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At least 181 records · Page 10

Wellbore Leakage Mitigation Using Advanced Mineral Precipitation Strategies (Final Scientific/Technical Report)

This research project, entitled Wellbore Leakage Mitigation using Advanced Mineral Precipitation Strategies, was directed toward advancing mineral precipitation technologies to seal wellbore leaks and other potential carbon dioxide (CO 2 ) leakage pathways, including compromised wellbore cement and fracture networks of varying geometries throughout the wellbore and surrounding formation. The advanced mineral sealing techniques were evaluated in the laboratory and the field to expand the range of temperature, pressure, and chemical conditions where mineral precipitation could be used. Rates of enzymatically or thermally induced calcium carbonate precipitation (EICP, TICP) were determined as well as rates of enzyme inactivation at elevated temperatures (>60 °C). Immobilization was shown to enhance the thermal stability of urease enzyme and provide protection from inhibition in low pH conditions. Mineral seals promoted by EICP and TICP were used to seal fractured composite (cement/sandstone) and shale cores in high pressure reactors operated at temperatures greater than 55 °C and 130 °C, respectively. A computational model was updated to model processes of EICP and TICP. The work resulted in a successful field test, which showed that EICP in the presence of low pH fluids (CO 2 -impacted brine) could promote permeability reduction and seal a channel in the near-wellbore environment.

54 ENVIRONMENTAL SCIENCES↗

Sensitivity of Terrestrial Water and Energy Budgets to CO2-Physiological Forcing: An Investigation Using an Offline Land Model

Increasing concentrations of atmospheric carbon dioxide (CO2) influence climate by suppressing canopy transpiration in addition to its well-known greenhouse gas effect. The decrease in plant transpiration is due to changes in plant physiology (reduced opening of plant stomata). Here, we quantify such changes in water flux for various levels of CO2 concentrations using the National Center for Atmospheric Research s (NCAR) Community Land Model. We find that photosynthesis saturates after 800 ppmv (parts per million, by volume) in this model. However, unlike photosynthesis, canopy transpiration continues to decline at about 5.1% per 100 ppmv increase in CO2 levels. We also find that the associated reduction in latent heat flux is primarily compensated by increased sensible heat flux. The continued decline in canopy transpiration and subsequent increase in sensible heat flux at elevated CO2 levels implies that incremental warming associated with the physiological effect of CO2 will not abate at higher CO2 concentrations, indicating important consequences for the global water and carbon cycles from anthropogenic CO2 emissions. Keywords: CO2-physiological effect, CO2-fertilization, canopy transpiration, water cycle, runoff, climate change 1.

Gopalakrishnan, Ranjith↗

Air‐Sea CO 2 Fluxes Localized by Topography in a Southern Ocean Channel

Abstract Air‐sea exchange of carbon dioxide (CO 2 ) in the Southern Ocean plays an important role in the global carbon budget. Previous studies have suggested that flow around topographic features of the Southern Ocean enhances the upward supply of carbon from the deep to the surface, influencing air‐sea CO 2 exchange. Here, we investigate the role of seafloor topography on the transport of carbon and associated air‐sea CO 2 flux in an idealized channel model. We find elevated CO 2 outgassing upstream of a seafloor ridge, driven by anomalous advection of dissolved inorganic carbon. Argo‐like Lagrangian particles in our channel model sample heterogeneously in the vicinity of the seafloor ridge, which could impact float‐based estimates of CO 2 flux.

59 BASIC BIOLOGICAL SCIENCES↗

Experimental Soil Warming and Permafrost Thaw Increase CH 4 Emissions in an Upland Tundra Ecosystem

