Near-complete depolymerization of polyesters with nano-dispersed enzymes.

Successfully interfacing enzymes and biomachinery with polymers affords on-demand modification and/or programmable degradation during the manufacture, utilization and disposal of plastics, but requires controlled biocatalysis in solid matrices with macromolecular substrates1-7. Embedding enzyme microparticles speeds up polyester degradation, but compromises host properties and unintentionally accelerates the formation of microplastics with partial polymer degradation6,8,9. Here we show that by nanoscopically dispersing enzymes with deep active sites, semi-crystalline polyesters can be degraded primarily via chain-end-mediated processive depolymerization with programmable latency and material integrity, akin to polyadenylation-induced messenger RNA decay10. It is also feasible to achieve processivity with enzymes that have surface-exposed active sites by engineering enzyme-protectant-polymer complexes. Poly(caprolactone) and poly(lactic acid) containing less than 2 weight per cent enzymes are depolymerized in days, with up to 98 per cent polymer-to-small-molecule conversion in standard soil composts and household tap water, completely eliminating current needs to separate and landfill their products in compost facilities. Furthermore, oxidases embedded in polyolefins retain their activities. However, hydrocarbon polymers do not closely associate with enzymes, as their polyester counterparts do, and the reactive radicals that are generated cannot chemically modify the macromolecular host. This study provides molecular guidance towards enzyme-polymer pairing and the selection of enzyme protectants to modulate substrate selectivity and optimize biocatalytic pathways. The results also highlight the need for in-depth research in solid-state enzymology, especially in multi-step enzymatic cascades, to tackle chemically dormant substrates without creating secondary environmental contamination and/or biosafety concerns.

Impact of bioenergy feedstock carbon farming on sustainable aviation fuel viability in the United States.

Biomass-derived sustainable aviation fuel holds significant potential for decarbonizing the aviation sector. Its long-term viability depends on crop choice, longevity of soil organic carbon (SOC) sequestration, and the biomass-to-biojet fuel conversion efficiency. We explored the impact of fuel price and SOC value on viable biojet fuel production scale by integrating an agroecosystem model with a field-to-biojet fuel production process model for 1,4-dimethylcyclooctane (DMCO), a representative high-performance biojet fuel molecule, from Miscanthus, sorghum, and switchgrass. Assigning monetary value to SOC sequestration results in substantially different outcomes than an increased fuel selling price. If SOC accumulation is valued at $185/ton CO2, planting Miscanthus for conversion to DMCO would be economically cost-competitive across 66% of croplands across the continental United States (US) by 2050 if conventional jet fuel remains at $0.74/L (in 2020 US dollars). Cutting the SOC sequestration value in half reduces the viable area to 54% of cropland, and eliminating any payment for SOC shrinks the viable area to 16%. If future biojet fuel prices increase to $1.24/L-Jet A-equivalent, 48 to 58% of the total cultivated land in the United States could support a more diverse set of feedstocks including Miscanthus, sorghum, or switchgrass. Among these options, only 8-14% of the area would be suitable exclusively for Miscanthus cultivation. These findings highlight the intersection of natural solutions for carbon removal and the use of deep-rooted feedstocks for biofuels and biomanufacturing. The results underscore the need to establish clear and consistent values for SOC sequestration to enable the future bioeconomy.

Complementary roles for mechanical and solvent-based recycling in low-carbon, circular polypropylene.

Plastic recycling presents a vexing challenge. Mechanical recycling offers substantial greenhouse gas emissions savings relative to virgin plastic production but suffers from degraded aesthetic and mechanical properties. Polypropylene, one of the most widely used and lowest-cost plastics, features methyl pendants along the polymer backbone, rendering it particularly susceptible to declining properties, performance, and aesthetics across a succession of mechanical recycles. Advanced processes, such as solvent-assisted recycling, promise near-virgin quality outputs at a greater energy and emissions footprint. Mechanical and advanced recycling are often presented as competing options, but real-world plastic waste streams are likely to require preprocessing regardless of whether they are routed to an advanced process. This study quantifies the life-cycle greenhouse gas implications of multiple recycling strategies and proposes a system in which mechanical and solvent-assisted recycling can be leveraged together to boost recycling rates and satisfy demand for a wider range of product applications. Polypropylene can be recovered from mixed-plastic bales produced at material recovery facilities and processed through mechanical recycling, with a varying fraction sent for further upgrading via solvent-assisted recycling to produce material approved for food packaging and other higher-quality applications. The resulting mechanically recycled rigid polypropylene reduces life-cycle greenhouse gas emissions by 80% relative to the same quantity of virgin material, while the upgraded higher-quality material achieves GHG savings of 30%.

