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Stable isotopes as tracers of methane dynamics in Everglades marshes with and without active populations of methane oxidizing bacteria

The stable carbon isotopic composition of CH4 is used to study the processes that affect it during transport through plants from sediment to the atmosphere. The enhancement of CH4 flux from Cladium and Eleocharis over the flux from open water or clipped sites indicated that these plants served as gas conduits between the sediments and the atmosphere. Lowering of the water table below the sediment surface caused an Everglades sawgrass marsh to shift from emission of CH4 to consumption of atmospheric CH4. Cladium transported gases passively mainly via molecular diffusion and/or effusion instead of actively via bulk flow. Stable isotropic data gave no evidence that CH4 oxidation was occurring in the rhizosphere of Cladium. Both CH4 stable carbon isotope and flux data indicated a lack of CH4 oxidation at the sediment-water interface in Everglades marl soils and its presence in peat soils where 40 to 92 percent of the flux across the sediment-water interface was oxidized.

Happell, James D.↗

Emissions of N2O, CH4 and CO2 from tropical forest soils

Emissions of nitrous oxide, methane, and carbon dioxide were measured at diverse locations in tropical forests of Brazil, Ecuador, and Puerto Rico using a static open chamber technique. Mean fluxes to the atmosphere were 1.7 x 10 to the 10th, -0.7 x 10 to the 10th, and 1.5 x 10 to the 14th molecules/sq cm per s for N2O, CH4, and CO2, respectively. The data indicate that tropical forests contribute a significant fraction of the global source for atmospheric N2O, about 40 percent of the current source, and possibly 75 percent of the preindustrial source. Methane is consumed by soils on average, but the sink is an insignificant part (less than 5 percent) of the atmospheric cycle for the gas. Emissions of CO2 from forest soils are higher at equatorial sites than at middle or high latitudes, as expected from ecological considerations. Soils emit CO2 at rates more than twice as large as the rate of carbon infall in litter; hence much of the emitted CO2 must arise from root metabolism.

Keller, Michael↗

The Decomposition of Carbonates and Organics on Mars

The return and analysis of pristine material that is relict of a putative period of chemical evolution is a fumdamental goal of the exobiological exploration of Mars. In order to accomplish this objective, it is desirable to find oxidant-free regions where pristine material can be accessed at the shallowest possible depth (ideally directly from the surface). The objective of our ongoing research is to understand the spatial and temporal distribution of oxidants in the martian regolith and the redox chemistry of the soil; in effect to understand the chemical mechanisms and kinetics relating to the in-situ destruction of organics and the formation of the reactive species responsible for the Viking biology results. In this work, we report on experimental studies of oxidizing processes that may contribute to carbonate and organic degradation on Mars. Organic molecules directly exposed to solar UV may decomposed either directly into CO2, or into more volatile organic fragments. Organic macromolecules not directly exposed to high UV flux are most likely to be affected by atmospheric oxidants which can diffuse to their surfaces. The oxidizing processes examined include: gas-phase oxidants, UV photolysis, and UV-assisted heterogeneous catalysis. For example, assuming a meteroritic infall rate of 4 x 10(exp -4) g/m^2yr (Flynn and McKay 1990) and a flux of organic carbon of 2 x 10(exp -5) g/m^2yr, laboratory measurements of the UV-assisted decomposition of benzenehexacarboxylic acid (mellitic acid, a likely intermediate of kerogen oxidation), indicate its decomposition rate on Mars would exceed the total flux of organic carbon to the planet by over four orders of magnitude. Our measurements indicate that although the decomposition temperature of kerogens in some cases exceeds the temperature limit of the Viking GCMS, it is unlikely kerogens or their decomposition intermediates were present at the Viking landings sites at levels above the GCMS detection limits.