Rapid Arctic warming is causing permafrost to thaw and exposing large quantities of soil organic carbon (C) to potential decomposition. In dry upland tundra systems, subsidence from thawing permafrost can increase surface soil moisture resulting in higher methane (CH 4 ) emissions from newly waterlogged soils. The proportion of C released as carbon dioxide (CO 2 ) and CH 4 remains uncertain as previously dry landscapes transition to a thawed state, resulting in both wetter and drier microsites. To address how thaw and moisture interact to affect total C emissions, here we measured CH 4 and CO 2 emissions from paired chambers across thaw and moisture gradients created by nine years of experimental soil warming in interior Alaska. Cumulative growing season (May–September) CH 4 emissions were elevated at both wetter (216.1–1,099.4 mg CH 4 -C m –2 ) and drier (129.7–392.3 mg CH 4 -C m –2 ) deeply thawed microsites relative to shallow thaw (55.6–215.7 mg CH 4 -C m –2 ) and increased with higher deep soil temperatures and permafrost thaw depth. Interannual variability in CH4 emissions was driven by wet conditions in graminoid-dominated plots that generated >70% of emissions in a wet year. Shoulder season emissions were equivalent to growing season CH 4 emissions rates in the deeply thawed, warmed soils, highlighting the importance of non-growing season CH 4 emissions. Net C sink potential was reduced in deeply thawed wet plots by 4%–42%, and by 3.5%–8% in deeply thawed drier plots due to anaerobic respiration, suggesting that some dry upland tundra landscapes may transition into stronger CH 4 sources in a warming Arctic.

54 ENVIRONMENTAL SCIENCES↗

High-temperature seals for supercritical carbon-dioxide (sCO 2 ) turbines (Final Report)

This is the final report for project DE-FE0031924 titled “High-temperature seals for supercritical carbon-dioxide (sCO 2 ) turbines.” The report provides a summary of the entire project efforts from October 2020 through December 2024 including the high-temperature commercial dry gas seal (DGS) tests and thermal modeling of Task 2, as well as the high-temperature, large-diameter seal design and high-temperature tests of large-diameter seals in Task 3. A key outcome of Task 2 was the testing completion of specially instrumented commercial DGS in the GE-SwRI Apollo sCO 2 compressor (27,000 rpm). Test data from the DGS showed elevated temperatures upwards of 350 o F, which are close to the higher operating temperature limit of the DGS. The temperature measurements provide insight into the expected thermal loads on DGS operating in high-speed sCO 2 compressor and provided test data for validation of an in-house thermal model of the compressor/seal. Under Task 2.0, this report also presents the development of a steady-state conjugate heat-transfer model of the DGS operating in the sCO 2 compressor – a first of its kind model for modeling heat transfer of sCO 2 in an actual operating compressor. The findings of the thermal model show a reasonable match between temperature predictions of the model and the measured temperature data, also pointing out the validity of the approach and assumptions made in modeling the flows, heat transfer coefficients and windage modeling in the rig. Under Task 3.0, this report presents the preliminary design of a large-diameter hybrid face seal (14 inch and 26-inch diameter) for field testing in a land-based GE turbine. The preliminary seal design effort presented in this report under project DE-FE0031924 builds on the development and successful laboratory testing for such large diameter hybrid face seal under the prior DE-FE0024007 project. Key aspects of seal fluid analyses with CFD, mechanical design considerations and assembly considerations in a land-based turbine are presented. Finally, under Task 3.0, this report also presents the continued high-temperature testing of the 14-inch diameter hybrid face seal developed previously under the DE-FE0024007 program. Specifically, test data demonstrating successful non-contact seal operation and seal effective leakage of 0.001-inch with seal inlet temperatures above 700 o F are presented in this report. Successful hybrid seal operation in a laboratory environment for a large diameter (14-inch) seal at temperatures above 700 o F is a major technological milestone for this technology.

01 COAL, LIGNITE, AND PEAT↗

Oligosaccharide production and signaling correlate with delayed flowering in an Arabidopsis genotype grown and selected in high [CO 2 ]

