Understanding Rapid PET Degradation via Reactive Molecular Dynamics Simulation and Kinetic Modeling.

As the demand for PET plastic products continues to grow, developing effective processes to reduce their pollution is of critical importance. Pyrolysis, a promising technology to produce lighter and recyclable components from wasted plastic products, has therefore received considerable attention. In this work, the rapid pyrolysis of PET was studied by using reactive molecular dynamics (MD) simulations. Mechanisms for yielding gas species were unraveled, which involve the generation of ethylene and TPA radicals from ester oxygen-alkyl carbon bond dissociation and condensation reactions to consume TPA radicals with the products of long chains containing a phenyl benzoate structure and CO2. As atomistic simulations are typically conducted at the time scale of a few nanoseconds, a high temperature (i.e., >1000 K) is adopted for accelerated reaction events. To apply the results from MD simulations to practical pyrolysis processes, a kinetic model based on a set of ordinary differential equations was established, which is capable of describing the key products of PET pyrolysis as a function of time and temperature. It was further exploited to determine the optimal reaction conditions for low environmental impact. Overall, this study conducted a detailed mechanism study of PET pyrolysis and established an effective kinetic model for the main species. The approach presented herein to extract kinetic information such as detailed kinetic constants and activation energies from atomistic MD simulations can also be applied to related systems such as the pyrolysis of other polymers.

Techno-economic and life cycle analysis of circular phosphorus systems in agriculture.

Fertilizer runoff is a global nuisance that disrupts biogeochemical cycles of nitrogen and phosphorus. We perform techno-economic and life cycle analyses of selected approaches for enabling a circular economy of phosphorus. We consider four schemes: capturing P with ion-exchange resins followed by precipitation, interception by wetland and recovery in char after biomass pyrolysis, removal by bioreactor and recovery in char after bioreactor substrate pyrolysis, and using legacy phosphorus accumulated in a saturated wetland to grow crops by wetlaculture. For each system, we analyze the mass flow, calculate the degree of circularity, and examine the feasibility by techno-economic and life cycle analyses. We find that although ion exchange outperforms the others, the associated economic and emissions burden are too high. Approaches that rely on wetlands are most economically attractive and can have lower impact. However, without policy interventions, the linear economy of phosphorus is likely to remain economically most attractive.

Metrics for a nature-positive world: A multiscale approach for absolute environmental sustainability assessment.

Absolute environmental sustainability (AES) metrics include nature's carrying capacity as a reference to provide insight into the extent to which human activities exceed ecosystem limits, and to encourage actions toward restoration and protection of nature. Existing methods for determining AES metrics rely on the frameworks of Planetary boundaries (PB) and Ecosystem Services. This work provides new insight into the relationship between these methods and demonstrates that AES metrics based on the framework of techno-ecological synergy (TES) are better suited to encouraging nature-positive decisions. PB-based AES metrics downscale planetary boundaries or upscale local ecosystem services, but they partition available services among all users across the planet and make limited use of biophysical information. In contrast, TES-based metrics follow a multiscale approach that accounts for local ecosystem services estimated by biophysical data and models, and combine them with downscaled services from multiple coarser scales. These metrics can provide credit to stakeholders for local ecosystem services, thus encouraging ecosystem protection and restoration. Generally, the PB framework focuses on processes of global importance which currently include nine planetary boundaries that are critical for global stability. The TES framework considers ecosystem services from local to global scales and can be used for determining absolute environmental sustainability precisely at any spatial scale. Theoretical analysis shows that TES-based metrics are more general and can be specialized to PB-based metrics under certain conditions. Through case studies at multiple spatial scales and for various ecosystem services, we show that TES-based metrics are more robust, less subjective, and better suited for encouraging transformation to a nature-positive world.

Quantification and valuation of ecosystem services in life cycle assessment: Application of the cascade framework to rice farming systems.