Quinn, Richard C.↗

Projections of Declining Surface-Water Availability for the Southwestern United States

Global warming driven by rising greenhouse-gas concentrations is expected to cause wet regions of the tropics and mid to high latitudes to get wetter and subtropical dry regions to get drier and expand polewards. Over southwest North America, models project a steady drop in precipitation minus evapotranspiration, P -- E, the net flux of water at the land surface, leading to, for example, a decline in Colorado River flow. This would cause widespread and important social and ecological consequences. Here, using new simulations from the Coupled Model Intercomparison Project Five, to be assessed in Intergovernmental Panel on Climate Change Assessment Report Five, we extend previous work by examining changes in P, E, runoff and soil moisture by season and for three different water resource regions. Focusing on the near future, 2021-2040, the new simulations project declines in surface-water availability across the southwest that translate into reduced soil moisture and runoff in California and Nevada, the Colorado River headwaters and Texas.

Seager, Richard↗

Evidence from massive siderite beds for a CO2-rich atmosphere before approximately 1.8 billion years ago

It is generally thought that, in order to compensate for lower solar flux and maintain liquid oceans on the early Earth, methane must have been an important greenhouse gas before approximately 2.2 billion years (Gyr) ago. This is based upon a simple thermodynamic calculation that relates the absence of siderite (FeCO3) in some pre-2.2-Gyr palaeosols to atmospheric CO2 concentrations that would have been too low to have provided the necessary greenhouse effect. Using multi-dimensional thermodynamic analyses and geological evidence, we show here that the absence of siderite in palaeosols does not constrain atmospheric CO2 concentrations. Siderite is absent in many palaeosols (both pre- and post-2.2-Gyr in age) because the O2 concentrations and pH conditions in well-aerated soils have favoured the formation of ferric (Fe3+)-rich minerals, such as goethite, rather than siderite. Siderite, however, has formed throughout geological history in subsurface environments, such as euxinic seas, where anaerobic organisms created H2-rich conditions. The abundance of large, massive siderite-rich beds in pre-1.8-Gyr sedimentary sequences and their carbon isotope ratios indicate that the atmospheric CO2 concentration was more than 100 times greater than today, causing the rain and ocean waters to be more acidic than today. We therefore conclude that CO2 alone (without a significant contribution from methane) could have provided the necessary greenhouse effect to maintain liquid oceans on the early Earth.

Greenhouse Effect↗

Assessment of landscape-scale fluxes of carbon dioxide and methane in subtropical coastal wetlands of South Florida

Coastal wetlands play a significant role in the storage of “blue carbon,” indicating their importance in the carbon biogeochemistry in the coastal zone and in global climate change mitigation strategies. We present airborne eddy covariance observations of CO 2 and CH 2 fluxes collected in southern Florida as part of the NASA BlueFlux mission during April 2022, October 2022, February 2023, and April 2023. The flux data generated from this mission consists of over 100 flight hours and more than 6,000 km of horizontal distance over coastal saline and freshwater wetlands. We find that the spatial and temporal heterogeneity in CO 2 and CH 2 exchange is primarily influenced by season, vegetation type, ecosystem productivity, and soil inundation. The largest CO 2 uptake fluxes of more than 20 μmol m -2 s -1 were observed over mangroves during all deployments and over swamp forests during flights in April. The greatest CH 4 effluxes of more than 250 nmol m -2 s -1 were measured at the end of the wet season in October 2022 over freshwater marshes and swamp shrublands. Although the combined Everglades National Park and Big Cypress National Preserve region was a net sink for carbon, CH 4 emissions reduced the ecosystem carbon uptake capacity (net CO 2 exchange rates) by 11%–91%. Average total net carbon exchange rates during the flight periods were −4 to −0.2 g CO 2 -eq m -2 d -1 . Our results highlight the importance of preserving mangrove forests and point to potential avenues of further research for greenhouse gas mitigation strategies.