Since industrialization began, atmospheric CO 2 ([CO 2 ]) has increased from 270 to 415 ppm and is projected to reach 800–1000 ppm this century. Some Arabidopsis thaliana (Arabidopsis) genotypes delayed flowering in elevated [CO 2 ] relative to current [CO 2 ], while others showed no change or accelerations. To predict genotype-specific flowering behaviors, we must understand the mechanisms driving flowering response to rising [CO 2 ]. [CO 2 ] changes alter photosynthesis and carbohydrates in plants. Plants sense carbohydrate levels, and exogenous carbohydrate application influences flowering time and flowering transcript levels. We asked how organismal changes in carbohydrates and transcription correlate with changes in flowering time under elevated [CO 2 ]. We used a genotype (SG) of Arabidopsis that was selected for high fitness at elevated [CO 2 ] (700 ppm). SG delays flowering under elevated [CO 2 ] (700 ppm) relative to current [CO 2 ] (400 ppm). We compared SG to a closely related control genotype (CG) that shows no [CO 2 ]-induced flowering change. We compared metabolomic and transcriptomic profiles in these genotypes at current and elevated [CO 2 ] to assess correlations with flowering in these conditions. While both genotypes altered carbohydrates in response to elevated [CO 2 ], SG had higher levels of sucrose than CG and showed a stronger increase in glucose and fructose in elevated [CO 2 ]. Both genotypes demonstrated transcriptional changes, with CG increasing genes related to fructose 1,6-bisphosphate breakdown, amino acid synthesis, and secondary metabolites; and SG decreasing genes related to starch and sugar metabolism, but increasing genes involved in oligosaccharide production and sugar modifications. Genes associated with flowering regulation within the photoperiod, vernalization, and meristem identity pathways were altered in these genotypes. Elevated [CO 2 ] may alter carbohydrates to influence transcription in both genotypes and delayed flowering in SG. Changes in the oligosaccharide pool may contribute to delayed flowering in SG. This work extends the literature exploring genotypic-specific flowering responses to elevated [CO 2 ].

59 BASIC BIOLOGICAL SCIENCES↗

Experimental and Computational Heat Transfer Study of sCO 2 Single-Jet Impingement

This study experimentally and computationally investigates the heat transfer capability of supercritical carbon dioxide (sCO 2 ) single jet impingement. The evaluated jet Reynolds number range is between 80,000 and 600,000, with a nondimensional jet-to-target surface spacing of 2.8. CO 2 -impinging jet stagnation conditions were maintained at approximately 200 bar and a temperature of ∼400 °C for most experiments. The goal is to understand how changes in the aforementioned parameters influence heat transfer between the working fluid and the heated surface. Additionally, due to the elevated Reynolds numbers and difference in thermodynamic properties between air and CO 2 , air-derived impingement correlations may not be appropriate for CO 2 impingement; these correlations will be evaluated against experimental sCO 2 impingement data. At the time of this study, no sCO 2 impingement data was available relevant to sCO 2 power cycles. The target surface is a 1.5-in. diameter copper block centered on the 3 mm jet orifice. A mica heating element bolted to the bottom of the copper block provides a uniform heat flux. Thermocouples embedded in the copper block are used to determine the surface temperature. Nusselt numbers obtained from experimental sCO 2 test data are compared to area-averaged Nusselt numbers from air-derived correlations. The comparisons showed that air correlations drastically underpredict the heat transfer when sCO 2 is used as the working fluid. A modified sCO 2 correlation using experimental data at discussed conditions is derived based on an existing air correlation. A CFD study is also performed to further investigate sCO 2 heat transfer characteristics, and assess the numerical model applicability to this problem type.

42 ENGINEERING↗

Throughfall-Reduction Drying Effects on Soil Respiration, Moisture, and Temperature in Four Distinct Lowland Panamanian Forests from 2015-2022

