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At least 1,045 records · Page 58

Leaf-cutting ant (Atta cephalotes) nests may be hotspots of methane and carbon dioxide emissions in tropical forests

Leaf-cutting ants of the genus Atta are widely distributed throughout the American tropics and subtropics and rival other herbivores in the consumption of surrounding foliage. Although numerous studies have been conducted on the role these insects play in herbivory and organic matter dynamics, only a handful of studies have examined their impacts on soil greenhouse gas emissions. Our study investigated fluxes of carbon dioxide (CO 2 ) and methane (CH 4 ) from three nests of Atta cephalotes using a portable greenhouse gas analyzer, and measured CO 2 and CH 4 emissions from soils containing nest holes that ranged 5.2–152.1 g CO 2 -C and –1.1 to 15,264.7 mg CH 4 -C m -2 day -1 , respectively. Fluxes of CO 2 and CH 4 were positively correlated above nest holes, but not in patches of soil away from leaf-cutting ant nests. Nearby non-nest soil emissions were significantly lower, ranging from 0.6 to 6.0 g CO 2 -C and –1.3 to 0.77 mg CH 4 -C m -2 day -1 . Fluxes of both gases among nests and among holes within a single nest were highly variable. This preliminary dataset is small in scale both temporarily and geographically, but the discovery of substantial greenhouse gas fluxes from Atta cephalotes nests may have important implications for carbon budgets of tropical and subtropical American forests. Further work will be necessary to determine the mechanisms behind enhanced greenhouse gas emissions from leaf-cutting ant nests, and how this may alter ecosystem-scale CO 2 emissions and CH 4 sink strength in tropical forest soils.

54 ENVIRONMENTAL SCIENCES↗

Spectral emission characteristics near 646 nm and plasma properties of laser-induced plasma of gaseous uranium hexafluoride

We present a detailed investigation of the temporal evolution of line and continuum emissions in laser-induced breakdown spectroscopy (LIBS) of gaseous uranium hexafluoride (UF 6 ), focusing on the spectral region near 646 nm. Spectral emission features, signal-to-background ratios (SBRs) of selected uranium lines, and spectral linewidths were examined under varying UF 6 pressures (15–60 Torr) and laser pulse energies (10–60 mJ). Higher pressures and pulse energies enhanced continuum emission and reduced SBRs but did not cause significant spectral congestion. Additional studies with the use of different laser systems, including nanosecond-pulsed Nd:YAG lasers (at fundamental and various harmonics) and a femtosecond-pulsed Ti:sapphire laser, revealed long-lived plasma continua in all cases. This persistent continuum is attributed to a pseudo-continuum from overlapping molecular emissions, as its intensity scales linearly with electron number density, deviating from the expected quadratic dependence of classical ion–electron interactions for free-free and free-bound continuum emission. Based on plasma persistence time, SBR, U II/U I intensity ratios, and electronic excitation temperature, no fundamental advantage was found for femtosecond-pulsed lasers over conventional nanosecond-pulsed ones for UF 6 enrichment assay with direct LIBS measurement.

Laser-induced breakdown spectroscopy↗

Hierarchical analysis of US electric vehicle subsidies for carbon emission mitigation

Electric vehicle (EV) adoptions are promoted with subsidies to reduce greenhouse gas emissions from ground transportation. In this paper, a hierarchical analysis is presented on the potential of greenhouse gas emission mitigation via the electric vehicle subsidy policy at state level in the US, through research of environmental and economic fundamentals of electric vehicle operations, energy consumptions, battery degradation and service life. It has been found that restructuring the federal subsidies to promote EV adoption can significantly reduce greenhouse gas emissions across the US. The reduction costs of greenhouse gas emissions vary between $\$1167.44$/ton in Vermont to $\$6880.13$/ton in Wyoming. A case study reveals that 15.24 % more greenhouse gas emissions can be reduced with a tiered federal subsidy structure. The restructuring of subsidies will also encourage the adoption of clean energies in the grid fuel mix and drive technological advancements to extend the battery lifetime in the future.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Life-Cycle Greenhouse Gas Emissions and Human Health Trade-Offs of Organic Waste Management Strategies