atmosphere↗

Ultraviolet Radiation on the Surface of Mars

An evaluation of the ultraviolet (UV) flux incident on the Martian surface is important for a number of issues. UV-induced photolysis of water changes the chemistry of the soil and atmosphere, inducing its oxidizing nature. Alternatively, UV may directly affect surface chemistry by generating silicate defects. UV also rapidly degrades organic material delivered by meteoritic infall. Consequently, UV affects the overall chemistry of the Martian surface and atmosphere. The extent of UV breakdown of organic molecules is also relevant to concerns regarding contaminants on lander or rover surfaces that could interfere with life-detection experiments causing "false positives". The radiation flux at a point on the surface of Mars depends on factors such as cloud cover, atmospheric dust loading, season, local time, and latitude. Previously, the UV spectrum incident on the surface of Mars has been calculated from a simple radiative transfer model. Limitations of this earlier model include no accounting for the effect of dust, which may be a perennial constituent of the atmosphere, and also the use of gas absorption data measured at room temperature that overestimate absorption for lower Martian temperatures. We present an updated model for UV radiation (200-400 nm) that incorporates dust and more recent data for the solar spectrum, gas absorption, and UV surface albedo. Additional information is contained in the original extended abstract.

Catling, D. C.↗

Rocket Exhaust Cratering: Lessons Learned from Viking and Apollo

During the Apollo and Viking programs NASA expended considerable effort to study the cratering of the regolith when a rocket launches or lands on it. That research ensured the success of those programs but also demonstrated that cratering will be a serious challenge for other mission scenarios. Unfortunately, because three decades have elapsed since NASA last performed a successful retro-rocket landing on a large planetary body - and ironically because Apollo and Viking were successful at minimizing the cratering effects - the space agency has a minimized sense of the seriousness of the issue. The most violent phase of a cratering event is when the static overpressure of the rocket exhaust exceeds the bearing capacity of the soil. This bearing capacity failure (BCF) punches a small and highly concave cup into the surface. The shape of the cup then redirects the supersonic jet - along with a large flux of high-velocity debris - directly toward the spacecraft. This has been observed in terrestrial experiments but never quantified analytically. The blast from such an event will be more than just quantitatively greater than the cratering that occurred in the Apollo and Viking programs. It will be qualitatively different, because BCF had been successfully avoided in all those missions. In fact, the Viking program undertook a significant research and development effort and redesigned the spacecraft specifically for the purpose of avoiding BCF [1]. (See Figure 1.) Because the Apollo and Viking spacecraft were successful at avoiding those cratering effects, it was unnecessary to understand them. As a result, the physics of a BCF-driven cratering event have never been well understood. This is a critical gap in our knowledge because BCF is unavoidable in the Martian environment with the large landers necessary for human exploration, and in Lunar landings it must also be addressed because it may occur depending upon the design specifics of the spacecraft and the weakening of the regolity by gas diffusion.

Metzger, Philip T.↗

Simulation of Radon-222 with the GEOS-Chem Global Model: Emissions, Seasonality, and Convective Transport