Objectives: Climatic drying is predicted for many tropical forests, yet effects on soil properties across moisture and soil gradients within tropical forests remain poorly characterized, hampering predictions of forest-climate feedbacks. We hypothesized that throughfall reduction (i.e. chronic drying) would suppress soil CO2 fluxes (i.e., respiration) in already-drier tropical forests by further reductions in soil moisture, but increases CO2 fluxes in wetter tropical forests by alleviating anaerobiosis and soil saturation. We conducted a field study in four distinct lowland Panamanian forests that vary in background rainfall and soil fertility. In each forest we constructed throughfall reduction structures that reduce moisture inputs to plots by ~50% (see methods). In drying and paired control plots we measured soil CO2 fluxes, soil moisture (volume/volume), soil temperature (°C), air temperature (°C), and forest floor biomass during wet-dry cycles (2015 – 2022). We also collected litterfall biomass and surveyed all tree species for diameter at breast height (dbh), and identified tree species in 2018 and 2019.Results:We found that soil moisture peaked in the wet season and declined in the dry season. Measured soil CO2 fluxes declined in the dry season and peaked in the early wet season ahead of peak soil moisture, resulting in a lower soil moisture optimum for respiration than previously modeled. Chronic throughfall exclusion also suppressed soil moisture across the four forests, and also initially suppressed soil CO2 fluxes across forests. There was sustained suppression of soil CO2 fluxes after four years in the wettest forest only (-28 ± 4% during the dry season), but elevated soil CO2 fluxes in a fertile forest after four years (+75 ± 28% during the late wet season). The unexpected negative drying effect in the wettest, most infertile forest could have resulted from reduced vertical flushing of nutrients into soils, as the drying effect increased with time. Including hydro-nutrient interactions in ecosystem models could improve predictions of tropical forest-climate feedbacks. Datasets included: Datasets included here include .csv and .xls files for soil respiration (carbon dioxide flux) collected using the LiCor (see methods), air temperature °C , soil moisture (vl/vl), and soil temperature °C. Soil moisture and soil temperature were collected at 0-10cm depths using hand-held probes (see methods). Data are on ~3 week timescales from 2015-2022 with some gaps. There is also a .kml file that includes coordinates for all 32 plots included in the study of four forests (n = 4 throughfall reduction and n = 4 control plots per site). No special software is needed to open these files.

54 ENVIRONMENTAL SCIENCES↗

Experimental and Computational Heat Transfer Study of sCO2 Single Jet Impingement

The present study experimentally investigates the heat transfer capability of supercritical carbon dioxide (sCO2) single-jet impingement. The evaluated jet Reynolds number range is between 80,000 and 1,000,000, with a non-dimensional jet-to-target surface spacing of 2.8. CO2- impinging jet stagnation conditions were maintained at approximately 20 MPa and a temperature of 673 K for most experiments. The goal is to understand how changes in the aforementioned parameters influence heat transfer between the working fluid and the heated surface. Additionally, due to the elevated Reynolds numbers and difference in thermodynamic properties between air and CO2, air-derived impingement correlations may not be appropriate for CO2 impingement; these correlations will be evaluated against experimental sCO2 impingement data. At the time of this study, no sCO2 impingement data was available relevant to sCO2 power cycles. The target surface is a 1.5-inch diameter copper block centered on the 3mm jet orifice. A mica heating element bolted to the bottom of the copper block provides a uniform heat flux. Thermocouples embedded in the copper block are used to determine the surface temperature. Nusselt numbers obtained from experimental sCO2 data are compared to area-averaged Nusselt numbers from air-derived correlations. The comparisons showed that air correlations drastically underpredict the heat transfer when sCO2 is used as the working fluid. A modified sCO2 correlation using experimental data at discussed conditions is derived based on an existing air correlation.

