Entropy consumption in primary photosynthesis

Knox and Parson have objected to our previous conclusion on possible negative entropy production during primary photochemistry, i.e., from photon absorption to primary charge separation, by considering a pigment system in which primary photochemistry is not specifically considered. This approach does not address our proposal. They suggest that when a pigment absorbs light and passes to an excited state, its entropy increases by hnu/T. This point is discussed in two ways: (i) from considerations based on the energy gap law for excited state relaxation; (ii) using classical thermodynamics, in which free energy is introduced into the pigment (antenna) system by photon absorption. Both approaches lead us to conclude that the excited state and the ground state are isoentropic, in disagreement with Knox and Parson. A discussion on total entropy changes specifically during the charge separation process itself indicates that this process may be almost isoentropic and thus our conclusions on possible negentropy production associated with the sequence of reactions which go from light absorption to the first primary charge separation event, due to its very high thermodynamic efficiency, remain unchanged.     

Entropy consumption in primary photosynthesis

Knox and Parson have objected to our previous conclusion on possible negative entropy production during primary photochemistry, i.e., from photon absorption to primary charge separation, by considering a pigment system in which primary photochemistry is not specifically considered. This approach does not address our proposal. They suggest that when a pigment absorbs light and passes to an excited state, its entropy increases by hν/T. This point is discussed in two ways: (i) from considerations based on the energy gap law for excited state relaxation; (ii) using classical thermodynamics, in which free energy is introduced into the pigment (antenna) system by photon absorption. Both approaches lead us to conclude that the excited state and the ground state are isoentropic, in disagreement with Knox and Parson. A discussion on total entropy changes specifically during the charge separation process itself indicates that this process may be almost isoentropic and thus our conclusions on possible negentropy production associated with the sequence of reactions which go from light absorption to the first primary charge separation event, due to its very high thermodynamic efficiency, remain unchanged.     

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.     

Photosynthesis and negative entropy production

The widely held view that the maximum efficiency of a photosynthetic pigment system is given by the Carnot cycle expression (1-T/Tr) for energy transfer from a hot bath (radiation at temperature Tr) to a cold bath (pigment system at temperature T) is critically examined and demonstrated to be inaccurate when the entropy changes associated with the microscopic process of photon absorption and photochemistry at the level of single photosystems are considered. This is because entropy losses due to excited state generation and relaxation are extremely small (DeltaS < T/Tr) and are essentially associated with the absorption-fluorescence Stokes shift. Total entropy changes associated with primary photochemistry for single photosystems are shown to depend critically on the thermodynamic efficiency of the process. This principle is applied to the case of primary photochemistry of the isolated core of higher plant photosystem I and photosystem II, which are demonstrated to have maximal thermodynamic efficiencies of xi > 0.98 and xi > 0.92 respectively, and which, in principle, function with negative entropy production. It is demonstrated that for the case of xi > (1-T/Tr) entropy production is always negative and only becomes positive when xi < (1-T/Tr).     

Minimum entropy production in photosynthesis

In this paper a flux-coupling model of photosynthesis is presented. By requiring minimum entropy production, it is found that the photosynthetic efficiency is essentially given by the square root of D/λ. D and λ are the diffusion coefficient and thermal conductivity of the rate-limiting processes in the chloroplast, respectively. For experimental values of D and λ, the efficiency is found to be 2.4–7.5%, with a likely value of 6.1%, whereas C4-plants are known to have an efficiency of 6.2%. We conclude that the process of photosynthesis is in quantitative agreement with the principle of minimum entropy production.     

Rhizosphere engineering for sustainable crop production: entropy-based insights

There is a growing interest in exploring interactions at root–soil interface in natural and agricultural ecosystems, but an entropy-based understanding of these dynamic rhizosphere processes is lacking. We have developed a new conceptual model of rhizosphere regulation by localized nutrient supply using thermodynamic entropy. Increased nutrient-use efficiency is achieved by rhizosphere management based on self-organization and minimized entropy via equilibrium attractors comprising (i) optimized root strategies for nutrient acquisition and (ii) improved information exchange related to root–soil–microbe interactions. The cascading effects through different hierarchical levels amplify the underlying processes in plant–soil system. We propose a strategy for manipulating rhizosphere dynamics and improving nutrient-use efficiency by localized nutrient supply with minimization of entropy to underpin sustainable food/feed/fiber production.     