Waste-to-energy systems can play an important role in diverting organic waste from landfills. However, real-world waste management can differ from idealized practices, and emissions driven by microbial communities and complex chemical processes are poorly understood. This study presents a comprehensive life-cycle assessment, using reported and measured data, of competing management alternatives for organic municipal solid waste including landfilling, composting, dry anaerobic digestion (AD) for the production of renewable natural gas (RNG), and dry AD with electricity generation. Landfilling is the most greenhouse gas (GHG)-intensive option, emitting nearly 400 kg CO 2e per tonne of organic waste. Composting raw organics resulted in the lowest GHG emissions, at -41 kg CO 2e per tonne of waste, while upgrading biogas to RNG after dry AD resulted in -36 to -2 kg CO 2e per tonne. Monetizing the results based on social costs of carbon and other air pollutant emissions highlights the importance of ground-level NH3 emissions from composting nitrogen-rich organic waste or post-AD solids. However, better characterization of material-specific NH 3 emissions from landfills and land-application of digestate is essential to fully understand the trade-offs between alternatives.

54 ENVIRONMENTAL SCIENCES↗

Greenhouse Gas Emissions and Decarbonization Potential of Global Fired Clay Brick Production

Fired clay bricks (FCBs) are a dominant building material globally due to their low cost and simplicity of production, especially in low- and middle-income countries. With a projected rising housing demand, commensurate growth in brick demand is anticipated, the production of which could result in significant greenhouse gas (GHG) emissions. Robust models are needed to estimate brick demand and emissions to systematically address decarbonization pathways. Few sources report production values; hence, we present two novel proxy models: (i) a consumption prediction model, relying on country-specific clay extraction data, dynamic building stock modeling, and average material intensity use allowing for projections to 2050; and (ii) a GHG emissions model, using literature-based data and production technology-specific inputs. Based on these models, the current global FCB consumption is estimated as 2.18 Gt annually, resulting in approximately 500 million tCO2e (1% of current global GHG emissions). If unaddressed, this fraction could increase to 3.5-5% in 2050 considering a moderate SSP 2-4.5 climate change mitigation scenario. Consequently, we explored three potential decarbonization pathways: (i) improving energy efficiency; (ii) shifting production to best practices; and (iii) replacing half of FCB demand with hollow concrete blocks, resulting in 27%, 49%, and 51% reduction in GHG emissions, respectively.

Olsson, Josefine A↗

Kβ X-ray Emission Spectroscopy as a Probe of Cu(I) Sites: Application to the Cu(I) Site in Preprocessed Galactose Oxidase

Cu(I) active sites in metalloproteins are involved in O 2 activation, but their O 2 reactivity is difficult to study due to the Cu(I) d 10 closed shell which precludes the use of conventional spectroscopic methods. Kβ X-ray emission spectroscopy (XES) is a promising technique for investigating Cu(I) sites as it detects photons emitted by electronic transitions from occupied orbitals. Here, we demonstrate the utility of Kβ XES in probing Cu(I) sites in model complexes and a metalloprotein. Using Cu(I)Cl, emission features from double-ionization (DI) states are identified using varying incident X-ray photon energies, and a reasonable method to correct the data to remove DI contributions is presented. Kβ XES spectra of Cu(I) model complexes, having biologically relevant N/S ligands and different coordination numbers, are compared and analyzed, with the aid of density functional theory (DFT) calculations, to evaluate the sensitivity of the spectral features to the ligand environment. While the low-energy Kβ 2,5 emission feature reflects the ionization energy of ligand np valence orbitals, the high-energy Kβ 2,5 emission feature corresponds to transitions from molecular orbitals (MOs) having mainly Cu 3d character with the intensities determined by ligand-mediated d–p mixing. A Kβ XES spectrum of the Cu(I) site in preprocessed galactose oxidase (GO pre ) supports the 1Tyr/2His structural model that was determined by our previous X-ray absorption spectroscopy and DFT study. Finally, the high-energy Kβ 2,5 emission feature in the Cu(I)-GO pre data has information about the MO containing mostly Cu 3d x 2 –y 2 character that is the frontier molecular orbital (FMO) for O 2 activation, which shows the potential of Kβ XES in probing the Cu(I) FMO associated with small-molecule activation in metalloproteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin-Correlated Radical Pairs as Magnetic Switches for Controlling Emissive Triplet States via Triplet–Triplet Energy Transfer