Richardson, John↗

AmeriFlux US-GL1 Stannard Rock

This is the AmeriFlux version of the carbon flux data for the site US-GL1 Stannard Rock. Site Description - Stannard Rock is located 39 km from the nearest shore (Keweenaw Peninsula) in Lake Superior, 44 miles NNE of Marquette, Michigan, and 24 miles ESE of Manitou Island. The site is located on the historic Stannard Rock Lighthouse, which was completed in 1882. Eddy covariance instrumentation was installed in 2008 by a network of scientists from both US and Canada, eventually to be called the Great Lakes Evaporation Network (GLEN). The intent of GLEN has been to provide observations of over-lake meteorology and evaporation, improve forecasting of Great Lakes water levels, and support a wide variety of stakeholders, including the National Weather Service (NWS), Environment and Climate Change Canada, National Oceanic and Atmospheric Administration, U.S. Coast Guard, recreational boaters and commercial shipping, emergency management officials, and the Great Lakes research community. The eddy covariance station along with other ancillary meteorological instrumentation is located at an approximate elevation of 39.2 meters above mean lake water level. Meteorological data from the lighthouse are sent to the National Data Buoy Center, where they can be viewed in real-time at http://www.ndbc.noaa.gov/station_page.php?station=stdm4 Uncorrected half-hour fluxes were computed directly on the logger using a 30-minute block averaging period as high-frequency data were not available. The half hour flux measurements downloaded from the datalogger were post-processed with the following filters and corrections. Latent and sensible heat and carbon dioxide fluxes were corrected with 2-D coordinate rotation. Although the primary objective of data collection at Stannard Rock was to quantify the evaporative flux, additional preliminary measurements of the carbon dioxide concentration and flux from the LI-7500 are also included in this dataset but it is advised to use the carbon data with caution. Carbon data reported in this dataset includes turbulent fluxes of CO2 with no storage correction (FC, µmol m-2 s-1) and CO2 density in mole fraction of wet air (CO2), which was originally output on the datalogger as average CO2 density (mg m-2 s-1) and converted into µmol mol-1 using air temperature and pressure in post-processing. Webb, Pearman, and Leuning terms were applied to account for density fluctuations for water vapor and CO2. Sonic path length, high-frequency attenuation and sensor separation were accounted for according to Horst and Massman, and the oxygen absorption correction for the KH2O hygrometer was also applied. Latent and sensible heat fluxes were assumed to be unrealistic above an absolute value of 1000 W m-2 and were removed. Both carbon flux (FC) and carbon dioxide mole fraction in wet air (CO2) and were assumed to be unrealistic above 1000 µmol m-2 s-1 and 1000 µmol mol-1 respectively. Spikes in latent and sensible heat and carbon fluxes and densities (often due to periods of precipitation) were identified by computing the mean and standard deviation over a moving, overlapping window of 336 half-hours (7 days), similar to Shao et al., and were removed when the flux was more than 1.5 standard deviations from the moving window’s mean. While Vickers and Mahrt use a threshold of 3.5 standard deviations from the mean, a conservative value of 1.5 was chosen due to the noisy nature of over-lake data at this particular site. This process was repeated twice for latent and sensible heat, and carbon dioxide fluxes and densities and therefore it is possible that some real, realistic data was filtered out in this process. No detrending was performed. As per AmeriFlux standards, no friction velocity (USTAR, m s-1) filtering was performed.

Spence, Chris↗

AmeriFlux FLUXNET-1F US-GL1 Stannard Rock

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-GL1 Stannard Rock. This is the FLUXNET version of the carbon flux data for the site US-GL1 Stannard Rock produced by applying the standard ONEFlux (1F) software. Site Description - Stannard Rock is located 39 km from the nearest shore (Keweenaw Peninsula) in Lake Superior, 44 miles NNE of Marquette, Michigan, and 24 miles ESE of Manitou Island. The site is located on the historic Stannard Rock Lighthouse, which was completed in 1882. Eddy covariance instrumentation was installed in 2008 by a network of scientists from both US and Canada, eventually to be called the Great Lakes Evaporation Network (GLEN). The intent of GLEN has been to provide observations of over-lake meteorology and evaporation, improve forecasting of Great Lakes water levels, and support a wide variety of stakeholders, including the National Weather Service (NWS), Environment and Climate Change Canada, National Oceanic and Atmospheric Administration, U.S. Coast Guard, recreational boaters and commercial shipping, emergency management officials, and the Great Lakes research community. The eddy covariance station along with other ancillary meteorological instrumentation is located at an approximate elevation of 39.2 meters above mean lake water level. Meteorological data from the lighthouse are sent to the National Data Buoy Center, where they can be viewed in real-time at http://www.ndbc.noaa.gov/station_page.php?station=stdm4 Uncorrected half-hour fluxes were computed directly on the logger using a 30-minute block averaging period as high-frequency data were not available. The half hour flux measurements downloaded from the datalogger were post-processed with the following filters and corrections. Latent and sensible heat and carbon dioxide fluxes were corrected with 2-D coordinate rotation. Although the primary objective of data collection at Stannard Rock was to quantify the evaporative flux, additional preliminary measurements of the carbon dioxide concentration and flux from the LI-7500 are also included in this dataset but it is advised to use the carbon data with caution. Carbon data reported in this dataset includes turbulent fluxes of CO2 with no storage correction (FC, µmol m-2 s-1) and CO2 density in mole fraction of wet air (CO2), which was originally output on the datalogger as average CO2 density (mg m-2 s-1) and converted into µmol mol-1 using air temperature and pressure in post-processing. Webb, Pearman, and Leuning terms were applied to account for density fluctuations for water vapor and CO2. Sonic path length, high-frequency attenuation and sensor separation were accounted for according to Horst and Massman, and the oxygen absorption correction for the KH2O hygrometer was also applied. Latent and sensible heat fluxes were assumed to be unrealistic above an absolute value of 1000 W m-2 and were removed. Both carbon flux (FC) and carbon dioxide mole fraction in wet air (CO2) and were assumed to be unrealistic above 1000 µmol m-2 s-1 and 1000 µmol mol-1 respectively. Spikes in latent and sensible heat and carbon fluxes and densities (often due to periods of precipitation) were identified by computing the mean and standard deviation over a moving, overlapping window of 336 half-hours (7 days), similar to Shao et al., and were removed when the flux was more than 1.5 standard deviations from the moving window’s mean. While Vickers and Mahrt use a threshold of 3.5 standard deviations from the mean, a conservative value of 1.5 was chosen due to the noisy nature of over-lake data at this particular site. This process was repeated twice for latent and sensible heat, and carbon dioxide fluxes and densities and therefore it is possible that some real, realistic data was filtered out in this process. No detrending was performed. As per AmeriFlux standards, no friction velocity (USTAR, m s-1) filtering was performed.