The integration of ecosystem service (ES) assessment with life cycle assessment (LCA) is important for developing decision support tools for environmental sustainability. A prequel study has proposed a 4-step methodology that integrates the ES cascade framework within the cause-effect chain of life cycle impact assessment (LCIA) to characterize the physical and monetary impacts on ES provisioning due to human interventions. We here follow the suggested steps in the abovementioned study, to demonstrate the first application of the integrated ES-LCIA methodology and the added value for LCA studies, using a case study of rice farming in the United States, China, and India. Four ES are considered, namely carbon sequestration, water provisioning, air quality regulation, and water quality regulation. The analysis found a net negative impact for rice farming systems in all three rice producing countries, meaning the detrimental impacts of rice farming on ES being greater than the induced benefits on ES. Compared to the price of rice sold in the market, the negative impacts represent around 2%, 6%, and 4% of the cost of 1 kg of rice from China, India, and the United States, respectively. From this case study, research gaps were identified in order to develop a fully operationalized ES-LCIA integration. With such a framework and guidance in place, practitioners can more comprehensively assess the impacts of life cycle activities on relevant ES provisioning, in both physical and monetary terms. This may in turn affect stakeholders' availability to receive such benefits from ecosystems in the long run.

Nature-Based Solutions Can Compete with Technology for Mitigating Air Emissions Across the United States.

Despite the proliferation of control technologies, air pollution remains a major concern across the United States, suggesting the need for a paradigm shift in methods for mitigating emissions. Based on data about annual emissions in U.S. counties and current land cover, we show that existing forest, grassland, and shrubland vegetation take up a significant portion of current U.S. emissions. Restoring land cover, where possible, to county-level average canopy cover can further remove pollution of SO2, PM10, PM2.5, and NO2 by an average of 27% through interception of particulate matter and absorption of gaseous pollutants. We find such nature-based solutions to be cheaper than technology for several National Emission Inventory sectors. Our results with and without monetary valuation of ecological cobenefits identify sectors and counties that are most economically attractive for nature-based solutions as compared to the use of pollution control technologies. We also estimate the sizes of urban and rural populations that would benefit from this novel ecosystem-based approach. This suggests that even though vegetation cannot fully negate the impact of emissions at all times, policies encouraging ecosystems as control measures in addition to technological solutions may promote large investments in ecological restoration and provide several societal benefits.

Toward Sustainable Chemical Engineering: The Role of Process Systems Engineering.

Products from chemical engineering are essential for human well-being, but they also contribute to the degradation of ecosystem goods and services that are essential for sustaining all human activities. To contribute to sustainability, chemical engineering needs to address this paradox by developing chemical products and processes that meet the needs of present and future generations. Unintended harm of chemical engineering has usually appeared outside the discipline's traditional system boundary due to shifting of impacts across space, time, flows, or disciplines, and exceeding nature's capacity to supply goods and services. Being a subdiscipline of chemical engineering, process systems engineering (PSE) is best suited for ensuring that chemical engineering makes net positive contributions to sustainable development. This article reviews the role of PSE in the quest toward a sustainable chemical engineering. It focuses on advances in metrics, process design, product design, and process dynamics and control toward sustainability. Efforts toward contributing to this quest have already expanded the boundary of PSE to consider economic, environmental, and societal aspects of processes, products, and their life cycles. Future efforts need to account for the role of ecosystems in supporting industrial activities, and the effects of human behavior and markets on the environmental impacts of chemical products. Close interaction is needed between the reductionism of chemical engineering science and the holism of process systems engineering, along with a shift in the engineering paradigm from wanting to dominate nature to learning from it and respecting its limits.

A Water-Withdrawal Input-Output Model of the Indian Economy.

Managing freshwater allocation for a highly populated and growing economy like India can benefit from knowledge about the effect of economic activities. This study transforms the 2003-2004 economic input-output (IO) table of India into a water withdrawal input-output model to quantify direct and indirect flows. This unique model is based on a comprehensive database compiled from diverse public sources, and estimates direct and indirect water withdrawal of all economic sectors. It distinguishes between green (rainfall), blue (surface and ground), and scarce groundwater. Results indicate that the total direct water withdrawal is nearly 3052 billion cubic meter (BCM) and 96% of this is used in agriculture sectors with the contribution of direct green water being about 1145 BCM, excluding forestry. Apart from 727 BCM direct blue water withdrawal for agricultural, other significant users include "Electricity" with 64 BCM, "Water supply" with 44 BCM and other industrial sectors with nearly 14 BCM. "Construction", "miscellaneous food products"; "Hotels and restaurants"; "Paper, paper products, and newsprint" are other significant indirect withdrawers. The net virtual water import is found to be insignificant compared to direct water used in agriculture nationally, while scarce ground water associated with crops is largely contributed by northern states.

