Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO2 to ethylene and CO.

Developing atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of [Formula: see text]-O-Cr6+ on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO2. Ethylene selectivity and utilization of converted CO2 can reach 100 % and 99.0% under 500 °C at ethane conversion of 9.6%, respectively. In-situ/ex-situ spectroscopic studies and DFT calculations reveal atomic synergies between acidic Zn and redox Cr sites. [Formula: see text] ([Formula: see text]) sites facilitate ß-C-H bond cleavage in ethane and the formation of Zn-Hδ- hydride, thereby the enhanced basicity promotes CO2 adsorption/activation and prevents ethane C-C bond scission. The redox Cr site accelerates CO2 dissociation by replenishing lattice oxygen and facilitates H2O formation/desorption. This study presents the advantages of the ABC concept, paving the way for the rational design of novel advanced catalysts.

Hydrogen Storage with Aluminum Formate, ALF: Experimental, Computational, and Technoeconomic Studies.

Long-duration storage of hydrogen is necessary for coupling renewable H2 with stationary fuel cell power applications. In this work, aluminum formate (ALF), which adopts the ReO3-type structure, is shown to have remarkable H2 storage performance at non-cryogenic (>120 K) temperatures and low pressures. The most promising performance of ALF is found between 120 K and 160 K and at 10 bar to 20 bar. The study illustrates H2 adsorption performance of ALF over the 77 K to 296 K temperature range using gas isotherms, in situ neutron powder diffraction, and DFT calculations, as well as technoeconomic analysis (TEA), illustrating ALF's competitive performance for long-duration storage versus compressed hydrogen and leading metal-organic frameworks. In the TEA, it is shown that ALF's storage capacity, when combined with a temperature/pressure swing process, has advantages versus compressed H2 at a fraction of the pressure (15 bar versus 350 bar). Given ALF's performance in the 10 bar to 20 bar regime under moderate cooling, it is particularly promising for use in safe storage systems serving fuel cells.

The environmental controls on efficiency of enhanced rock weathering in soils.

Enhanced rock weathering (ERW) in soils is a promising carbon removal technology, but the realistically achievable efficiency, controlled primarily by in situ weathering rates of the applied rocks, is highly uncertain. Here we explored the impacts of coupled biogeochemical and transport processes and a set of primary environmental and operational controls, using forsterite as a proxy mineral in soils and a multiphase multi-component reactive transport model considering microbe-mediated reactions. For a onetime forsterite application of ~ 16 kg/m2, complete weathering within five years can be achieved, giving an equivalent carbon removal rate of ~ 2.3 kgCO2/m2/yr. However, the rate is highly variable based on site-specific conditions. We showed that the in situ weathering rate can be enhanced by conditions and operations that maintain high CO2 availability via effective transport of atmospheric CO2 (e.g. in well-drained soils) and/or sufficient biogenic CO2 supply (e.g. stimulated plant-microbe processes). Our results further highlight that the effect of increasing surface area on weathering rate can be significant-so that the energy penalty of reducing the grain size may be justified-only when CO2 supply is nonlimiting. Therefore, for ERW practices to be effective, siting and engineering design (e.g. optimal grain size) need to be co-optimized.

Environmental and Economic Impacts of Managing Nutrients in Digestate Derived from Sewage Sludge and High-Strength Organic Waste.

Increasingly stringent limits on nutrient discharges are motivating water resource recovery facilities (WRRFs) to consider the implementation of sidestream nutrient removal or recovery technologies. To further increase biogas production and reduce landfilled waste, WRRFs with excess anaerobic digestion capacity can accept other high-strength organic waste (HSOW) streams. The goal of this study was to characterize and evaluate the life-cycle global warming potential (GWP), eutrophication potential, and economic costs and benefits of sidestream nutrient management and biosolid management strategies following digestion of sewage sludge augmented by HSOW. Five sidestream nutrient management strategies were analyzed using environmental life-cycle assessment (LCA) and life-cycle cost analysis (LCCA) for codigestion of municipal sewage sludge with and without HSOW. As expected, thermal stripping and ammonia stripping were characterized by a much lower eutrophication potential than no sidestream treatment; significantly higher fertilizer prices would be needed for this revenue stream to cover the capital and chemical costs. Composting all biosolids dramatically reduced the GWP relative to the baseline biosolid option but had slightly higher eutrophication potential. These complex environmental and economic tradeoffs require utilities to consider their social, environmental, and economic values in addition to present or upcoming nutrient discharge limits prior to making decisions in sidestream and biosolids management.

Higher FORTA (Fit fOR The Aged) scores are associated with poor functional outcomes, dementia, and mortality in older people.