Spence, Chris [Environment and Climate Change Cana↗

Climatic controls on soil and saprock nitrogen distribution and persistence in the Sierra Nevada

Nitrogen (N) is an essential nutrient in soil that regulates plant growth, terrestrial sequestration of atmospheric carbon dioxide, and persistence of organic compounds. However, major knowledge gaps remain about how climate change may impact N accumulation and persistence, especially in deep soil and saprock (friable weakly weathered bedrock). Our objective was to understand how climate impacts the accumulation of N in soil and saprock and how climate impacts soil N distribution, persistence, and mechanisms of N persistence. We investigated N concentration in bulk soil and density fractions. We estimated N persistence along a bio-climatic sequence—sites range from a low-elevation oak savannah, mid-elevation pine-oak/mixed-conifer forest, to a high-elevation subalpine forest—in the southern Sierra Nevada in California. A combination of radiocarbon and elemental composition measurements along with a first-order kinetic model was used. The N concentration in the bulk soil and density fractions declined with depth, and there was a relatively greater mineral-associated heavy fraction (HF) N in deeper samples. The cooler/wetter mixed conifer site held 37% of profile N in saprock, which was greater than that of the entire soil profile at the drier/hotter oak savannah. The majority of N in soil, which was in the HF, was not influenced by climate proxies tested. However, both unprotected and occluded fractions of N were strongly influenced by climate. Soil N mean residence time (MRT) showed that drier/hotter climates have a shorter MRT, compared to mid-elevation sites with cooler/wetter climates. The effect of climate on deep saprock N storage might be indirect, primarily through climatic influence on the thickness of saprock. Overall, our findings suggest the mineral-associated HF N pool will not be vulnerable to changes in climate and will continue to contribute to the persistent soil N pool. The amount of topsoil and subsoil unprotected and occluded N can be explained by gross primary productivity and mean annual precipitation indicating that changes in climate can influence N partitioning. N stored in deep soil and saprock may be less vulnerable to climate than N stored in drier/hotter climates with less deeply stored N. It is critical to dig deeper to understand terrestrial ecosystems’ response to climate.

58 GEOSCIENCES↗

Porewater constituents inhibit microbially mediated greenhouse gas production (GHG) and regulate the response of soil organic matter decomposition to warming in anoxic peat from a Sphagnum -dominated bog

Abstract Northern peatlands store approximately one-third of terrestrial soil carbon. Climate warming is expected to stimulate the microbially mediated degradation of peat soil organic matter (SOM), leading to increasing greenhouse gas (GHG; carbon dioxide, CO2; methane, CH4) production and emission. Porewater dissolved organic matter (DOM) plays a key role in SOM decomposition; however, the mechanisms controlling SOM decomposition and its response to warming remain unclear. The temperature dependence of GHG production and microbial community dynamics were investigated in anoxic peat from a Sphagnum-dominated peatland. In this study, peat decomposition, which was quantified by GHG production and carbon substrate utilization is limited by terminal electron acceptors (TEA) and DOM, and these controls of microbially mediated SOM degradation are temperature-dependent. Elevated temperature led to a slight decrease in microbial diversity, and stimulated the growth of specific methanotrophic and syntrophic taxa. These results confirm that DOM is a major driver of decomposition in peatland soils contains inhibitory compounds, but the inhibitory effect is alleviated by warming.

