Thermodynamics of Energy Production from Biomass

With high quality petroleum running out in the next 50 years, the world governments and petrochemical industry alike are looking at biomass as a substitute refinery feedstock for liquid fuels and other bulk chemicals. New large plantations are being established in many countries, mostly in the tropics, but also in China, North America, Northern Europe, and in Russia. These industrial plantations will impact the global carbon, nitrogen, phosphorus, and water cycles in complex ways. The purpose of this paper is to use thermodynamics to quantify a few of the many global problems created by industrial forestry and agriculture. It is assumed that a typical tree biomass-for-energy plantation is combined with an efficient local pelleting facility to produce wood pellets for overseas export. The highest biomass-to-energy conversion efficiency is afforded by an efficient electrical power plant, followed by a combination of the FISCHER-TROPSCH diesel fuel burned in a 35%-efficient car, plus electricity. Wood pellet conversion to ethanol fuel is always the worst option. It is then shown that neither a prolific acacia stand in Indonesia nor an adjacent eucalypt stand is “sustainable.” The acacia stand can be made “sustainable” in a limited sense if the cumulative free energy consumption in wood drying and chipping is cut by a factor of two by increased reliance on sun-drying of raw wood. The average industrial sugarcane-for-ethanol plantation in Brazil could be “sustainable” if the cane ethanol powered a 60%-efficient fuel cell that, we show, does not exist. With some differences (ethanol distillation vs. pellet production), this sugarcane plantation performs very similarly to the acacia plantation, and is unsustainable in conjunction with efficient internal combustion engines.     

Improvements in Life Cycle Energy Efficiency and Greenhouse Gas Emissions of Corn-Ethanol

Corn-ethanol production is expanding rapidly with the adoption of improved technologies to increase energy efficiency and profitability in crop production, ethanol conversion, and coproduct use. Life cycle assessment can evaluate the impact of these changes on environmental performance metrics. To this end, we analyzed the life cycles of corn-ethanol systems accounting for the majority of U.S. capacity to estimate greenhouse gas (GHG) emissions and energy efficiencies on the basis of updated values for crop management and yields, biorefinery operation, and coproduct utilization. Direct-effect GHG emissions were estimated to be equivalent to a 48% to 59% reduction compared to gasoline, a twofold to threefold greater reduction than reported in previous studies. Ethanol-to-petroleum output/input ratios ranged from 10:1 to 13:1 but could be increased to 19:1 if farmers adopted high-yield progressive crop and soil management practices. An advanced closed-loop biorefinery with anaerobic digestion reduced GHG emissions by 67% and increased the net energy ratio to 2.2, from 1.5 to 1.8 for the most common systems. Such improved technologies have the potential to move corn-ethanol closer to the hypothetical performance of cellulosic biofuels. Likewise, the larger GHG reductions estimated in this study allow a greater buffer for inclusion of indirect-effect land-use change emissions while still meeting regulatory GHG reduction targets. These results suggest that corn-ethanol systems have substantially greater potential to mitigate GHG emissions and reduce dependence on imported petroleum for transportation fuels than reported previously.     

What Is Resource Consumption and How Can It Be Measured?

When analyzing the metabolism of our economy, the usual choice for a measure of resource consumption is the throughput of matter and energy. This, however, cannot be sufficient, since consumption by definition is always relating to the destruction or transformation, and hence a change in quality, not only in quantity, of material or energy flows. Here, an approach is presented that takes the entropy production associated with any process as a measure for the resource consumption of that process. Entropy production is thereby used to approximate the intuitive notion of consumption, which can best be described by the term loss of potential utility. This article delivers theoretical evidence for the validity of this choice, and a second article in a future issue will present an application taken from the metallurgical sector. The related concept of exergy analysis is discussed and compared against the entropy approach.     

Necessity and Inefficiency in the Generation of Waste

The laws of thermodynamics are employed as an analytical framework within which results about society's metabolism may be rigorously deduced in energetic and material terms. We demonstrate that the occurrence of waste is an unavoidable necessity in the industrial production of desired goods. Although waste is thus an essential qualitative element of industrial production, the quantitative extent to which waste occurs may vary within certain limits according to the degree of thermodynamic (in) efficiency with which these processes are operated. We discuss the question of which proportion of the amount of waste currently generated is due to thermodynamic necessity and which proportion is due to thermodynamic inefficiency.     