Radon-222 (Rn-222) is a short-lived radioactive gas naturally emitted from land surfaces and has long been used to assess convective transport in atmospheric models. In this study, we simulate Rn-222 using the GEOS-Chem chemical transport model to improve our understanding of Rn-222 emissions and surface concentration seasonality and characterize convective transport associated with two Goddard Earth Observing System (GEOS) meteorological products, the Modern-Era Retrospective analysis for Research and Applications (MERRA) and GEOS Forward Processing (GEOS-FP). We evaluate four global Rn-222 emission scenarios by comparing model results with observations at 51 surface sites. The default emission scenario in GEOS-Chem yields a moderate agreement with surface observations globally (68.9 % of data within a factor of 2) and a large underestimate of winter surface Rn-222 concentrations at Northern Hemisphere midlatitudes and high latitudes due to an oversimplified formulation of Rn-222 emission fluxes (1 atom cm−2 s−1 over land with a reduction by a factor of 3 under freezing conditions). We compose a new global Rn-222 emission scenario based on Zhang et al. (2011) and demonstrate its potential to improve simulated surface Rn-222 concentrations and seasonality. The regional components of this scenario include spatially and temporally varying emission fluxes derived from previous measurements of soil radium content and soil exhalation models, which are key factors in determining Rn-222 emission flux rates. However, large model underestimates of surface Rn-222 concentrations still exist in Asia, suggesting unusually high regional Rn-222 emissions. We therefore propose a conservative upscaling factor of 1.2 for Rn-222 emission fluxes in China, which was also constrained by observed deposition fluxes of 210Pb (a progeny of Rn-222). With this modification, the model shows better agreement with observations in Europe and North America (> 80 % of data within a factor of 2) and reasonable agreement in Asia (close to 70 %). Further constraints on Rn-222 emissions would require additional concentration and emission flux observations in the central United States, Canada, Africa, and Asia. We also compare and assess convective transport in model simulations driven by MERRA and GEOS-FP using observed Rn-222 vertical profiles in northern midlatitude summer and from three short-term airborne campaigns. While simulations with both GEOS products are able to capture the observed vertical gradient of Rn-222 concentrations in the lower troposphere (0–4 km), neither correctly represents the level of convective detrainment, resulting in biases in the middle and upper troposphere. Compared with GEOS-FP, MERRA leads to stronger convective transport of Rn-222, which is partially compensated for by its weaker large-scale vertical advection, resulting in similar global vertical distributions of Rn-222 concentrations between the two simulations. This has important implications for using chemical transport models to interpret the transport of other trace species when these GEOS products are used as driving meteorology.

Bo Zhang↗

Harmonising the Land-Use Flux Estimates of Global Models and National Inventories for 2000–2020

As the focus of climate policy shifts from pledges to implementation, there is a growing need to track progress on climate change mitigation at the country level, particularly for the land-use sector. Despite new tools and models providing unprecedented monitoring opportunities, striking differences remain in estimations of anthropogenic land-use CO 2 fluxes between, on the one hand, the national greenhouse gas inventories (NGHGIs) used to assess compliance with national climate targets under the Paris Agreement and, on the other hand, the Global Carbon Budget and Intergovernmental Panel on Climate Change (IPCC) assessment reports, both based on global bookkeeping models (BMs). Recent studies have shown that these differences are mainly due to inconsistent definitions of anthropogenic CO 2 fluxes in managed forests. Countries assume larger areas of forest to be managed than BMs do, due to a broader definition of managed land in NGHGIs. Additionally, the fraction of the land sink caused by indirect effects of human-induced environmental change (e.g. fertilisation effect on vegetation growth due to increased atmospheric CO 2 concentration) on managed lands is treated as non-anthropogenic by BMs but as anthropogenic in most NGHGIs. We implement an approach that adds the CO 2 sink caused by environmental change in countries' managed forests (estimated by 16 dynamic global vegetation models, DGVMs) to the land-use fluxes from three BMs. This sum is conceptually more comparable to NGHGIs and is thus expected to be quantitatively more similar. Our analysis uses updated and more comprehensive data from NGHGIs than previous studies and provides model results at a greater level of disaggregation in terms of regions, countries and land categories (i.e. forest land, deforestation, organic soils, other land uses). Our results confirm a large difference (6.7 GtCO 2 yr −1 ) in global land-use CO 2 fluxes between the ensemble mean of the BMs, which estimate a source of 4.8 GtCO 2 yr −1 for the period 2000–2020, and NGHGIs, which estimate a sink of −1.9 GtCO 2 yr −1 in the same period. Most of the gap is found on forest land (3.5 GtCO 2 yr −1 ), with differences also for deforestation (2.4 GtCO 2 yr −1 ), for fluxes from other land uses (1.0 GtCO 2 yr −1 ) and to a lesser extent for fluxes from organic soils (0.2 GtCO2 yr−1). By adding the DGVM ensemble mean sink arising from environmental change in managed forests (−6.4 GtCO 2 yr −1 ) to BM estimates, the gap between BMs and NGHGIs becomes substantially smaller both globally (residual gap: 0.3 GtCO 2 yr −1 ) and in most regions and countries. However, some discrepancies remain and deserve further investigation. For example, the BMs generally provide higher emissions from deforestation than NGHGIs and, when adjusted with the sink in managed forests estimated by DGVMs, yield a sink that is often greater than NGHGIs. In summary, this study provides a blueprint for harmonising the estimations of anthropogenic land-use fluxes, allowing for detailed comparisons between global models and national inventories at global, regional and country levels. This is crucial to increase confidence in land-use emissions estimates, support investments in land-based mitigation strategies and assess the countries' collective progress under the Global Stocktake of the Paris Agreement.