Economic Dependence of U.S. Industrial Sectors on Animal-Mediated Pollination Service.

Declining animal pollinator health and diversity in the U.S. is a matter of growing concern and has particularly gained attention since the emergence of colony collapse disorder (CCD) in 2006. Failure to maintain adequate animal-mediated pollination service to support increasing demand for pollination-dependent crops poses risks for the U.S. economy. We integrate the Economic Input-Output (EIO) model and network analysis with data on pollinator dependence of crops to understand the economic dependence of U.S. industrial sectors on animal-mediated pollination service. The novelty of this work lies in its ability to identify industrial sectors and industrial communities (groups of closely linked sectors) that are most vulnerable to scarcity of pollination service provided by various animal species. While the economic dependence of agricultural sectors on pollination service is significant (US$14.2-23.8 billion), the higher-order economic dependence of the rest of the U.S. industrial sectors is substantially high as well (US$10.3-21.1 billion). The results are compelling as they highlight the critical importance of animal-induced pollination service for the U.S. economy, and the need to account for the role of ecosystem goods and services in product life cycles.

Allocation Games: Addressing the Ill-Posed Nature of Allocation in Life-Cycle Inventories.

Allocation is required when a life cycle contains multi-functional processes. One approach to allocation is to partition the embodied resources in proportion to a criterion, such as product mass or cost. Many practitioners apply multiple partitioning criteria to avoid choosing one arbitrarily. However, life cycle results from different allocation methods frequently contradict each other, making it difficult or impossible for the practitioner to draw any meaningful conclusions from the study. Using the matrix notation for life-cycle inventory data, we show that an inventory that requires allocation leads to an ill-posed problem: an inventory based on allocation is one of an infinite number of inventories that are highly dependent upon allocation methods. This insight is applied to comparative life-cycle assessment (LCA), in which products with the same function but different life cycles are compared. Recently, there have been several studies that applied multiple allocation methods and found that different products were preferred under different methods. We develop the Comprehensive Allocation Investigation Strategy (CAIS) to examine any given inventory under all possible allocation decisions, enabling us to detect comparisons that are not robust to allocation, even when the comparison appears robust under conventional partitioning methods. While CAIS does not solve the ill-posed problem, it provides a systematic way to parametrize and examine the effects of partitioning allocation. The practical usefulness of this approach is demonstrated with two case studies. The first compares ethanol produced from corn stover hydrolysis, corn stover gasification, and corn grain fermentation. This comparison was not robust to allocation. The second case study compares 1,3-propanediol (PDO) produced from fossil fuels and from biomass, which was found to be a robust comparison.

Techno-ecological synergy: a framework for sustainable engineering.

Even though the importance of ecosystems in sustaining all human activities is well-known, methods for sustainable engineering fail to fully account for this role of nature. Most methods account for the demand for ecosystem services, but almost none account for the supply. Incomplete accounting of the very foundation of human well-being can result in perverse outcomes from decisions meant to enhance sustainability and lost opportunities for benefiting from the ability of nature to satisfy human needs in an economically and environmentally superior manner. This paper develops a framework for understanding and designing synergies between technological and ecological systems to encourage greater harmony between human activities and nature. This framework considers technological systems ranging from individual processes to supply chains and life cycles, along with corresponding ecological systems at multiple spatial scales ranging from local to global. The demand for specific ecosystem services is determined from information about emissions and resource use, while the supply is obtained from information about the capacity of relevant ecosystems. Metrics calculate the sustainability of individual ecosystem services at multiple spatial scales and help define necessary but not sufficient conditions for local and global sustainability. Efforts to reduce ecological overshoot encourage enhancement of life cycle efficiency, development of industrial symbiosis, innovative designs and policies, and ecological restoration, thus combining the best features of many existing methods. Opportunities for theoretical and applied research to make this framework practical are also discussed.

