Integrated Assessment of the Leading Paths to Mitigate CO2 Emissions from the Organic Chemical and Plastics Industry.

The chemical industry is a major and growing source of CO2 emissions. Here, we extend the principal U.S.-based integrated assessment model, GCAM, to include a representation of steam cracking, the dominant process in the organic chemical industry today, and a suite of emerging decarbonization strategies, including catalytic cracking, lower-carbon process heat, and feedstock switching. We find that emerging catalytic production technologies only have a small impact on midcentury emissions mitigation. In contrast, process heat generation could achieve strong mitigation, reducing associated CO2 emissions by ∼76% by 2050. Process heat generation is diversified to include carbon capture and storage (CCS), hydrogen, and electrification. A sensitivity analysis reveals that our results for future net CO2 emissions are most sensitive to the amount of CCS deployed globally. The system as defined cannot reach net-zero emissions if the share of incineration increases as projected without coupling incineration with CCS. Less organic chemicals are produced in a net-zero CO2 future than those in a no-policy scenario. Mitigation of feedstock emissions relies heavily on biogenic carbon used as an alternative feedstock and waste treatment of plastics. The only scenario that delivers net-negative CO2 emissions from the organic chemical sector (by 2070) combines greater use of biogenic feedstocks with a continued reliance on landfilling of waste plastic, versus recycling or incineration, which has trade-offs.

If humans design the planet: A call for psychological scientists to engage with climate engineering.

As efforts to control climate change gain momentum, so too does the possibility that some global actor(s) will deploy one or more forms of climate engineering. Climate engineering refers to large-scale and deliberate activities intended to change either the carbon-balance or energy-balance of the planet. Climate engineering approaches are untested, involve deep uncertainty, and have far-reaching consequences. Nevertheless, many scientists expect that, relative to conventional mitigation approaches, some climate-engineering approaches will prove less expensive and will require less coordination. They will also have more potential for unilateral deployment. Decisions to pursue climate engineering involve several psychosocial dimensions related to attitude and preference formation, decision making under uncertainty, interpersonal coordination, and health and well-being. Even the prospect of climate engineering could affect norms, goals, and beliefs. The field of psychological science should prepare to help society responsibly consider climate engineering alongside more conventional climate-change responses. This article lays out some initial questions and issues a call to action. It aims to provide common ground for a conversation between climatologists, policymakers, psychological scientists, and members of the public on the important behavioral touchpoints of climate engineering. (PsycInfo Database Record (c) 2021 APA, all rights reserved).

Targeted Permeability Control in the Subsurface via Calcium Silicate Carbonation.

Efforts to develop safe and effective next-generation energy and carbon-storage technologies in the subsurface require novel means to control undesired fluid migration. Here we demonstrate that the carbonation of calcium silicates can produce reaction products that dramatically reduce the permeability of porous media and that are stable. Most calcium silicates react with CO2 to form solid carbonates but some polymorphs (here, pseudowollastonite, CaSiO3) can react to form a range of crystalline calcium silicate hydrates (CCSHs) at intermediate pH. High-pressure (1.1-15.5 MPa) column and batch experiments were conducted at a range of temperatures (75-150 °C) and reaction products were characterized using SEM-EDS and synchrotron µXRD and µXRF. Two characteristics of CCSH precipitation were observed, revealing unique properties for permeability control relative to carbonate precipitates. First, precipitation of CCSHs tends to occur on the surface of sand grains and into pore throats, indicating that small amounts of precipitation relative to the total pore volume can effectively block flow, compared to carbonates which precipitate uniformly throughout the pore space. Second, the precipitated CCSHs are more stable at low pH conditions, which may form more secure barriers to flow, compared to carbonates, which dissolve under acidic conditions.

Mitigating Climate Change at the Carbon Water Nexus: A Call to Action for the Environmental Engineering Community.

Environmental engineers have played a critical role in improving human and ecosystem health over the past several decades. These contributions have focused on providing clean water and air as well as managing waste streams and remediating polluted sites. As environmental problems have become more global in scale and more deeply entrenched in sociotechnical systems, the discipline of environmental engineering must grow to be ready to respond to the challenges of the coming decades. Here we make the case that environmental engineers should play a leadership role in the development of climate change mitigation technologies at the carbon-water nexus (CWN). Climate change, driven largely by unfettered emissions of fossil carbon into the atmosphere, is a far-reaching and enormously complex environmental risk with the potential to negatively affect food security, human health, infrastructure, and other systems. Solving this problem will require a massive mobilization of existing and innovative new technology. The environmental engineering community is uniquely positioned to do pioneering work at the CWN using a skillset that has been honed, solving related problems. The focus of this special issue, on "The science and innovation of emerging subsurface energy technologies," provides one example domain within which environmental engineers and related disciplines are beginning to make important contributions at the CWN. In this article, we define the CWN and describe how environmental engineers can bring their considerable expertise to bear in this area. Then we review some of the topics that appear in this special issue, for example, mitigating the impacts of hydraulic fracturing and geologic carbon storage, and we provide perspective on emergent research directions, for example, enhanced geothermal energy, energy storage in sedimentary formations, and others.