Song, Tianze (ORCID:0000000282060247)↗

The Surface Chemistry of Methanol on Pd(111) and H–Pd(111) Surfaces: C–O Bond Cleavage and the Effects of Metal Hydride Formation

Palladium catalysts are frequently employed in processes where methanol is an energy vector or carrier, being useful for the synthesis of methanol from mixtures of carbon dioxide and hydrogen (CO 2 /H 2 ) or its steam reforming on demand. Results of synchrotron-based ambient pressure X-ray photoelectron spectroscopy for the adsorption of methanol on a Pd(111) model catalyst show a rich surface chemistry and complex phenomena that strongly depend on pressure and temperature. At low pressures (< 10 -6 Torr) and temperatures (< 300 K), CO is the dominant decomposition product. Further, as the pressure increases, cleavage of C-H, O-H and C-O bonds is observed, and at elevated temperatures (400-600 K) the formation of CO and CH x /C fragments compete on the surface. Thus, existing reaction networks for methanol decomposition must be modified. Furthermore, surface and subsurface hydrogen (coming from PdH x ) play a significant role in the stability and removal of CH x and C species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Duke Forest FACE (FACTS-I): Plant and Soil Response Data

This dataset describing the responses of plant and soil pools and fluxes to elevated atmospheric CO2 concentration and increased nitrogen supply was collected from Duke Forest Free Air CO2 Enrichment (FACE) – Forest-Atmosphere Carbon Transfer and Storage (FACTS-I) experiment from 1996 to 2012. The dataset includes data files for allometry (diameter at breast height, tree height, and height to live crown base), leaf area index, biomass (stem, branch, foliage, and root biomass, tree density, and basal area), net primary productivity (stem, branch, foliage, reproductive, and coarse root NPP), sap flux density, soil CO2 efflux, and stem temperature. Data files were formatted as .csv (Microsoft Excel or other spreadsheet programs can be used to read the format) and file descriptions, including variable name, unit, and data range, can be found in ‘FileDescription_[data_name].txt’ files. The Duke FACE experiment was in a loblolly pine (Pinus taeda L.) plantation established in 1983. Naturally regenerated broadleaved species including sweetgum (Liquidambar styraciflua L.) and tulip poplar (Liriodendron tulipifera L.), mostly in the overstory, and winged elm (Ulmus alata Michx.) and red maple (Acer rubrum L.) were common in the understory. The FACE experiment commenced with two plots (plots 7-8) in 1994 (Oren et al. 2001), with six additional plots (plots 1-6) coming online on 27 August 1996. CO2 enrichment was terminated on 31 October 2010 and post-enrichment data collection continued through 2012. Complete fertilization was applied annually to half of plots 7-8 from 1998 to 2004. The nutrient addition experiment expanded to half of plots 1-6 with a common protocol of N-fertilization in 2005 and continued until 2012. The levels of treatment in this dataset were expressed as ambient CO2 (AMB) or elevated CO2 (ELE) for CO2 treatment and control soil (CONT) or fertilized soil (FERT) for N treatment, respectively.