Accounting for the biogeochemical cycle of nitrogen in input-output life cycle assessment.

Nitrogen is indispensable for sustaining human activities through its role in the production of food, animal feed, and synthetic chemicals. This has encouraged significant anthropogenic mobilization of reactive nitrogen and its emissions into the environment resulting in severe disruption of the nitrogen cycle. This paper incorporates the biogeochemical cycle of nitrogen into the 2002 input-output model of the U.S. economy. Due to the complexity of this cycle, this work proposes a unique classification of nitrogen flows to facilitate understanding of the interaction between economic activities and various flows in the nitrogen cycle. The classification scheme distinguishes between the mobilization of inert nitrogen into its reactive form, use of nitrogen in various products, and nitrogen losses to the environment. The resulting inventory and model of the US economy can help quantify the direct and indirect impacts or dependence of economic sectors on the nitrogen cycle. This paper emphasizes the need for methods to manage the N cycle that focus not just on N losses, which has been the norm until now, but also include other N flows for a more comprehensive view and balanced decisions. Insight into the N profile of various sectors of the 2002 U.S. economy is presented, and the inventory can also be used for LCA or Hybrid LCA of various products. The resulting model is incorporated in the approach of Ecologically-Based LCA and available online.

Multi-scale modeling for sustainable chemical production.

With recent advances in metabolic engineering, it is now technically possible to produce a wide portfolio of existing petrochemical products from biomass feedstock. In recent years, a number of modeling approaches have been developed to support the engineering and decision-making processes associated with the development and implementation of a sustainable biochemical industry. The temporal and spatial scales of modeling approaches for sustainable chemical production vary greatly, ranging from metabolic models that aid the design of fermentative microbial strains to material and monetary flow models that explore the ecological impacts of all economic activities. Research efforts that attempt to connect the models at different scales have been limited. Here, we review a number of existing modeling approaches and their applications at the scales of metabolism, bioreactor, overall process, chemical industry, economy, and ecosystem. In addition, we propose a multi-scale approach for integrating the existing models into a cohesive framework. The major benefit of this proposed framework is that the design and decision-making at each scale can be informed, guided, and constrained by simulations and predictions at every other scale. In addition, the development of this multi-scale framework would promote cohesive collaborations across multiple traditionally disconnected modeling disciplines to achieve sustainable chemical production.

Techno-ecological synergy as a path toward sustainability of a North American residential system.

For any human-designed system to be sustainable, ecosystem services that support it must be readily available. This work explicitly accounts for this dependence by designing synergies between technological and ecological systems. The resulting techno-ecological network mimics nature at the systems level, can stay within ecological constraints, and can identify novel designs that are economically and environmentally attractive that may not be found by the traditional design focus on technological options. This approach is showcased by designing synergies for a typical American suburban home at local and life cycle scales. The objectives considered are carbon emissions, water withdrawal, and cost savings. Systems included in the design optimization include typical ecosystems in suburban yards: lawn, trees, water reservoirs, and a vegetable garden; technological systems: heating, air conditioning, faucets, solar panels, etc.; and behavioral variables: heating and cooling set points. The ecological and behavioral design variables are found to have a significant effect on the three objectives, in some cases rivaling and exceeding the effect of traditional technological options. These results indicate the importance and benefits of explicitly including ecosystems in the design of sustainable systems, something that is rarely done in existing methods.

Reinforced wind turbine blades--an environmental life cycle evaluation.

A fiberglass composite reinforced with carbon nanofibers (CNF) at the resin-fiber interface is being developed for potential use in wind turbine blades. An energy and midpoint impact assessment was performed to gauge impacts of scaling production to blades 40 m and longer. Higher loadings force trade-offs in energy return on investment and midpoint impacts relative to the base case while remaining superior to thermoelectric power generation in these indicators. Energy-intensive production of CNFs forces impacts disproportionate to mass contribution. The polymer nanocomposite increases a 2 MW plant's global warming potential nearly 100% per kWh electricity generated with 5% CNF by mass in the blades if no increase in electrical output is realized. The relative scale of impact must be compensated by systematic improvements whether by deployment in higher potential zones or by increased life span; the trade-offs are expected to be significantly lessened with CNF manufacturing maturity. Significant challenges are faced in evaluating emerging technologies including uncertainty in future scenarios and process scaling. Inventories available for raw materials and monte carlos analysis have been used to gain insight to impacts of this development.