Environmental Life Cycle Analysis of Water and CO2-Based Fracturing Fluids Used in Unconventional Gas Production.

Many of the environmental impacts associated with hydraulic fracturing of unconventional gas wells are tied to the large volumes of water that such operations require. Efforts to develop nonaqueous alternatives have focused on carbon dioxide as a tunable working fluid even though the full environmental and production impacts of a switch away from water have yet to be quantified. Here we report on a life cycle analysis of using either water or CO2 for gas production in the Marcellus shale. The results show that CO2-based fluids, as currently conceived, could reduce greenhouse gas emissions by 400% (with sequestration credit) and water consumption by 80% when compared to conventional water-based fluids. These benefits are offset by a 44% increase in net energy use when compared to slickwater fracturing as well as logistical barriers resulting from the need to move and store large volumes of CO2. Scenario analyses explore the outlook for CO2, which under best-case conditions could eventually reduce life cycle energy, water, and greenhouse gas (GHG) burdens associated with fracturing. To achieve these benefits, it will be necessary to reduce CO2 sourcing and transport burdens and to realize opportunities for improved energy recovery, averted water quality impacts, and carbon storage.

CO2 deserts: implications of existing CO2 supply limitations for carbon management.

Efforts to mitigate the impacts of climate change will require deep reductions in anthropogenic CO2 emissions on the scale of gigatonnes per year. CO2 capture and utilization and/or storage technologies are a class of approaches that can substantially reduce CO2 emissions. Even though examples of this approach, such as CO2-enhanced oil recovery, are already being practiced on a scale >0.05 Gt/year, little attention has been focused on the supply of CO2 for these projects. Here, facility-scale data newly collected by the U.S. Environmental Protection Agency was processed to produce the first comprehensive map of CO2 sources from industrial sectors currently supplying CO2 in the United States. Collectively these sources produce 0.16 Gt/year, but the data reveal the presence of large areas without access to CO2 at an industrially relevant scale (>25 kt/year). Even though some facilities with the capability to capture CO2 are not doing so and in some regions pipeline networks are being built to link CO2 sources and sinks, much of the country exists in "CO2 deserts". A life cycle analysis of the sources reveals that the predominant source of CO2, dedicated wells, has the largest carbon footprint further confounding prospects for rational carbon management strategies.

Pilot-scale data provide enhanced estimates of the life cycle energy and emissions profile of algae biofuels produced via hydrothermal liquefaction.

Life cycle assessment (LCA) has been used widely to estimate the environmental implications of deploying algae-to-energy systems even though no full-scale facilities have yet to be built. Here, data from a pilot-scale facility using hydrothermal liquefaction (HTL) is used to estimate the life cycle profiles at full scale. Three scenarios (lab-, pilot-, and full-scale) were defined to understand how development in the industry could impact its life cycle burdens. HTL-derived algae fuels were found to have lower greenhouse gas (GHG) emissions than petroleum fuels. Algae-derived gasoline had significantly lower GHG emissions than corn ethanol. Most algae-based fuels have an energy return on investment between 1 and 3, which is lower than petroleum biofuels. Sensitivity analyses reveal several areas in which improvements by algae bioenergy companies (e.g., biocrude yields, nutrient recycle) and by supporting industries (e.g., CO2 supply chains) could reduce the burdens of the industry.

CO2 adhesion on hydrated mineral surfaces.