The light/dark cycle operation with an hour-scale period enhances caffeine production by Coffea arabica cells

The intermittent light irradiation with an hour-scale period is used for producing caffeine by Coffea arabica cells. Three factors concerning the light/dark cycle operation such as light intensity, the length of the cycle (period), and the ratio of the illumination time to the dark time (light/dark ratio) were investigated to optimize the caffeine production efficiency regarding light consumption. The light/dark ratio of 1/1 enhanced caffeine production, reaching the same level as continuous light; thus, the intermittent light irradiation improved the production efficiency twofold. The production was not influenced by the period, but was determined by light intensity regardless of intermittent or continuous light irradiation.     

Entropy principle for human development, growth and aging

Entropy productions within nude subjects in respiration calorimeters are calculated from the corresponding energetic data obtained by Du Bois et al. (1952, J. Nutr. 48, 257-293.). The entropy production for men is constant at environmental temperatures from 24-34 degrees C. The metabolic entropy production comprises 98.6% of the total entropy production. The entropy production for women shows a minimum at 30 degrees C (the middle of the neutral zone), a small rise in the cold zone and a trend toward a rise in the warm zone; the average entropy production for women is 8.7% smaller than that for men. The entropy production rises from 0-2 years of age, and decreases rapidly from 2-25 years of age and then gradually to 85 years of age. The entropy production does not seem to achieve a minimum or a level in the lives of men and women. Based on these results, a three-stage hypothesis of entropy production in human life is proposed.     

Thermodynamics of Terrestrial Evolution

The causal element of biological evolution and development can be understood in terms of a potential function which is generalized from the variational principles of irreversible thermodynamics. This potential function is approximated by the rate of entropy production in a configuration space which admits of macroscopic excursions by fluctuation and regression as well as microscopic ones. Analogously to Onsager's dissipation function, the potential takes the form of a saddle surface in this configuration space. The path of evolution following from an initial high dissipation state within the fixed constraint provided by the invariant energy flux from the sun tends toward the stable saddle point by a series of spontaneous regressions which lower the entropy production rate and by an alternating series of spontaneous fluctuations which introduce new internal constraints and lead to a higher entropy production rate. The potential thus rationalizes the system's observed tendency toward "chemical imperialism" (high dissipation) while simultaneously accommodating the development of "dynamic efficiency" and complication (low dissipation).     

Energy transformation and entropy production in living systems I. Applications to embryonic growth

Generalized material and energy balances are presented for biological systems that experience negligible kinetic, elastic, and potential energy changes. The balances are used to characterize the mass changes and energy transformations that occur in the developing avian embryo, using as an example a consistent set of data for the chicken egg. It is shown that the rate of total chemical energy turnover by the embryo is a quantity of interest and that this rate is not necessarily equivalent to the metabolic rate that is predicted from heat transfer measurements or oxygen consumption rates. The energy required for evaporative water loss is accounted for in the overall energy balance. Using the results of the energy calculations and a generalized expression for the rates of internal and total entropy production, the Prigogine-Wiame hypothesis is examined for the developing embryo with two different assumptions regarding the efficiency of biomass conversion. An order of magnitude analysis of the internal heat-conduction term is performed to show that the chemical reaction term dominates the entropy production relation. The constant efficiency case is shown to be in agreement with the Prigogine-Wiame hypothesis for the data used in the analysis.     

Effects of exercise and chills on entropy production in human body

Entropy flows and changes of entropy content for naked subjects in the respiration calorimeter in exercise and chills are calculated from the energetic data given by Hardy et al. (1938, J. Nutr. 16, 477) and Du Bois (1939, Bull. N.Y. Acad. Med. 15, 143). By use of these values, entropy productions in the human body in exercise and chills are estimated. The entropy production in mild exercise is 1.5-2.4 times as great as that in basal conditions. The entropy production in violent exercise is six to eight times as great as that before exercise. The entropy production in chills in cold environments is about twice as large as that in basal conditions. The entropy production in a malarial chill is about four times of that in normal subjects. These increases in entropy production will be due to the increase in heat production within the body. It seems that there is a parallel between energy and entropy viewpoints for human physiology.     