Assessing resource intensity and renewability of cellulosic ethanol technologies using eco-LCA.

Recognizing the contributions of ecosystem services and the lack of their comprehensive accounting in life cycle assessment (LCA), an in-depth analysis of their contribution in the life cycle of cellulosic ethanol derived from five different feedstocks was conducted, with gasoline and corn ethanol as reference fuels. The relative use intensity of natural resources encompassing land and ecosystem goods and services by cellulosic ethanol was estimated using the Eco-LCA framework. Despite being resource intensive compared to gasoline, cellulosic ethanol offers the possibility of a reduction in crude oil consumption by as much as 96%. Soil erosion and land area requirements can be sources of concern for cellulosic ethanol derived directly from managed agriculture. The analysis of two broad types of thermodynamic metrics, namely: various types of physical return on investment and a renewability index, which indicate competitiveness and sustainability of cellulosic ethanol, respectively, show that only ethanol from waste resources combines a favorable thermodynamic return on investment with a higher renewability index. However, the production potential of ethanol from waste resources is limited. This finding conveys a possible dilemma of biofuels: combining high renewability, high thermodynamic return on investment, and large production capacity may remain elusive. A plot of renewability versus energy return on investment is suggested as one of the options for providing guidance on future biofuel selection.

Appreciating the role of thermodynamics in LCA improvement analysis via an application to titanium dioxide nanoparticles.

Although many regard it as the most important step of life cycle assessment, improvement analysis is given relatively little attention in the literature. Most available improvement approaches are highly subjective, and traditional LCA methods often do not account for resources other than fossil fuels. In this work exergy is evaluated as a thermodynamically rigorous way of identifying process improvement opportunities. As a case study, a novel process for producing titanium dioxide nanoparticles is considered. A traditional impact assessment, a first law energy analysis, and an exergy analysis are done at both the process and life cycle scales. The results indicate that exergy analysis provides insights not available via other methods, especially for identifying unit operations with the greatest potential for improvement. Exergetic resource accounting at the life cycle scale shows that other materials are at least as significant as fossil fuels for the production of TiO2 nanoparticles in this process.

Accounting for ecosystem services in Life Cycle Assessment, Part II: toward an ecologically based LCA.

Despite the essential role of ecosystem goods and services in sustaining all human activities, they are often ignored in engineering decision making, even in methods that are meant to encourage sustainability. For example, conventional Life Cycle Assessment focuses on the impact of emissions and consumption of some resources. While aggregation and interpretation methods are quite advanced for emissions, similar methods for resources have been lagging, and most ignore the role of nature. Such oversight may even result in perverse decisions that encourage reliance on deteriorating ecosystem services. This article presents a step toward including the direct and indirect role of ecosystems in LCA, and a hierarchical scheme to interpret their contribution. The resulting Ecologically Based LCA (Eco-LCA) includes a large number of provisioning, regulating, and supporting ecosystem services as inputs to a life cycle model at the process or economy scale. These resources are represented in diverse physical units and may be compared via their mass, fuel value, industrial cumulative exergy consumption, or ecological cumulative exergy consumption or by normalization with total consumption of each resource or their availability. Such results at a fine scale provide insight about relative resource use and the risk and vulnerability to the loss of specific resources. Aggregate indicators are also defined to obtain indices such as renewability, efficiency, and return on investment. An Eco-LCA model of the 1997 economy is developed and made available via the web (www.resilience.osu.edu/ecolca). An illustrative example comparing paper and plastic cups provides insight into the features of the proposed approach. The need for further work in bridging the gap between knowledge about ecosystem services and their direct and indirect role in supporting human activities is discussed as an important area for future work.

Accounting for ecosystem services in life cycle assessment, Part I: a critical review.