Magnetic fields offer a powerful means to control molecular emission, enabling quantum sensing and spin-level control of chemical reactions. Here, we demonstrate a strategy to magnetically control red to near-infrared phosphorescence via triplet–triplet energy transfer (TTET) from donor–chiral bridge–acceptor (D−χ–A) molecules that generate spin-correlated radical pairs (SCRPs) upon photoexcitation. These SCRPs yield non-emissive triplet excited states whose formation is sensitive to magnetic fields. Here, by transferring this energy to emissive Pt- and Pd-based π-extended porphyrins, we enable magnetic control over phosphorescence that would otherwise be unresponsive to weak magnetic fields (<1 T). This approach establishes a platform for quantifying magnetic field effects on silent triplet states while extending magnetically responsive emission into the near-infrared. Coupling SCRP-based molecular magnetic switches to long-wavelength emissive acceptors offers a new way for probing and modulating spin-dependent processes and triplet-state populations in molecular systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sensitized Near-Infrared Emission of SiGe Nanocrystals via Heterostructuring with Quasi Two-Dimensional Perovskite

The near-infrared (NIR) emission of silicon–germanium alloy nanocrystals (SiGe NCs) was sensitized by heterostructuring with a quasi two-dimensional (Q-2D) perovskite (CsPbBr 3 blended with butylammonium bromide (BABr)). Colloidal SiGe NCs were synthesized by using a nonthermal plasma method with chloride precursors. As-synthesized SiGe NCs showed no detectable photoluminescence (PL). Embedding the SiGe NCs within the perovskite matrix via spin coating led to a heterostructure exhibiting dual emissions: green emission at 520 nm from the perovskite and NIR emission at 1035 nm from the SiGe NCs. Time-integrated and resolved PL measurements and transient absorption spectroscopy revealed energy transfer from the perovskite to the SiGe NCs, which sensitized the NIR emission from the SiGe NCs and quenched the green PL for the perovskite. These results demonstrate that Ge alloying can effectively tune the bandgap of Si NCs and highlight the feasibility of heterostructuring perovskites and photoluminescent NCs to enhance or activate their PL. In conclusion, this approach broadens their potential applications in the NIR region.

36 MATERIALS SCIENCE↗

Source-Resolved Inversion of Elemental Carbon Emissions in California Using Log-Space Bayesian Inference

Elemental carbon (EC), operationally quantified by thermal-optical analysis, is widely used as a proxy for black carbon (BC) relevant to short-term climate forcing and public health. Current EC emission inventories remain highly uncertain, with persistent discrepancies between bottom-up and top-down estimates. In this study, we develop a source-resolved, log-space Bayesian inversion framework applied to estimate California’s statewide EC emissions in 2019. By integrating surface EC measurements from the EPA’s Air Quality System network with high-resolution source contributions simulated by a chemical transport model, we identify a one-third underestimation in the existing statewide EC inventory, requiring an increase of the total from a prior of 8.58 [5.49–13.75] Gg year–1 to a posterior estimate of 12.78 [10.71–15.37] Gg year–1. This discrepancy is primarily driven by substantial underestimations in the power and industrial and off-road mobile sectors. Furthermore, population-weighted exposure analysis reveals a marked sectoral divergence between emission mass and health burden: off-road mobile sources dominate both emissions and exposure, accounting for 31% of statewide exposure, while residential wood combustion contributes 26% of total exposure despite comprising only 19% of total emissions, due to its source proximity to population. These findings underscore the need to update sector-specific EC speciation profiles and demonstrate that mitigation strategies targeting off-road mobile sources and residential wood combustion are critical for reducing EC-related health impacts in California.