Giacomo Grassi↗

Monitoring of Volcanogenic CO2-Induced Tree Kills with AVIRIS Image Data at Mammoth Mountain, California

Elevated cold CO2 emissions from the flank of Mammoth Mountain volcano on the southwest rim of the Long Valley Caldera, eastern California, have been the cause of over 100 acres of dead trees in that area since 1990. The source of the CO2 gas is thought to be from one or more magmatic intrusion(s) beneath Mammoth Mountain and is probably related to a period of seismic unrest that began in 1989. The gas rises to the surface probably from depths of a few kilometers, along faults and fracture zones. The gas is at ambient temperature and diffuses from the soil rather than discharging from distinct vents. Typically, soil gas concentrations in tree-kill areas range from 10% to over 90% CO2 by volume, as compared to normal background of < 1% in healthy forest. The gas composition is predominantly CO2 mixed with air (sulfur gases are not elevated), and C and He isotopic ratios are consistent with a magmatic origin for the gas. The total CO2 emission has been estimated at 1200 tons/day, comparable to the emissions at Kilauea. Some of the dead trees are as old as 250 years, suggesting that similar anomalous gas discharge has not occurred over the previous few hundred years. The delta C-13/12 ratio in the Mammoth Mountain CO2 emission averages about -4.5 (PDB standard). This is consistent with a mantle source for the carbon. However, the large volume of the emission suggests that not all of the CO2 is necessarily being generated from the 1989 intrusion. The voluminous gas could be leaking from a vapor-rich zone, capped by an impermeable layer, that was supplied CO2 from degassing of many small magma bodies that intruded beneath the mountain over a period of decades or centuries. Earthquakes in 1989 could have fractured the capping layer and provided pathways for the escape Of CO2 to the surface. Alternatively, some of the CO2 could be derived from contact metamorphism of carbonate rocks intruded by magma. Carbonate-bearing Paleozoic roof pendents crop out in close proximity to Mammoth Mountain. It is possible that similar rocks could occur at depth beneath Mammoth Mountain, and could have contributed CO2 from thermal decomposition caused from recent intrusions. We hope to determine the C-13/12 ratio of a suite of samples to demonstrate if the carbonate rocks could be the source of at least part of the 1990-97 CO2 emission. To better understand the behavior of the CO2 gas, we have used hyperspectral imagery data of Mammoth Mountain acquired from the Airborne Visual/Infrared Imaging Spectrometer (AVIRIS) to map out areas of dead trees. The areas of tree kill have increased in size from about 50 acres in 1994 to about 100 acres in 1997. Tree kill is the major surface manifestation of the carbon dioxide flux at Mammoth Mountain, is widely dispersed, and has been cursorily mapped by regular field mapping techniques in the area. Initial investigations using airborne digital imagery from the Thematic Mapper Simulator (NS001) and AVIRIS instruments have shown extremely encouraging results for complete delineation of the vegetation anomalies. The most successful maps (when compared with ground truth) were developed using AVIRIS data with spectral angle mapper and matched filter algorithms with a data set that was reduced to maximum variance via the minimum noise fraction transformation. The result of this work is a series of maps that show the tree kill areas occurring in an halo-pattern surrounding the base of Mammoth Mountain. We are applying these same techniques to earlier AVIRIS images of Mammoth Mountain to examine the progression of the tree kill areas over time. Temporal maps of the tree kill areas may assist in constructing a picture of the structure beneath Mammoth Mountain.

Hausback, Brian P.↗