Entropy flow and entropy production in the human body in basal conditions

Entropy inflow and outflow for the naked human body in basal conditions in the respiration calorimeter due to infrared radiation, convection, evaporation of water and mass-flow are calculated by use of the energetic data obtained by Hardy & Du Bois. Also, the change of entropy content in the body is estimated. The entropy production in the human body is obtained as the change of entropy content minus the net entropy flow into the body. The entropy production thus calculated becomes positive. The magnitude of entropy production per effective radiating surface area does not show any significant variation with subjects. The entropy production is nearly constant at the calorimeter temperatures of 26-32 degrees C; the average in this temperature range is 0.172 J m-2 sec-1 K-1. The forced air currents around the human body and also clothing have almost no effect in changing the entropy production. Thus, the entropy production of the naked human body in basal conditions does not depend on its environmental factors.     

不同海拔高度高寒草甸光能利用效率的遥感模拟

利用植被光合模型模拟了藏北高原3个海拔高度(4300,4500 m和4700 m)的高寒草甸生态系统的光能利用效率.海拔4500 m的光能利用效率均值(0.47 g C/MJ)显著高于海拔4300 m(0.38 g C/MJ)和4700 m(0.35 g C/MJ),而海拔4300 m和4700 m两者间差异不显著.相关分析和多重逐步回归分析表明,影响每个海拔光能利用效率季节变化的主要因子为空气温度,相对湿度以及地表水分指数,这3个因子共同解释了99％以上的光能利用效率的季节变化,其中空气温度的贡献最大,相对湿度的贡献次之,地表水分指数的贡献最小,这说明在3个海拔的任何一个海拔高度,温度对光能利用效率季节变化的胁迫作用大于水分对光能利用效率季节变化的胁迫作用.多重逐步线性回归分析表明,生长季节均土壤含水量是决定生长季节均光能利用效率沿海拔高度分布的主导因子.单因子线性回归分析表明,地表水分指数可以定量化高寒嵩草草甸生态系统水分状况,它同时可以反应土壤水分、近地表空气湿度以及生态系统植被含水量状态.因此,在高寒嵩草草甸生态系统,用地表水分指数反应生态系统尺度水分对光能利用效率的胁迫作用是可行的.     

Balancing the energy flow from captured light to biomass under fluctuating light conditions

The balance of energy flow from light absorption into biomass was investigated under simulated natural light conditions in the diatom Phaeodactylum tricornutum and the green alga Chlorella vulgaris. The energy balance was quantified by comparative analysis of carbon accumulation in the new biomass with photosynthetic electron transport rates per absorbed quantum, measured both by fluorescence quenching and oxygen production. The difference between fluorescence- and oxygen-based electron flow is defined as 'alternative electron cycling'. The photosynthetic efficiency of biomass production was found to be identical for both algae under nonfluctuating light conditions. In a fluctuating light regime, a much higher conversion efficiency of photosynthetic energy into biomass was observed in the diatom compared with the green alga. The data clearly show that the diatom utilizes a different strategy in the dissipation of excessively absorbed energy compared with the green alga. Consequently, in a fluctuating light climate, the differences between green algae and diatoms in the efficiency of biomass production per photon absorbed are caused by the different amount of alternative electron cycling.     

Entropy balance of white-tailed deer during a winter night

The entropy budget of a white-tailed deer (50kg) on a maintenance diet and a full-feed diet in a standing posture in an open field under clear nocturnal skies with an air temperature of −20°C is investigated based on the energetics given by Moen. Entropy inflow into a white-tailed deer due to infra-red radiation and entropy outflows from a deer due to infra-red radiation, convection, evaporation of water and conduction to ingested food are calculated. Also the entropy production due to metabolic heat production is estimated. Net entropy flow into a deer from its environment becomes negative. On the assumption that a white-tailed deer is in a steady state in entropy, the total entropy production in a deer on a maintenance diet becomes +0.46 J/sec/K. Positiveness of the entropy production shows that the Second Law of Thermodynamics certainly holds in a white-tailed deer. The entropy production per effective radiating surface area of a deer on a maintenance diet is 0.32×10⁻⁴ J/cm²/sec/K. On the other hand, the entropy production in a deer on a full-feed diet is 0.59 J/sec/K and that per effective surface area is 0.41×10⁻⁴ J/cm²/sec/K. Uptake of 1 g of food produces 22 J/K of entropy within the body of a white-tailed deer. Comparison is made with the results for entropy production in a lizard and in plant leaves.     