Zhang, Jie↗

Carbon-13 Radiofrequency Amplification by Stimulated Emission of Radiation of the Hyperpolarized Ketone and Hemiketal Forms of Allyl [1- 13 C]Pyruvate

13 C hyperpolarized pyruvate is an emerging MRI contrast agent for sensing molecular events in cancer and other diseases with aberrant metabolic pathways. This metabolic contrast agent can be produced via several hyperpolarization techniques. Despite remarkable success in research settings, widespread clinical adoption faces substantial roadblocks because the current sensing technology utilized to sense this contrast agent requires the excitation of 13 C nuclear spins that also need to be synchronized with MRI field gradient pulses. Here, we demonstrate sensing of hyperpolarized allyl [1- 13 C]pyruvate via the stimulated emission of radiation that mitigates the requirements currently blocking broader adoption. Specifically, 13 C Radiofrequency Amplification by Stimulated Emission of Radiation ( 13 C RASER) was obtained after pairwise addition of parahydrogen to a pyruvate precursor, detected in a commercial inductive detector with a quality factor (Q) of 32 for sample concentrations as low as 0.125 M with 13 C polarization of 4%. Moreover, parahydrogen-induced polarization allowed for the preparation of a mixture of ketone and hemiketal forms of hyperpolarized allyl [1- 13 C]pyruvate, which are separated by 10 ppm in 13 C NMR spectra. This is a good model system to study the simultaneous 13 C RASER signals of multiple 13 C species. This system models the metabolic production of hyperpolarized [1- 13 C]lactate from hyperpolarized [1- 13 C]pyruvate, which has a similar chemical shift difference. Our results show that 13 C RASER signals can be obtained from both species simultaneously when the emission threshold is exceeded for both species. On the other hand, when the emission threshold is exceeded only for one of the hyperpolarized species, 13 C stimulated emission is confined to this species only, therefore enabling the background-free detection of individual hyperpolarized 13 C signals. Furthermore, the reported results pave the way to novel sensing approaches of 13 C hyperpolarized pyruvate, potentially unlocking hyperpolarized 13 C MRI on virtually any MRI system–an attractive vision for the future molecular imaging and diagnostics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Life Cycle Greenhouse Gas Emissions of Biogas Upgrading for Fuel Production

Waste-to-Renewable Natural Gas (RNG) offers a promising solution to alleviating waste management challenges by converting waste into renewable fuels. Here, this process can significantly reduce greenhouse gas (GHG) emissions, as demonstrated through a comprehensive life cycle analysis. Biogas upgrading is essential to enhance the methane concentration, though it could be energy-intensive and susceptible to methane slippage. Four commonly adopted biogas upgrading technologies, including pressure swing adsorption, membrane separation, chemical absorption, and water scrubbing, are considered. Our study evaluates the life cycle GHG emissions of RNG production from major sources of waste in the U.S. including wastewater sludge, food waste, landfill gas, dairy cow manure, and swine manure. Meta-analysis was conducted to assess methane slippage and energy consumption of biogas upgrading and associated GHG emissions, while accounting for potential avoided emissions from conventional waste management, which vary widely (ranging from −481.0 to 101.8 g CO 2 -eq/MJ). Under default upstream assumptions, representative carbon intensity of RNG varies from about −125 g of CO 2 -eq/MJ (dairy cow manure) to about 41 g of CO 2 -eq/MJ (wastewater sludge). We also explored RNG applications in producing hydrogen, ammonia, and compressed/liquefied forms. These findings highlight the potential of RNG and RNG-derived fuels to reduce GHG emissions and bolster the U.S. energy supply.