Environmental Assessment of Wood‐Based Biofuel Production and Consumption Scenarios in Norway

In Norway, the boreal forest offers a considerable resource base, and emerging technologies may soon make it commercially viable to convert these resources into low‐carbon biofuels. Decision makers are required to make informed decisions about the environmental implications of wood biofuels today that will affect the medium‐ and long‐term development of a wood‐based biofuels industry in Norway. We first assess the national forest‐derived resource base for use in biofuel production. A set of biomass conversion technologies is then chosen and evaluated for scenarios addressing biofuel production and consumption by select industry sectors. We then apply an environmentally extended, mixed‐unit, two‐region input?output model to quantify the global warming mitigation and fossil fuel displacement potentials of two biofuel production and consumption scenarios in Norway up to 2050. We find that a growing resource base, when used to produce advanced biofuels, results in cumulative global warming mitigation potentials of between 58 and 83 megatonnes of carbon dioxide equivalents avoided (Mt‐CO₂‐eq.‐avoided) in Norway, depending on the biofuel scenario. In recent years, however, the domestic pulp and paper industry—due to increasing exposure to international competition, capacity reductions, and increasing production costs—has been in decline. In the face of a declining domestic pulp and paper industry, imported pulp and paper products are required to maintain the demand for these goods and thus the greenhouse gas (GHG) emissions of the exporting region embodied in Norway's pulp and paper imports reduce the systemwide benefit in terms of avoided greenhouse gas emissions by 27%.     

Helping Students Reconstruct Conceptions of Thermodynamics: Energy and Heat

Thermodynamics, specifically energy and heat, is a major concept in the foundations of physics and physical science. To determine a strategy to teach thermodynamics meaningfully, the authors conducted classroom action research using interviews to determine secondary physics students' current conceptions of thermodynamics. On the basis of the findings, the authors developed and implemented a science unit to facilitate students' reconstructions of their ideas toward more scientifically appropriate concepts. The lessons, using a learning cycle strategy, and results of the pre- and post-interviews are presented.     

Thermodynamics of Agricultural Sustainability: The Case of US Maize Agriculture

This paper considers the local, field-scale sustainability of a productive industrial maize agrosystem that has replaced a fertile grassland ecosystem.

Using the revised thermodynamic approach of Svirezhev (1998 Svirezhev, Y. M. 1998. “Thermodynamic orientors: How to use Thermodynamic concepts in ecology”. In Eco Targets, Goal Functions, and Orientors, 102–122. Berlin: Springer Verlag. [Crossref] [Google Scholar], 2000 Svirezhev, Y. M. 2000. Thermodynamics and ecology. Ecological Modelling, 132: 11–22. [Crossref], [Web of Science ®] [Google Scholar]) and Steinborn and Svirezhev (2000) Steinborn, W. and Svirezhev, Y. M. 2000. Entropy as an indicator of sustainability in agro-ecosystems: North Germany case study. Ecol. Mode., 133: 247–257. [Crossref], [Web of Science ®] [Google Scholar], it is shown that currently this agrosystem is unsustainable in the U.S., with or without tilling the soil. The calculated average erosion rates of soil necessary to dissipate the entropy produced by U.S. maize agriculture, 23–45 t ha^?1 yr^?1, are bounded from above by an experimental estimate of mean soil erosion by conventional agriculture worldwide, 47 t ha^?1 yr^?1, (Montgomery, 2007 Montgomery, D. R. 2007. Soil erosion and agricultural sustainability. PNAS, 104(33): 13268–13272. [Crossref], [PubMed], [Web of Science ®] [Google Scholar]). Between 1982 and 1997, US agriculture caused an estimated 7–23 t ha^?1 yr^?1 of average erosion with the mean of 15 t ha^?1 yr^?1 (USDA-NRCS Database). The lower mean erosion rate of no till agriculture, 1.5 t ha^?1 yr^?1 (Montgomery, 2007 Montgomery, D. R. 2007. Soil erosion and agricultural sustainability. PNAS, 104(33): 13268–13272. [Crossref], [PubMed], [Web of Science ®] [Google Scholar]), necessitates the elimination of weeds and pests with field chemicals—with the ensuing chemical and biological soil degradation, and chemical runoff—to dissipate the produced entropy. The increased use of field chemicals that replace tillers is equivalent to the killing or injuring of up to 300 kg ha^?1 yr^?1 of soil flora and fauna. Additional soil degradation, not calculated here, occurs by acidification, buildup of insoluble metal compounds, and buildup of toxic residues from field chemicals. The degree of unsustainability of an average U.S. maize field is high, requiring 6–13 times more energy to reverse soil erosion and degradation, etc., than the direct energy inputs to maize agriculture. This additional energy, if spent, would not increase maize yields. The calculated “critical yield” of “organic” maize agriculture that does not use field chemicals and fossil fuels is only 30 percent lower than the average maize yield of 8.7 tons per hectare (～140 bu/acre) assumed here. This critical yield would not likely be achieved and sustained by large monocultures, but might be achieved by more balanced organic polycultures (Baum et al., 2008 Baum, A. W., Patzek, T. W., Bender, M., Renich, S. and Jackson, W. 2008. The Visible, Sustainable Farm: A Comprehensive Energy Analysis of a Midwestern Farm 1–34. Posted at petroleum.berkeley.edu/papers/Biofuels/SSF?Report3-051408.pdf [Google Scholar]).     