A theoretical prediction of the normal cardiac oxygen consumption

A model is described from which the entropy production associated with the process of transporting oxygen and carbon dioxide between the lungs and the muscles of the body can be calculated. The two entropy sources which are assumed to be the dominant ones for this process are the entropy production associated with the metabolism of the heart and the entropy production associated with the diffusion of oxygen and carbon dioxide into and out of the blood. The hypothesis that the observed blood flow is the one for which a given amount of oxygen and carbon dioxide is transported between the lungs and the muscles with minimum total entropy production is used to predict the value of the slope of the cardiac oxygen consumption vs. blood flow curve. At a blood flow of 15 liters/min, the predicted value of the slope of this curve is 1.2 ml/liter.     

What Is Resource Consumption and How Can It Be Measured?

In the first part of this series of two articles, an approach was presented that takes the entropy production associated with any process as a measure of 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 presents an application example from the metallurgical sector. The related concept of exergy analysis is discussed and compared against the entropy approach. It was found that the production of 1 ton of refined copper generates 90.2 megajoules per Kelvin of entropy. A comparison with exergy analyses of copper production processes from the literature shows agreement at least on the order of magnitude. While results in one case deviate from the entropy analysis by about 40%, in another case the deviation is about 160%. One can only speculate on the reasons for this discrepancy, without knowing the exact process specifications of the processes analyzed. For entropy production as a measure for resource consumption, a baseline for comparison and interpretation of the results based on natural entropy disposal and reduction mechanisms is suggested.     

On the relationship between dissipation and the rate of spontaneous entropy production from linear irreversible thermodynamics

When systems are far from equilibrium, the temperature, the entropy and the thermodynamic entropy production are not defined and the Gibbs entropy does not provide useful information about the physical properties of a system. Furthermore, far from equilibrium, or if the dissipative field changes in time, the spontaneous entropy production of linear irreversible thermodynamics becomes irrelevant. In 2000 we introduced a definition for the dissipation function and showed that for systems of arbitrary size, arbitrarily near or far from equilibrium, the time integral of the ensemble average of this quantity can never decrease. In the low-field limit, its ensemble average becomes equal to the spontaneous entropy production of linear irreversible thermodynamics. We discuss how these quantities are related and why one should use dissipation rather than entropy or entropy production for non-equilibrium systems.     

Introducing extra NADPH consumption ability significantly increases the photosynthetic efficiency and biomass production of cyanobacteria

Increasing photosynthetic efficiency is crucial to increasing biomass production to meet the growing demands for food and energy. Previous theoretical arithmetic analysis suggests that the light reactions and dark reactions are imperfectly coupled due to shortage of ATP supply, or accumulation of NADPH. Here we hypothesized that solely increasing NADPH consumption might improve the coupling of light reactions and dark reactions, thereby increasing the photosynthetic efficiency and biomass production. To test this hypothesis, an NADPH consumption pathway was constructed in cyanobacterium Synechocystis sp. PCC 6803. The resulting extra NADPH-consuming mutant grew much faster and achieved a higher biomass concentration. Analyses of photosynthesis characteristics showed the activities of photosystem II and photosystem I and the light saturation point of the NADPH-consuming mutant all significantly increased. Thus, we demonstrated that introducing extra NADPH consumption ability is a promising strategy to increase photosynthetic efficiency and to enable utilization of high-intensity lights.     

Entropy budgets of soybean and bur oak leaves at night

From energy budgets of soybean [ Glycine max (L.) Merr. cv. Chippewa] and bur oak ( Quercus macrocarpa ) leaves at night, entropy fluxes into or out of leaves are calculated. The absorbed entropy balances with the emitted entropy; this is not the case for leaves during the day and for an animal at night. On the assumption that the entropy in leaves is at steady state, entropy production in leaves becomes small and almost zero. Since entropy production is a measure of activity in organisms, the activity in leaves is small at night; this is in contrast to leaves during the day. Thus, a large portion of the activity in leaves is "on" in the daytime and "off" at night. Most of the activity in leaves may be triggered by solar radiation.