Hydrated mineral surfaces in the environment are generally hydrophilic but in certain cases can strongly adhere CO2, which is largely nonpolar. This adhesion can significantly alter the wettability characteristics of the mineral surface and consequently influence capillary/residual trapping and other multiphase flow processes in porous media. Here, the conditions influencing adhesion between CO2 and homogeneous mineral surfaces were studied using static pendant contact angle measurements and captive advancing/receding tests. The prevalence of adhesion was sensitive to both surface roughness and aqueous chemistry. Adhesion was most widely observed on phlogopite mica, silica, and calcite surfaces with roughness on the order of ~10 nm. The incidence of adhesion increased with ionic strength and CO2 partial pressure. Adhesion was very rarely observed on surfaces equilibrated with brines containing strong acid or base. In advancing/receding contact angle measurements, adhesion could increase the contact angle by a factor of 3. These results support an emerging understanding of adhesion of, nonpolar nonaqueous phase fluids on mineral surfaces influenced by the properties of the electrical double layer in the aqueous phase film and surface functional groups between the mineral and CO2.

Wettability phenomena at the CO2-brine-mineral interface: implications for geologic carbon sequestration.

Geologic carbon sequestration (GCS) in deep saline aquifers results in chemical and transport processes that are impacted by the wettability characteristics of formation solid phases in contact with connate brines and injected CO(2). Here, the contact angle (θ) at the CO(2)-brine-mineral interface is studied for several representative solids including quartz, microcline, calcite, kaolinite, phlogopite, and illite under a range of GCS conditions. All were found to be water wetting (θ < 30°) with subtle but important differences in contact angles observed between the surfaces. Temperature and pressure conditions affected the results but did not produce discernible trends common to all surfaces. Brine composition, in terms of pH and ionic strength, was a better predictor of interfacial behavior. For the nonclays, the wettability is impacted by the pH at the point of zero charge of the solid. For the clays, the response was more complex. Under nonequilibrium conditions, hysteretic effects were observed when CO(2) was dissolving into the bulk fluid and this effect varied between minerals. Contact angle was found to decrease during the CO(2) phase transition from supercritical or liquid phase to gas phase. These results are useful for developing a more complete understanding of leakage through caprocks and capillary trapping in GCS.

Comparison of algae cultivation methods for bioenergy production using a combined life cycle assessment and life cycle costing approach.

Algae are an attractive energy source, but important questions still exist about the sustainability of this technology on a large scale. Two particularly important questions concern the method of cultivation and the type of algae to be used. This present study combines elements of life cycle analysis (LCA) and life cycle costing (LCC) to evaluate open pond (OP) systems and horizontal tubular photobioreactors (PBRs) for the cultivation of freshwater (FW) or brackish-to-saline water (BSW) algae. Based on the LCA, OPs have lower energy consumption and greenhouse gas emissions than PBRs; e.g., 32% less energy use for construction and operation. According to the LCC, all four systems are currently financially unattractive investments, though OPs are less so than PBRs. BSW species deliver better energy and GHG performance and higher profitability than FW species in both OPs and PBRs. Sensitivity analyses suggest that improvements in critical cultivation parameters (e.g., CO(2) utilization efficiency or algae lipid content), conversion parameters (e.g., anaerobic digestion efficiency), and market factors (e.g., costs of CO(2) and electricity, or sale prices for algae biodiesel) could alter these results.

Algae biodiesel has potential despite inconclusive results to date.

A meta-analysis of several published life cycle assessments of algae-to-energy systems was developed to better understand the environmental implications of deploying this technology at large scales. Taken together, results from these six studies seemed largely inconclusive because of differences in modeling assumptions and system boundaries. To overcome this, the models were normalized using a generic pathway for cultivating algae in open ponds, converting it into biodiesel, and processing the nonlipid fraction using anaerobic digestion. Meta-analysis results suggest that algae-based biodiesel would result in energy consumption and greenhouse gas emissions on par with terrestrial alternatives such as corn ethanol and soy biodiesel. Net energy ratio and normalized greenhouse gas emissions were 1.4 MJ produced/MJ consumed and 0.19 kg CO(2)-equivalent/km traveled, respectively. A scenario analysis underscores the extent to which breakthroughs in key technologies are needed before algae-derived fuels become an attractive alternative to conventional biofuels.

Environmental impacts of algae-derived biodiesel and bioelectricity for transportation.

Algae are a widely touted source of bioenergy with high yields, appreciable lipid contents, and an ability to be cultivated on marginal land without directly competing with food crops. Nevertheless, recent work has suggested that large-scale deployment of algae bioenergy systems could have unexpectedly high environmental burdens. In this study, a "well-to-wheel" life cycle assessment was undertaken to evaluate algae's potential use as a transportation energy source for passenger vehicles. Four algae conversion pathways resulting in combinations of bioelectricity and biodiesel were assessed for several relevant nutrient procurement scenarios. Results suggest that algae-to-energy systems can be either net energy positive or negative depending on the specific combination of cultivation and conversion processes used. Conversion pathways involving direct combustion for bioelectricity production generally outperformed systems involving anaerobic digestion and biodiesel production, and they were found to generate four and fifteen times as many vehicle kilometers traveled (VKT) per hectare as switchgrass or canola, respectively. Despite this, algae systems exhibited mixed performance for environmental impacts (energy use, water use, and greenhouse gas emissions) on a "per km" basis relative to the benchmark crops. This suggests that both cultivation and conversion processes must be carefully considered to ensure the environmental viability of algae-to-energy processes.

