17 product. The inverse system calculates flux corrections to the prior fluxes in the form of a relatively smooth field multiplied by high-resolution patterns of the prior flux uncertainties for land and ocean, following the coastlines and fine-scale vegetation productivity gradients. The resulting flux estimates improved the fit to the observations taken at continuous observation sites, reproducing both the seasonal and short-term concentration variabilities including high CO2 concentration events associated with anthropogenic emissions. The use of a high-resolution atmospheric transport in global CO2 flux inversions has the advantage of better resolving the transported mixed signals from the anthropogenic and biospheric sources in densely populated continental regions. Thus, it has the potential to achieve better separation between fluxes from terrestrial ecosystems and strong localized sources, such as anthropogenic emissions and forest fires. Further improvements in the modelling system are needed as our posterior fit was better than that of the National Oceanic and Atmospheric Administration (NOAA)'s CarbonTracker for only a fraction of the monitoring sites, i.e. mostly at coastal and island locations where background and local flux signals are mixed.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2021
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  • 9
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 20, No. 8 ( 2020-04-24), p. 4787-4807
    Abstract: Abstract. Perfluorocarbons (PFCs) are potent greenhouse gases with global warming potentials up to several thousand times greater than CO2 on a 100-year time horizon. The lack of any significant sinks for PFCs means that they have long atmospheric lifetimes of the order of thousands of years. Anthropogenic production is thought to be the only source for most PFCs. Here we report an update on the global atmospheric abundances of the following PFCs, most of which have for the first time been analytically separated according to their isomers: c-octafluorobutane (c-C4F8), n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14), and n-hexadecafluoroheptane (n-C7F16). Additionally, we report the first data set on the atmospheric mixing ratios of perfluoro-2-methylpentane (i-C6F14). The existence and significance of PFC isomers have not been reported before, due to the analytical challenges of separating them. The time series spans a period from 1978 to the present. Several data sets are used to investigate temporal and spatial trends of these PFCs: time series of air samples collected at Cape Grim, Australia, from 1978 to the start of 2018; a time series of air samples collected between July 2015 and April 2017 at Tacolneston, UK; and intensive campaign-based sampling collections from Taiwan. Although the remote “background” Southern Hemispheric Cape Grim time series indicates that recent growth rates of most of these PFCs are lower than in the 1990s, we continue to see significantly increasing mixing ratios that are between 6 % and 27 % higher by the end of 2017 compared to abundances measured in 2010. Air samples from Tacolneston show a positive offset in PFC mixing ratios compared to the Southern Hemisphere baseline. The highest mixing ratios and variability are seen in air samples from Taiwan, which is therefore likely situated much closer to PFC sources, confirming predominantly Northern Hemispheric emissions for most PFCs. Even though these PFCs occur in the atmosphere at levels of parts per trillion molar or less, their total cumulative global emissions translate into 833 million metric tonnes of CO2 equivalent by the end of 2017, 23 % of which has been emitted since 2010. Almost two-thirds of the CO2 equivalent emissions within the last decade are attributable to c-C4F8, which currently also has the highest emission rates that continue to grow. Sources of all PFCs covered in this work remain poorly constrained and reported emissions in global databases do not account for the abundances found in the atmosphere.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
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  • 10
    In: Atmospheric Chemistry and Physics, Copernicus GmbH, Vol. 20, No. 15 ( 2020-08-13), p. 9525-9546
    Abstract: Abstract. The hydroxyl radical (OH), which is the dominant sink of methane (CH4), plays a key role in closing the global methane budget. Current top-down estimates of the global and regional CH4 budget using 3D models usually apply prescribed OH fields and attribute model–observation mismatches almost exclusively to CH4 emissions, leaving the uncertainties due to prescribed OH fields less quantified. Here, using a variational Bayesian inversion framework and the 3D chemical transport model LMDz, combined with 10 different OH fields derived from chemistry–climate models (Chemistry–Climate Model Initiative, or CCMI, experiment), we evaluate the influence of OH burden, spatial distribution, and temporal variations on the global and regional CH4 budget. The global tropospheric mean CH4-reaction-weighted [OH] ([OH]GM-CH4) ranges 10.3–16.3×105 molec cm−3 across 10 OH fields during the early 2000s, resulting in inversion-based global CH4 emissions between 518 and 757  Tg yr−1. The uncertainties in CH4 inversions induced by the different OH fields are similar to the CH4 emission range estimated by previous bottom-up syntheses and larger than the range reported by the top-down studies. The uncertainties in emissions induced by OH are largest over South America, corresponding to large inter-model differences of [OH] in this region. From the early to the late 2000s, the optimized CH4 emissions increased by 22±6  Tg yr−1 (17–30  Tg yr−1), of which ∼25  % (on average) offsets the 0.7  % (on average) increase in OH burden. If the CCMI models represent the OH trend properly over the 2000s, our results show that a higher increasing trend of CH4 emissions is needed to match the CH4 observations compared to the CH4 emission trend derived using constant OH. This study strengthens the importance of reaching a better representation of OH burden and of OH spatial and temporal distributions to reduce the uncertainties in the global and regional CH4 budgets.
    Type of Medium: Online Resource
    ISSN: 1680-7324
    Language: English
    Publisher: Copernicus GmbH
    Publication Date: 2020
    detail.hit.zdb_id: 2092549-9
    detail.hit.zdb_id: 2069847-1
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