If life cycle oriented methods are to encourage sustainable development, they must account for the role of ecosystem goods and services, since these form the basis of planetary activities and human well-being. This article reviews methods that are relevant to accounting for the role of nature and that could be integrated into life cycle oriented approaches. These include methods developed by ecologists for quantifying ecosystem services, by ecological economists for monetary valuation, and life cycle methods such as conventional life cycle assessment, thermodynamic methods for resource accounting such as exergy and emergy analysis, variations of the ecological footprint approach, and human appropriation of net primary productivity. Each approach has its strengths: economic methods are able to quantify the value of cultural services; LCA considers emissions and assesses their impact; emergy accounts for supporting services in terms of cumulative exergy; and ecological footprint is intuitively appealing and considers biocapacity. However, no method is able to consider all the ecosystem services, often due to the desire to aggregate all resources in terms of a single unit. This review shows that comprehensive accounting for ecosystem services in LCA requires greater integration among existing methods, hierarchical schemes for interpreting results via multiple levels of aggregation, and greater understanding of the role of ecosystems in supporting human activities. These present many research opportunities that must be addressed to meet the challenges of sustainability.

Thermodynamic metrics for aggregation of natural resources in life cycle analysis: insight via application to some transportation fuels.

While methods for aggregating emissions are widely used and standardized in life cycle assessment (LCA), there is little agreement about methods for aggregating natural resources for obtaining interpretable metrics. Thermodynamic methods have been suggested including energy, exergy, and emergy analyses. This work provides insight into the nature of thermodynamic aggregation, including assumptions about substitutability between resources and loss of detailed information about the data being combined. Methods considered include calorific value or energy, industrial cumulative exergy consumption (ICEC) and its variations, and ecological cumulative exergy consumption (ECEC) or emergy. A hierarchy of metrics is proposed that spans the range from detailed data to aggregate metrics. At the fine scale, detailed data can help identify resources to whose depletion the selected product is most vulnerable. At the coarse scale, new insight is provided about thermodynamic aggregation methods. Among these, energy analysis is appropriate only for products that rely primarily on fossil fuels, and it cannot provide a useful indication of renewability. Exergy-based methods can provide results similar to energy analysis by including only nonrenewable fuels but can also account for materials use and provide a renewability index. However, ICEC and its variations do not address substitutability between resources, causing its results to be dominated by dilute and low-quality resources such as sunlight. The use of monetary values to account for substitutability does not consider many ecological resources and may not be appropriate for the analysis of emerging products. ECEC or emergy explicitly considers substitutability and resource quality and provides more intuitive results but is plagued by data gaps and uncertainties. This insight is illustrated via application to the life cycles of gasoline, diesel, corn ethanol, and soybean biodiesel. Here, aggregate metrics reveal the dilemma facing the choice of fuels: high return on investment versus high renewability.

Carbon nanofiber polymer composites: evaluation of life cycle energy use.

Holistic evaluation of emerging nanotechnologies using systems analysis is pivotal for guiding their safe and sustainable development. While toxicity studies of engineered nanomaterials are essential, understanding of the potential large scale impacts of nanotechnology is also critical for developing sustainable nanoproducts. This work evaluates the life cycle energetic impact associated with the production and use of carbon nanofiber (CNF) reinforced polymer nanocomposites (PNC). Specifically, both simple CNF and carbon nanofiber-glass fiber (CNF-GF) hybrid PNCs are evaluated and compared with steel for equal stiffness design. Life cycle inventory is developed based on published literature and best available engineering information. A cradle-to-gate comparison suggests that for equal stiffness design, CNF reinforced PNCs are 1.6-12 times more energy intensive than steel. It is anticipated that the product use phase may strongly influence whether any net savings in life cycle energy consumption can be realized. A case study involving the use of CNF and CNF-GF reinforced PNCs in the body panels of automobiles highlights that the use of PNCs with lower CNF loading ratios has the potential for net life cycle energy savings relative to steel owing to improved fuel economy benefits. Other factors such as cost, toxicity impact of CNF, and end-of-life issues specific to CNFs need to be considered to evaluate the final economic and environmental performance of CNF reinforced PNC materials.