Environmental life cycle comparison of algae to other bioenergy feedstocks.

Algae are an attractive source of biomass energy since they do not compete with food crops and have higher energy yields per area than terrestrial crops. In spite of these advantages, algae cultivation has not yet been compared with conventional crops from a life cycle perspective. In this work, the impacts associated with algae production were determined using a stochastic life cycle model and compared with switchgrass, canola, and corn farming. The results indicate that these conventional crops have lower environmental impacts than algae in energy use, greenhouse gas emissions, and water regardless of cultivation location. Only in total land use and eutrophication potential do algae perform favorably. The large environmental footprint of algae cultivation is driven predominantly by upstream impacts, such as the demand for CO(2) and fertilizer. To reduce these impacts, flue gas and, to a greater extent, wastewater could be used to offset most of the environmental burdens associated with algae. To demonstrate the benefits of algae production coupled with wastewater treatment, the model was expanded to include three different municipal wastewater effluents as sources of nitrogen and phosphorus. Each provided a significant reduction in the burdens of algae cultivation, and the use of source-separated urine was found to make algae more environmentally beneficial than the terrestrial crops.

Comparison of life cycle emissions and energy consumption for environmentally adapted metalworking fluid systems.

A number of environmentally adapted lubricants have been proposed in response to the environmental and health impacts of metalworking fluids (MWFs). The alternatives typically substitute petroleum with vegetable-based components and/or deliver minimum quantities of lubricant in gas rather than water, with the former strategy being more prevalent than the latter. A comparative life cycle assessment of water- and gas-based systems has shown that delivery of lubricants in air rather than water can reduce solid waste by 60%, water use by 90%, and aquatic toxicity by 80%, while virtually eliminating occupational health concerns. However, air-delivery of lubricants cannot be used for severe machining operations due to limitations of cooling and lubricant delivery. For such operations, lubricants delivered in supercritical carbon dioxide (scCO2) are effective while maintaining the health and environmental advantages of air-based systems. Although delivery conditions were found to significantly influence the environmental burdens of all fluids, energy consumption was relatively constant under expected operating conditions. Global warming potential (GWP) increased when delivering lubricants in gas rather than water though all classes of MWFs have low GWP compared with other factory operations. It is therefore concluded that the possibility of increased GWP when switching to gas-based MWFs is a reasonable tradeoff for definite and large reductions in aquatic toxicity, water use, solid waste, and occupational health risks.

Design of hard water stable emulsifier systems for petroleum- and bio-based semi-synthetic metalworking fluids.

Metalworking fluids (MWFs) increase productivity and the quality of manufacturing operations by cooling and lubricating during metal forming and cutting processes. Despite their widespread use, they pose significant health and environmental hazards throughout their life cycle. An obvious environmental improvement to MWF technology would be to improve the lifetime of the fluid while utilizing more environmentally friendly and less energy-consuming materials without compromising existing performance levels. This investigation focuses on the design of mixed anionionc:nonionic emulsifier systems for petroleum and bio-based MWFs that improve fluid lifetime by providing emulsion stability under hard water conditions, a common cause of emulsion destabilization leading to MWF disposal. Experimental conditions were designed to evaluate the impact of emulsifier structural characteristics (straight chain, branched tail, branched head) and the molar ratios of anionic to nonionic surfactant and oil to total surfactant. Results from the 2500 formulations generated indicate that the use of a twin-headed anionic surfactant can provide improved hard water stability for both mineral oil- and vegetable oil-based formulations, even in the absence of a chelating agent and a coupler. Results also suggest that an oil:total surfactant molar ratio of 0.5 or less is necessary for particle size stability in hard water conditions for these systems. The newly developed petroleum and bio-based formulations with improved hard water stability are competitive with commercially available MWFs in performance evaluations for tramp oil rejection, contact angle, and tapping torque efficiency. These results can be used to design MWF formulations with fewer components and extended lifetime under hard water conditions, both of which would lead to a reduction in the life cycle environmental impact of MWFs.