Biogas upgrades↗

An Analysis of Abandoned Oil Well Characteristics Affecting Methane Emissions Estimates in the Cherokee Platform in Eastern Oklahoma

Anthropogenic activities increase methane emissions, contributing to greenhouse gas levels and adversely affecting the environment. Abandoned oil and gas wells potentially leak methane, but data are limited. We analyze methane emissions from abandoned wells (n = 179) in the Cherokee Platform in Oklahoma, a previously unaccounted basin, and compare emissions factors (EFs) to those in the Greenhouse Gas Inventory. We compare the contribution of various characteristics to the propensity for leakage. Higher emissions were observed with shallower wells and with unplugged wells. Plugged wells (n = 20) had an average EF of 96 ± 429 g/day and 65 ± 294 g/day for unplugged wells (n = 159). The majority of wells had no detectable leak. We calculated ethane EFs based on geochemical analysis of gas samples, finding higher EFs for unplugged (1.2 ± 5.5 g/day) versus plugged (0.9 ± 4.6 g/day) wells. The data indicate that in addition to the location of abandoned wells, physical characteristics are necessary to consider in estimating methane emissions.

58 GEOSCIENCES↗

Upscaling Wetland Methane Emissions From the FLUXNET–CH4 Eddy Covariance Network (UpCH4 v1.0): Model Development, Network Assessment, and Budget Comparison

Wetlands are responsible for 20%–31% of global methane (CH 4 ) emissions and account for a large source of uncertainty in the global CH 4 budget. Data-driven upscaling of CH 4 fluxes from eddy covariance measurements can provide new and independent bottom-up estimates of wetland CH 4 emissions. Here, we develop a six-predictor random forest upscaling model (UpCH4), trained on 119 site-years of eddy covariance CH 4 flux data from 43 freshwater wetland sites in the FLUXNET-CH4 Community Product. Network patterns in site-level annual means and mean seasonal cycles of CH 4 fluxes were reproduced accurately in tundra, boreal, and temperate regions (Nash-Sutcliffe Efficiency ~0.52–0.63 and 0.53). UpCH4 estimated annual global wetland CH 4 emissions of 146 ± 43 TgCH 4 y –1 for 2001–2018 which agrees closely with current bottom-up land surface models (102–181 TgCH 4 y –1 ) and overlaps with top-down atmospheric inversion models (155–200 TgCH 4 y –1 ). However, UpCH4 diverged from both types of models in the spatial pattern and seasonal dynamics of tropical wetland emissions. We conclude that upscaling of eddy covariance CH 4 fluxes has the potential to produce realistic extra-tropical wetland CH 4 emissions estimates which will improve with more flux data. To reduce uncertainty in upscaled estimates, researchers could prioritize new wetland flux sites along humid-to-arid tropical climate gradients, from major rainforest basins (Congo, Amazon, and SE Asia), into monsoon (Bangladesh and India) and savannah regions (African Sahel) and be paired with improved knowledge of wetland extent seasonal dynamics in these regions.

54 ENVIRONMENTAL SCIENCES↗

Sensitive Response of Atmospheric Oxidative Capacity to the Uncertainty in the Emissions of Nitric Oxide (NO) From Soils in Amazonia

Abstract Soils are a major source of nitrogen oxides, which in the atmosphere help govern its oxidative capacity. Thus the response of soil nitric oxide (NO) emissions to forcings such as warming or forest loss has a meaningful impact on global atmospheric chemistry. We find that the soil emission rate of NO in Amazonia from a common inventory is biased low by at least an order of magnitude in comparison to tower‐based observations. Accounting for this regional bias decreases the modeled global methane lifetime by 1.4%–2.6%. In comparison, a fully deforested Amazonia, representing a 37% decrease in global emissions of isoprene, decreases methane lifetime by at most 4.6%, highlighting the sensitive response of oxidation rates to changes in emissions of NO compared to those of terpenes. Our results demonstrate that improving our understanding of soil NO emissions will yield a more accurate representation of atmospheric oxidative capacity.

Geology↗

Has Reducing Ship Emissions Brought Forward Global Warming?