Comparing in planta accumulation with microbial routes to set targets for a cost-competitive bioeconomy.

Plants and microbes share common metabolic pathways for producing a range of bioproducts that are potentially foundational to the future bioeconomy. However, in planta accumulation and microbial production of bioproducts have never been systematically compared on an economic basis to identify optimal routes of production. A detailed technoeconomic analysis of four exemplar compounds (4-hydroxybenzoic acid [4-HBA], catechol, muconic acid, and 2-pyrone-4,6-dicarboxylic acid [PDC]) is conducted with the highest reported yields and accumulation rates to identify economically advantaged platforms and breakeven targets for plants and microbes. The results indicate that in planta mass accumulation ranging from 0.1 to 0.3 dry weight % (dwt%) can achieve costs comparable to microbial routes operating at 40 to 55% of maximum theoretical yields. These yields and accumulation rates are sufficient to be cost competitive if the products are sold at market prices consistent with specialty chemicals ($20 to $50/kg). Prices consistent with commodity chemicals will require an order-of-magnitude-greater accumulation rate for plants and/or yields nearing theoretical maxima for microbial production platforms. This comparative analysis revealed that the demonstrated accumulation rates of 4-HBA (3.2 dwt%) and PDC (3.0 dwt%) in engineered plants vastly outperform microbial routes, even if microbial platforms were to reach theoretical maximum yields. Their recovery and sale as part of a lignocellulosic biorefinery could enable biofuel prices to be competitive with petroleum. Muconic acid and catechol, in contrast, are currently more attractive when produced microbially using a sugar feedstock. Ultimately, both platforms can play an important role in replacing fossil-derived products.

Corridor-Level Impacts of Battery-Electric Heavy-Duty Trucks and the Effects of Policy in the United States.

Electrifying freight trucks will be key to alleviating air pollution burdens on disadvantaged communities and mitigating climate change. The United States plans to pursue this aim by adding vehicle charging infrastructure along specific freight corridors. This study explores the coevolution of the electricity grid and freight trucking landscape using an integrated assessment framework to identify when each interstate and drayage corridor becomes advantageous to electrify from a climate and human health standpoint. Nearly all corridors achieve greenhouse gas emission reductions if electrified now. Most can reduce health impacts from air pollution if electrified by 2040 although some corridors in the Midwest, South, and Mid-Atlantic regions remain unfavorable to electrify from a human health standpoint, absent policy support. Recent policy, namely, the Inflation Reduction Act, accelerates this timeline to 2030 for most corridors and results in net human health benefits on all corridors by 2050, suggesting that near-term investments in truck electrification, particularly drayage corridors, can meaningfully reduce climate and health burdens.

Co-Processing Agricultural Residues and Wet Organic Waste Can Produce Lower-Cost Carbon-Negative Fuels and Bioplastics.

Scalable, low-cost biofuel and biochemical production can accelerate progress on the path to a more circular carbon economy and reduced dependence on crude oil. Rather than producing a single fuel product, lignocellulosic biorefineries have the potential to serve as hubs for the production of fuels, production of petrochemical replacements, and treatment of high-moisture organic waste. A detailed techno-economic analysis and life-cycle greenhouse gas assessment are developed to explore the cost and emission impacts of integrated corn stover-to-ethanol biorefineries that incorporate both codigestion of organic wastes and different strategies for utilizing biogas, including onsite energy generation, upgrading to bio-compressed natural gas (bioCNG), conversion to poly(3-hydroxybutyrate) (PHB) bioplastic, and conversion to single-cell protein (SCP). We find that codigesting manure or a combination of manure and food waste alongside process wastewater can reduce the biorefinery's total costs per metric ton of CO2 equivalent mitigated by half or more. Upgrading biogas to bioCNG is the most cost-effective climate mitigation strategy, while upgrading biogas to PHB or SCP is competitive with combusting biogas onsite.

Private and External Costs and Benefits of Replacing High-Emitting Peaker Plants with Batteries.