54 ENVIRONMENTAL SCIENCES↗

Robotic Technology for Exploration of Venus

Venus, the "greenhouse planet", is a scientifically fascinating place. A huge number of important scientific questions remain to be answered. Venus is sometimes called Earth's "sister planet" due to the fact that it is closest to the Earth in distance and similar to Earth in size. Despite its similarity to Earth, however, the climate of Venus is vastly different from Earth's. Understanding the atmosphere, climate, geology, and history of Venus could shed considerable light on our understanding of our own home planet. The surface of Venus is a hostile environment, with an atmosperic pressure of over 90 bar of carbon dioxide, temperature of 450 C, and shrouded in sulphuric-acid clouds. Venus has been explored by a number of missions from Earth, including the Russian Venera missions which landed probes on the surface, the American Pioneer missions which flew both orbiters and atmospheric probes to Venus, the Russian "Vega" mission, which floated balloons in the atmosphere of Venus, and most recently the American Magellan mission which mapped the surface by radar imaging. While these missions have answered basic questions about Venus, telling us the surface temperature and pressure, the elevations and topography of the continents, and the composition of the atmosphere and clouds, scientific mysteries still abound. Venus is of considerable interest to terrestrial atmospheric science, since of all the planets in the solar system, it is the closest analogue to the Earth in terms of atmosphere. Yet Venus' atmosphere is an example of "runaway greenhouse effect." Understanding the history and the dynamics of Venus' atmosphere could tell us considerable insight about the workings of the atmosphere of the Earth. It also has some interest to astrobiology-- could life have existed on Venus in an earlier, pre-greenhouse-effect phase? Could life still be possible in the temperate middle-atmosphere of Venus? The geology of Venus also has interest in the study of Earth. surface robot will require new technologies; specifically, it will require electronics, scientific instruments, power supplies, and mechanical linkages designed to operate at a temperature above 450 C-hot enough to melt the solder on a standard electronic circuit board. This will require devices made from advanced semiconductor materials, such as silicon carbide, or even new approaches, such as micro-vacuum tube electronics. Such materials are now being developed in the laboratory.

Landis, Geoffrey A.↗

Two Air Quality Regimes in Total Column NO2 over the Gulf of Mexico in May 2019: Shipboard and Satellite Views

The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico was conducted in May 2019 by NASA and the Bureau of Ocean Energy Management to determine the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns over the Outer Continental Shelf. Featured were nitrogen dioxide (NO 2 ) instruments (Pandora, Teledyne API analyzer) at Cocodrie, LA (29.26°, -90.66°), and on the Research Vessel Point Sur operating off the Louisiana coast with measurements of ozone, carbon monoxide and volatile organic compounds (VOC). The findings: (1) All NO 2 observations revealed two atmospheric regimes over the Gulf, the first influenced by tropical air in 10-14 May, the second influenced by flow from urban areas on 15-17 May; (2) Comparisons of OMI v4 and TROPOMI v1.3 TC (total column) NO 2 data with shipboard Pandora NO 2 column observations averaged 13% agreement with the largest difference during 15-17 May (~20%). At Cocodrie, the satellite-Pandora agreement was ~5%. (3) Three new-model Pandora instruments displayed a TC NO 2 precision of 0.01 Dobson Units (~5%); (4) Regions of smaller, older natural gas operations showed high methane readings from leakage; elevated VOC were also detected. Neither satellite nor spectrometer captured the magnitude of ambient NO 2 variability near ONG platforms. Given an absence of regular air quality monitoring over the Gulf of Mexico, SCOAPE data constitute a baseline against which future observations can be compared.

Nitrogen dioxide↗

Atmosphere Processing Module Automation and Catalyst Durability Analysis for Mars ISRU Pathfinder

The Mars In-Situ Resource Utilization Pathfinder was designed to create fuel using components found in the planet’s atmosphere and regolith for an ascension vehicle to return a potential sample return or crew return vehicle from Mars. The Atmosphere Processing Module (APM), a subunit of the pathfinder, uses cryocoolers to isolate and collect carbon dioxide from Mars simulant gas. The carbon dioxide is fed with hydrogen into a Sabatier reactor where methane is produced. The APM is currently undergoing the final stages of testing at Kennedy Space Center prior to process integration testing with the other subunits of the pathfinder. The automation software for the APM cryocoolers was tested and found to perform nominally. The catalyst used for the Sabatier reactor was investigated to determine the factors contributing to catalyst failure. The results from the catalyst testing require further analysis, but it appears that the rapid change in temperature during reactor start up or the elevated operating temperature is responsible for the changes observed in the catalyst.

Atmosphere Processing Module↗