Life Cycle of Titanium Dioxide Nanoparticle Production

Life cycle impact of emissions, energy requirements, and exergetic losses are calculated for a novel process for producing titanium dioxide nanoparticles from an ilmenite feedstock. The Altairnano hydrochloride process analyzed is tailored for the production of nanoscale particles, unlike established commercial processes. The life cycle energy requirements for the production of these particles is compared with that of traditional building materials on a per unit mass basis. The environmental impact assessment and energy analysis results both emphasize the use of nonrenewable fossil fuels in the upstream life cycle. Exergy analysis shows fuel losses to be secondary to material losses, particularly in the mining of ilmenite ore. These analyses are based on the same inventory data. The main contributions of this work are to provide life cycle inventory of a nanomanufacturing process and reveal potential insights from exergy analysis that are not available from other methods.     

Analysis of Water Sorption Isotherms of Superabsorbent Polymers by Solution Thermodynamics

Water sorption isotherms of superabsorbent polymers were measured, and their affinity for water was evaluated by solution thermodynamics. The results provide basic data for the functional packaging of food to control the water content of food during its transportation or storage. Water activity above 0.9 was measured by adding a specific amount of water to the samples, while that below 0.9 was measured with apparatus for evaluating water sorption isotherms. Thus, water sorption isotherms for superabsorbent polymers were obtained up to a water activity of approximately 0.98. The amount of water sorbed by the superabsorbent polymers was influenced by the type of functional groups in the polymers, and not by the degree of cross-linking in the polymers. The integral Gibbs free energy, which is the most suitable parameter for evaluating the affinity of a material for water, was evaluated from the water sorption isotherms by using solution thermodynamics.     

Thermodynamics and dynamics of the formation of spherical lipid vesicles

We propose a free energy expression accounting for the formation of spherical vesicles from planar lipid membranes and derive a Fokker–Planck equation for the probability distribution describing the dynamics of vesicle formation. We find that formation may occur as an activated process for small membranes and as a transport process for sufficiently large membranes. We give explicit expressions for the transition rates and the characteristic time of vesicle formation in terms of the relevant physical parameters.     

An Indicator to Evaluate the Thermodynamic Maturity of Industrial Process Units in Industrial Ecology

The article suggests a measure to evaluate the thermodynamic maturity of industrial systems at the level of single process units. The measure can be quantified with reasonable confidence on the basis of entropy production as defined by irreversible thermodynamics theory. It quantifies, for one process unit, the distance between its actual state of operation and its state with minimum entropy production or optimum exergy efficiency, when the two states are constrained with a fixed production capacity of the process unit. We suggest that the minimum entropy production state is a mature state, or that processes that operate at this state are mature. We propose to call the measure the thermodynamic maturity indicator (π), and we define it as the ratio between the minimum entropy production and the actual entropy production. We calculated π on the basis of literature data for some examples of industrial process units in the chemical and process industry (i.e., heat exchanger, chemical reactor, distillation column, and paper drying machine). The proposed thermodynamic measure should be of interest for industrial ecology because it emerges from the entropy production rate, a dynamic function that can be optimized and used to understand the thermodynamic limit to improving the exergy efficiency of industrial processes. Although not a tool for replacing one process with another or comparing one technology to another, π may be used to assess actual operation states of single process units in industrial ecology.     