PURPOSE: Higher Fit fOR The Aged (FORTA) scores have been shown to be negatively associated with adverse clinical outcomes in older hospitalized patients. This has not been evaluated in other health care settings. The aim of this study was to examine the association of the FORTA score with relevant outcomes in the prospective AgeCoDe-AgeQualiDe cohort of community-dwelling older people. In particular, the longitudinal relation between the FORTA score and mortality and the incidence of dementia was evaluated. METHODS: Univariate and multivariate correlations between the FORTA score and activities of daily living (ADL) or instrumental activities of daily living (IADL) as well as comparisons between high vs. low FORTA scores were conducted. RESULTS: The FORTA score was significantly correlated with ADL/IADL at baseline and at all follow-up visits (p < 0.0001). ADL/IADL results of participants with a low FORTA score were significantly better than in those with high FORTA scores (p < 0.0001). The FORTA score was also significantly (p < 0.0001) correlated with ADL/IADL in the multivariate analysis. Moreover, the mean FORTA scores of participants with dementia were significantly higher (p < 0.0001) than in those without dementia at follow-up visits 6 through 9. The mean FORTA scores of participants who died were significantly higher than those of survivors at follow-up visits 7 (p < 0.05), 8 (p < 0.001), and 9 (p < 0.001). CONCLUSION: In this study, an association between higher FORTA scores and ADL as well as IADL was demonstrated in community-dwelling older adults. Besides, higher FORTA scores appear to be linked to a higher incidence of dementia and even mortality.

Artificial Intelligence Approach for Estimating Dairy Methane Emissions.

California's dairy sector accounts for ∼50% of anthropogenic CH4 emissions in the state's greenhouse gas (GHG) emission inventory. Although California dairy facilities' location and herd size vary over time, atmospheric inverse modeling studies rely on decade-old facility-scale geospatial information. For the first time, we apply artificial intelligence (AI) to aerial imagery to estimate dairy CH4 emissions from California's San Joaquin Valley (SJV), a region with ∼90% of the state's dairy population. Using an AI method, we process 316,882 images to estimate the facility-scale herd size across the SJV. The AI approach predicts herd size that strongly (>95%) correlates with that made by human visual inspection, providing a low-cost alternative to the labor-intensive inventory development process. We estimate SJV's dairy enteric and manure CH4 emissions for 2018 to be 496-763 Gg/yr (mean = 624; 95% confidence) using the predicted herd size. We also apply our AI approach to estimate CH4 emission reduction from anaerobic digester deployment. We identify 162 large (90th percentile) farms and estimate a CH4 reduction potential of 83 Gg CH4/yr for these large facilities from anaerobic digester adoption. The results indicate that our AI approach can be applied to characterize the manure system (e.g., use of an anaerobic lagoon) and estimate GHG emissions for other sectors.

Fertilizer demand and potential supply through nutrient recovery from organic waste digestate in California.

Diversion of organic waste from landfills offers an opportunity to recover valuable nutrients such as nitrogen and phosphorus that are typically discarded. Although prior research has explored the potential for buildout of anaerobic digestion (AD) infrastructure to treat organic waste and generate energy, a better understanding is needed of the nutrient recovery potential from the solid and liquid byproducts (digestate) resulting from AD of these waste streams. We quantified the system-wide mass of nutrients that can potentially be recovered in California by integrating current and potential future AD facilities with existing nutrient recovery technologies. Based on a profitable build-out scenario for AD, the potential for nitrogen and phosphorus recovery by mass was greatest from municipal sewage sludge. The nutrient recovery (% total mass) was determined for three different end products for the combined organic waste streams: liquid fertilizer [38% of the total recovered nitrogen (TN)], struvite [50% TN, 66% total phosphorous (TP)], and compost (12% TN, 34% TP). Based on the profitable build-out scenario of AD facilities in California, the recovered nutrients would offset an estimated 11% of TN and 29% of TP of in-state synthetic fertilizer demand, whereas a scenario in which all technically recoverable biomass is collected and treated could offset 44% of TN and 97% of TP demand.

Cost and Life-Cycle Greenhouse Gas Implications of Integrating Biogas Upgrading and Carbon Capture Technologies in Cellulosic Biorefineries.