Falling costs of lithium-ion (Li-ion) batteries have made them attractive for grid-scale energy storage applications. Energy storage will become increasingly important as intermittent renewable generation and more frequent extreme weather events put stress on the electricity grid. Environmental groups across the United States are advocating for the replacement of the highest-emitting power plants, which run only at times of peak demand, with Li-ion battery systems. We analyze the life-cycle cost, climate, and human health impacts of replacing the 19 highest-emitting peaker plants in California with Li-ion battery energy storage systems (BESS). Our results show that designing Li-ion BESS to replace peaker plants puts them at an economic disadvantage, even if facilities are only sized to meet 95% of the original plants' load events and are free to engage in arbitrage. However, five of 19 potential replacements do achieve a positive net present value after including monetized climate and human health impacts. These BESS cycle far less than typical front-of-the-meter batteries and rely on the frequency regulation market for most of their revenue. All projects offer net air pollution benefits but increase net greenhouse gas emissions due to electricity demand during charging and upstream emissions from battery manufacturing.

Greenhouse Gas and Air Pollutant Emissions from Composting.

Composting can divert organic waste from landfills, reduce landfill methane emissions, and recycle nutrients back to soils. However, the composting process is also a source of greenhouse gas and air pollutant emissions. Researchers, regulators, and policy decision-makers all rely on emissions estimates to develop local emissions inventories and weigh competing waste diversion options, yet reported emission factors are difficult to interpret and highly variable. This review explores the impacts of waste characteristics, pretreatment processes, and composting conditions on CO2, CH4, N2O, NH3, and VOC emissions by critically reviewing and analyzing 388 emission factors from 46 studies. The values reported to date suggest that CH4 is the single largest contributor to 100-year global warming potential (GWP100) for yard waste composting, comprising approximately 80% of the total GWP100. For nitrogen-rich wastes including manure, mixed municipal organic waste, and wastewater treatment sludge, N2O is the largest contributor to GWP100, accounting for half to as much as 90% of the total GWP100. If waste is anaerobically digested prior to composting, N2O, NH3, and VOC emissions tend to decrease relative to composting the untreated waste. Effective pile management and aeration are key to minimizing CH4 emissions. However, forced aeration can increase NH3 emissions in some cases.

Accumulation of high-value bioproducts in planta can improve the economics of advanced biofuels.

Coproduction of high-value bioproducts at biorefineries is a key factor in making biofuels more cost-competitive. One strategy for generating coproducts is to directly engineer bioenergy crops to accumulate bioproducts in planta that can be fractionated and recovered at biorefineries. Here, we develop quantitative insights into the relationship between bioproduct market value and target accumulation rates by investigating a set of industrially relevant compounds already extracted from plant sources with a wide range of market prices and applications, including <$10/kg (limonene, latex, and polyhydroxybutyrate [PHB]), $10 to $100/kg (cannabidiol), and >$100/kg (artemisinin). These compounds are used to identify a range of mass fraction thresholds required to achieve net economic benefits for biorefineries and the additional amounts needed to reach a target $2.50/gal biofuel selling price, using cellulosic ethanol production as a test case. Bioproduct market prices and recovery costs determine the accumulation threshold; we find that moderate- to high-value compounds (i.e., cannabidiol and artemisinin) offer net economic benefits at accumulation rates of just 0.01% dry weight (dwt) to 0.02 dwt%. Lower-value compounds, including limonene, latex, and PHB, require at least an order-of-magnitude greater accumulation to overcome additional extraction and recovery costs (0.3 to 1.2 dwt%). We also find that a diversified approach is critical. For example, global artemisinin demand could be met with fewer than 10 biorefineries, while global demand for latex is equivalent to nearly 180 facilities. Our results provide a roadmap for future plant metabolic engineering efforts aimed at increasing the value derived from bioenergy crops.

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.

Performance-Based Payments for Soil Carbon Sequestration Can Enable a Low-Carbon Bioeconomy.

Incentivizing bioenergy crop production in locations with marginal soils, where low-input perennial crops can provide net carbon sequestration and economic benefits, will be crucial to building a successful bioeconomy. We developed an integrated assessment framework to compare switchgrass cultivation with corn-soybean rotations on the basis of production costs, revenues, and soil organic carbon (SOC) sequestration at a 100 m spatial resolution. We calculated profits (or losses) when marginal lands are converted from a corn-soy rotation to switchgrass across a range of farm gate biomass prices and payments for SOC sequestration in the State of Illinois, United States. The annual net SOC sequestration and switchgrass yields are estimated to range from 0.1 to 0.4 Mg ha-1 and 7.3 to 15.5 Mg dry matter ha-1, respectively, across the state. Without payments for SOC sequestration, only a small fraction of marginal corn-soybean land would achieve a 20% profit margin if converted to switchgrass, but $40-80 Mg-1 CO2e compensation could increase the economically viable area by 140-414%. With the compensation, switchgrass cultivation for 10 years on 1.6 million ha of marginal land in Illinois will produce biomass worth $1.6-2.9 billion (0.95-1.8 million Mg dry biomass) and mitigate 5-22 million Mg CO2e.