Abstract Ships brighten low marine clouds from emissions of sulfur and aerosols, resulting in visible “ship tracks”. In 2020, new shipping regulations mandated an ∼80% reduction in the allowed fuel sulfur content. Recent observations indicate that visible ship tracks have decreased. Model simulations indicate that since 2020 shipping regulations have induced a net radiative forcing of +0.12 Wm −2 . Analysis of recent temperature anomalies indicates Northern Hemisphere surface temperature anomalies in 2022–2023 are correlated with observed cloud radiative forcing and the cloud radiative forcing is spatially correlated with the simulated radiative forcing from the 2020 shipping emission changes. Shipping emissions changes could be accelerating global warming. To better constrain these estimates, better access to ship position data and understanding of ship aerosol emissions are needed. Understanding the risks and benefits of emissions reductions and the difficultly in robust attribution highlights the large uncertainty in attributing proposed deliberate climate intervention.

54 ENVIRONMENTAL SCIENCES↗

A Lake Biogeochemistry Model for Global Methane Emissions: Model Development, Site‐Level Validation, and Global Applicability

Abstract Lakes are important sentinels of climate change and may contribute over 30% of natural methane (CH 4 ) emissions; however, no earth system model (ESM) has represented lake CH 4 dynamics. To fill this gap, we refined a process‐based lake biogeochemical model to simulate global lake CH 4 emissions, including representation of lake bathymetry, oxic methane production (OMP), the effect of water level on ebullition, new non‐linear CH 4 oxidation kinetics, and the coupling of sediment carbon pools with in‐lake primary production and terrigenous carbon loadings. We compiled a lake CH 4 data set for model validation. The model shows promising performance in capturing the seasonal and inter‐annual variabilities of CH 4 emissions at 10 representative lakes for different lake types and the variations in mean annual CH 4 emissions among 106 lakes across the globe. The model reproduces the variations of the observed surface CH 4 diffusion and ebullition along the gradients of lake latitude, depth, and surface area. The results suggest that OMP could play an important role in surface CH 4 diffusion, and its relative importance is higher in less productive and/or deeper lakes. The model performance is improved for capturing CH 4 outgassing events in non‐floodplain lakes and the seasonal variability of CH 4 ebullition in floodplain lakes by representing the effect of water level on ebullition. The model can be integrated into ESMs to constrain global lake CH 4 emissions and climate‐CH 4 feedback.

54 ENVIRONMENTAL SCIENCES↗

Broadband nonreciprocal thermal emissivity and absorptivity

A body that violates Kirchhoff’s law of thermal radiation exhibits an inequality in its spectral directional absorptivity and emissivity. Achieving such an inequality is of fundamental interest as well as a prerequisite for achieving thermodynamic limits in photonic energy conversion and radiative cooling. Thus far, inequalities in the spectral directional emissivity and absorptivity have been limited to narrow spectral resonances, or wavelengths well beyond the infrared regime4. Bridging the gap from basic demonstrations to practical applications requires control over a broad spectral range of the unequal spectral directional absorptivity and emissivity. In this work, we demonstrate broadband nonreciprocal thermal emissivity and absorptivity by measuring the thermal emissivity and absorptivity of gradient epsilon-near-zero InAs layers of subwavelength thicknesses (50 nm and 150 nm) with an external magnetic field. The effect occurs in a spectral range (12.5–16 μm) that overlaps with the infrared transparency window and is observed at moderate (1 T) magnetic fields.

42 ENGINEERING↗

The sponge effect and carbon emission mitigation potentials of the global cement cycle

Cement plays a dual role in the global carbon cycle like a sponge: its massive production contributes significantly to present-day global anthropogenic CO 2 emissions, yet its hydrated products gradually reabsorb substantial amounts of atmospheric CO 2 (carbonation) in the future. The role of this sponge effect along the cement cycle (including production, use, and demolition) in carbon emissions mitigation, however, remains hitherto unexplored. Here, we quantify the effects of demand- and supply-side mitigation measures considering this material-energy-emissions-uptake nexus, finding that climate goals would be imperiled if the growth of cement stocks continues. Future reabsorption of CO 2 will be significant (~30% of cumulative CO 2 emissions from 2015 to 2100), but climate goal compliant net CO 2 emissions reduction along the global cement cycle will require both radical technology advancements (e.g., carbon capture and storage) and widespread deployment of material efficiency measures, which go beyond those envisaged in current technology roadmaps.

54 ENVIRONMENTAL SCIENCES↗