Thermodynamics of peptide binding to the transporter associated with antigen processing (TAP)

The ATP-binding cassette (ABC) transporter TAP plays an essential role in antigen processing and immune response to infected or malignant cells. TAP translocates proteasomal degradation products from the cytosol into the endoplasmic reticulum, where MHC class I molecules are loaded with these peptides. Kinetically stable peptide-MHC complexes are transported to the cell surface for inspection by cytotoxic T lymphocytes. The transport cycle of TAP is initiated by peptide binding, which is responsible for peptide selection and for stimulation of ATP-hydrolysis and subsequent translocation. Here we have analysed the driving forces for the formation of the peptide-TAP complex by kinetic and thermodynamic methods. First, the apparent peptide association and dissociation rates were determined at various temperatures. Strikingly, very high activation energies for apparent association (E(a)(ass)=106 kJmol(-1)) and dissociation (E(a)(diss)=80 kJmol(-1)) of the peptide-TAP complex were found. Next, the temperature-dependence of the peptide affinity constants was investigated by equilibrium-binding assays. Along with calculations of free enthalpy deltaG, enthalpy deltaH and entropy deltaS, a large positive change in heat capacity was resolved (deltaC degrees =23 kJmol(-1)K(-1)), indicating a fundamental structural reorganization of the TAP complex upon peptide binding. The inspection of the conformational entropy reveals that approximately one-fourth of all TAP residues is rearranged. These thermodynamic studies indicate that at physiological temperature, peptide binding is endothermic and driven by entropy.     

Thermodynamics of DNA packaging inside a viral capsid: the role of DNA intrinsic thickness

We characterize the equilibrium thermodynamics of a thick polymer confined in a spherical region of space. This is used to gain insight into the DNA packaging process. The experimental reference system for the present study is the recent characterization of the loading process of the genome inside the phi29 bacteriophage capsid. Our emphasis is on the modelling of double-stranded DNA as a flexible thick polymer (tube) instead of a beads-and-springs chain. By using finite-size scaling to extrapolate our results to genome lengths appropriate for phi29, we find that the thickness-induced force may account for up to half the one measured experimentally at high packing densities. An analogous agreement is found for the total work that has to be spent in the packaging process. Remarkably, such agreement can be obtained in the absence of any tunable parameters and is a mere consequence of the DNA thickness. Furthermore, we provide a quantitative estimate of how the persistence length of a polymer depends on its thickness. The expression accounts for the significant difference in the persistence lengths of single and double-stranded DNA (again with the sole input of their respective sections and natural nucleotide/base-pair spacing).     

Distribution of boron in the environment

The findings of a study to identify and quantify the orders of magnitude for major reservoirs and flows of boron (B) in the environment are outlined. The orders of magnitude for B reservoirs and flows arising through natural processes, such as the hydrological cycle and volcanism, are compared with those arising from anthropogenic activities, such as coal combustion and the extraction and use of borates for commercial purposes. The major stores and reservoirs for B have been identified, in order of magnitude, as the continental and oceanic crusts (10¹⁸ kg B), the oceans (10¹⁵ kg B), groundwater (10¹¹ kg B), ice (10¹¹ kg B), coal deposits (10¹⁰ kg B), commercial borate deposits (10¹⁰ kg B), biomass (10¹⁰ kg B), and surface waters (10⁸ kg B). The largest flows of B in the environment arise from the movement of B into the atmosphere from oceans, at between 1.3 * 10⁹ kg and 4.5 * 10⁹ kg B per annum. Other hydrological flows are also important. Drainage from soil systems into groundwaters and surface waters accounts for between 4.3 * 10⁸ kg and 1.3 * 10⁹ kg B per annum. B mining and volcanic eruptions represent the next most significant B flows, accounting for approx 4.0 * 10⁸ kg and 3.0 * 10⁸ kg B, respectively.     

Temperature and the Life Cycle of Heterodera zeae

Development of the corn cyst nematode, Heterodera zeae, was studied in growth chambers at 20, 25, 29, 33, and 36 ± 1 C on Zea mays cv. Pioneer 3184. The optimum temperature for reproduction appeared to be 33 C, at which the life cycle, from second-stage juvenile (J2) to J2, was completed in 15-18 days; at 36 C, 19-20 days were required. Juveniles emerged from eggs within 28 days at 29 C and after 42 days at 25 C. Although J2 were present within eggs after 63 days at 20 C, emergence was not observed up to 99 days after inoculation. Female nematodes produced fewer eggs at 20 C than at higher temperatures.