Health and Climate Impacts from Long-Haul Truck Electrification.

Long-haul truck electrification has attracted nascent policy support, but the potential health and climate impacts remain uncertain. Here, we developed an integrated assessment approach with high spatial-temporal (km and hourly) resolution to characterize the causal chain from truck operation to charging loads, electricity grid response, changes in emissions and atmospheric concentrations, and the resulting health and climate impacts across the United States. Compared to future diesel trucks, electrified trucking's net health benefits are concentrated only along the West Coast with a business-as-usual electricity grid. However, with an 80%-renewable electricity grid, most regions would experience net health benefits, and the economic value of avoided climate and health damages exceeds $5 billion annually, an 80% reduction relative to future diesel trucks. Electric trucks with larger batteries may increase health and climate impacts due to additional trips needed to compensate for the payload penalty, but a 2× improvement in the battery specific energy (to ∼320 Wh/kg) could eliminate the additional trips.

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.

Air Pollutant Emission Rates for Dry Anaerobic Digestion and Composting of Organic Municipal Solid Waste.

Dry anaerobic digestion (AD) of organic municipal solid waste (MSW) followed by composting of the residual digestate is a waste diversion strategy that generates biogas and soil amendment products. The AD-composting process avoids methane (CH4) emissions from landfilling, but emissions of other greenhouse gases, odorous/toxic species, and reactive compounds can affect net climate and air quality impacts. In situ measurements of key sources at two large-scale industrial facilities in California were conducted to quantify pollutant emission rates across the AD-composting process. These measurements established a strong relationship between flared biogas ammonia (NH3) content and emitted nitrogen oxides (NOx), indicating that fuel NOx formation is significant and dominates over the thermal or prompt NOx pathways when biogas NH3 concentration exceeds ∼200 ppm. Composting is the largest source of CH4, carbon dioxide (CO2), nitrous oxide (N2O), and carbon monoxide (CO) emissions (∼60-70%), and dominate NH3, hydrogen sulfide (H2S), and volatile organic compounds (VOC) emissions (>90%). The high CH4 contribution to CO2-equivalent emissions demonstrates that composting can be an important CH4 source, which could be reduced with improved aeration. Controlling greenhouse gas and toxic/odorous emissions from composting offers the greatest mitigation opportunities for reducing the climate and air quality impacts of the AD-composting process.

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.

Accelerating the Deployment of Anaerobic Digestion to Meet Zero Waste Goals.

The U.S. places approximately 53% of its total municipal solid waste (MSW) in landfills, but state and local governments across the country are now setting ambitious environmental and waste diversion policies requiring, among other things, diversion and utilization of organics. Municipalities across the U.S. are employing anaerobic digestion (AD) as part of their strategy to divert organic MSW from landfills, produce biogas, and yield other beneficial coproducts such as compost and fertilizer. However, AD faces many technical, regulatory, and economic barriers to greater deployment, including upstream waste contamination, local odor and air pollution concerns, lengthy siting and permitting processes, and requirements and sizable costs for interconnecting to the electric grid. We identify a combination of scientific, operational, and policy advancements that are needed to address these barriers.

Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment.

Decarbonizing the transportation sector is critical to achieving global climate change mitigation. Although biofuels will play an important role in conventional gasoline and diesel applications, bioderived solutions are particularly important in jet fuels and lubricants, for which no other viable renewable alternatives exist. Producing compounds for jet fuel and lubricant base oil applications often requires upgrading fermentation products, such as alcohols and ketones, to reach the appropriate molecular-weight range. Ketones possess both electrophilic and nucleophilic functionality, which allows them to be used as building blocks similar to alkenes and aromatics in a petroleum refining complex. Here, we develop a method for selectively upgrading biomass-derived alkyl methyl ketones with >95% yields into trimer condensates, which can then be hydrodeoxygenated in near-quantitative yields to give a new class of cycloalkane compounds. The basic chemistry developed here can be tailored for aviation fuels as well as lubricants by changing the production strategy. We also demonstrate that a sugarcane biorefinery could use natural synergies between various routes to produce a mixture of lubricant base oils and jet fuels that achieve net life-cycle greenhouse gas savings of up to 80%.

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%.