Gaseous streams in biorefineries have been undervalued and underutilized. In cellulosic biorefineries, coproduced biogas is assumed to be combusted alongside lignin to generate process heat and electricity. Biogas can instead be upgraded to compressed biomethane and used as a transportation fuel. Capturing CO2-rich streams generated in biorefineries can also contribute to greenhouse gas (GHG) mitigation goals. We explore the economic and life-cycle GHG impacts of biogas upgrading and CO2 capture and storage (CCS) at ionic liquid-based cellulosic ethanol biorefineries using biomass sorghum. Without policy incentives, biorefineries with biogas upgrading systems can achieve a comparable minimum ethanol selling price (MESP) and reduced GHG footprint ($1.38/liter gasoline equivalent (LGE) and 12.9 gCO2e/MJ) relative to facilities that combust biogas onsite ($1.34/LGE and 24.3 gCO2e/MJ). Incorporating renewable identification number (RIN) values advantages facilities that upgrade biogas relative to other options (MESP of $0.72/LGE). Incorporating CCS increases the MESP but dramatically decreases the GHG footprint (-21.3 gCO2e/MJ for partial, -110.7 gCO2e/MJ for full CCS). The addition of CCS also decreases the cost of carbon mitigation to as low as $52-$78/t CO2, depending on the assumed fuel selling price, and is the lowest-cost option if both RIN and California's Low Carbon Fuel Standard credits are incorporated.

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 CO2e per tonne of organic waste. Composting raw organics resulted in the lowest GHG emissions, at -41 kg CO2e per tonne of waste, while upgrading biogas to RNG after dry AD resulted in -36 to -2 kg CO2e 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 NH3 emissions from landfills and land-application of digestate is essential to fully understand the trade-offs between alternatives.

Role of Digestate and Biochar in Carbon-Negative Bioenergy.

Digestate and biochar can be land applied to sequester carbon and improve net primary productivity, but the achievable scale is tied to expected growth in bioenergy production and land available for application. We use an attributional life-cycle assessment approach to estimate the greenhouse gas (GHG) emissions and carbon storage potential of biochar, digested solids, and composted digested solids generated from organic waste in California as a test case. Our scenarios characterize changes in organic waste production, bioenergy facility build-out, bioenergy byproduct quality, and soil response. Moderate to upper bound growth in the bioenergy sector with annual byproduct disposal over 100 years could provide a cumulative GHG offset of 50-400 MMTCO2 equiv, with an additional 80-300 MMTC sequestered in soils. This corresponds to net GHG mitigation over 100 years equivalent to 340-1500 MMTCO2 equiv (80-350% of California's annual emissions). In most scenarios, there is sufficient working land to apply all available biochar and digestate, although land becomes a constraint if the soil's rest time between applications increases from 5 to 15 years.

Dynamic Geospatial Modeling of the Building Stock To Project Urban Energy Demand.

In the United States, buildings account for more than 40% of total energy consumption and the evolution of the urban form will impact the effectiveness of strategies to reduce energy use and mitigate emissions. This paper presents a broadly applicable approach for modeling future commercial, residential, and industrial floorspace, thermal consumption (heating and cooling), and associated GHG emissions at the tax assessor land parcel level. The approach accounts for changing building standards and retrofitting, climate change, and trends in housing and industry. We demonstrate the automated workflow for California and project building stock, thermal energy consumption, and associated GHG emissions out to 2050. Our results suggest that if buildings in California have long lifespans, and minimal energy efficiency improvements compared to building codes reflective of 2008, then the state will face a 20% or higher increase in thermal energy consumption by 2050. Baseline annual GHG emissions associated with thermal energy consumption in the modeled building stock in 2016 is 34% below 1990 levels (110 Mt CO2eq/y). While the 2020 targets for the reduction of GHG emissions set by the California Senate Bill 350 have already been met, none of our scenarios achieve >80% reduction from 1990 levels by 2050, despite assuming an 86% reduction in electricity carbon intensity in our "Low Carbon" scenario. The results highlight the challenge California faces in meeting its new energy efficiency targets unless the State's building stock undergoes timely and strategic turnover, paired with deep retrofitting of existing buildings and natural gas equipment.

Bioenergy Potential from Food Waste in California.

Food waste makes up approximately 15% of municipal solid waste generated in the United States, and 95% of food waste is ultimately landfilled. Its bioavailable carbon and nutrient content makes it a major contributor to landfill methane emissions, but also presents an important opportunity for energy recovery. This paper presents the first detailed analysis of monthly food waste generation in California at a county level, and its potential contribution to the state's energy production. Scenarios that rely on excess capacity at existing anaerobic digester (AD) and solid biomass combustion facilities, and alternatives that allow for new facility construction, are developed and modeled. Potential monthly electricity generation from the conversion of gross food waste using a combination of AD and combustion varies from 420 to 700 MW, averaging 530 MW. At least 66% of gross high moisture solids and 23% of gross low moisture solids can be treated using existing county infrastructure, and this fraction increases to 99% of high moisture solids and 55% of low moisture solids if waste can be shipped anywhere within the state. Biogas flaring practices at AD facilities can reduce potential energy production by 10 to 40%.