Journal of Cleaner Production 10 (2002) 225235 www.cleanerproduction.

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A uniform denition and quantitative basis for industrial ecology

T.P. Seager *, T.L. Theis
Center for Environmental Management, Environmental Manufacturing Management Program, Clarkson University, P.O. Box 5715, 104 Rowley Laboratories, Potsdam, NY 13699, USA Received 9 January 2001; accepted 15 August 2001

Abstract Industrial ecology (IE) has been characterized by a fragmented approach encompassing a number of different perspectives and analytical techniques. A uniform framework has yet to be established or proposed. This paper partially addresses this shortcoming by tracing some of the historical and intellectual antecedents of the eld, providing a clear and concise lexicon of the biological analogue, and contrasting the two most promising analytical methods by which IE research may be carried out: life cycle assessment (LCA) and systems analysis. Although a number of comparative environmental metrics may be employed in cost-minimization or thermodynamic efciency studies, no single measure is sufciently developed to prioritize among qualitatively disparate types of environmental impacts. It is argued herein that the concept of chemical exergy of mixing may be the most promising basis for the development of a uniform, broad-based measure of chemical pollution, and that such a measure could signicantly advance a scientic approach to IE. Some theoretical background is presented, although the reasoning herein is intended to be accessible to an interdisciplinary audience. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Industrial ecology; Exergy; Environmental metrics

1. Intellectual and historical antecedents As an emerging science, industrial ecology (IE) has been accessible to researchers from a number of different disciplines [1], however, it has yet to establish a consistent denition or a uniform analytical framework in part explaining why the concept of a natural analogue for study of industrial systems is far from universally embraced among environmental engineers, scientists or managers. IE has been variously described as a paradigm shift [2], a broad umbrella of concepts, rather than a unied theoretical construct [3] and an aggregation of trends (that) is still being dened by its proponents [4]. A broad review of the historical origins of the term shows that a myriad of denitions, descriptions and new terms have appeared, disappeared or reappeared in the literature only to confuse experts and neophytes alike. A new terminology or vocabulary must eventually

be established that reects the evolution of scientic thought [5]. A comprehensive literature review shows that there has been considerable uncertainty as to what IE is or should be. In the seminal paper which popularized the neologism, Frosch and Gallapoulos [6] proposed that industrial systems would function more efciently and with fewer environmental impacts if they were modeled after natural ecosystems wherein the consumption of energy and materials is optimized, waste generation minimized, and the efuents of one process serve as the raw materials for another process.1 This supposition is an extension of what Ayres [7] called industrial metabolism and characterized as the energy-and-value-yield1 The paper mentions two additional terms that become important to future discussions. Dematerialization is dened as the use of plastics, composites, and high-strength alloys to reduce the mass of products, and cited as an important trend in the auto industry wherein cars are becoming lighter, more fuel efcient, but also increasingly difcult to recycle as the materials from which they are manufactured become more diverse and complicated. Additionally, the paper refers to the life cycle of various industrial materials (e.g. metals and plastics), in which the origin, use and eventual fate of the materials are studied together to identify opportunities for resource savings.

* Corresponding author. Tel.: +1-315-268-3856; fax: +1-315-2684291. E-mail addresses: seagertp@clarkson.edu (T.P. Seager), theist@clarkson.edu (T.L. Theis).

0959-6526/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved. PII: S 0 9 5 9 - 6 5 2 6 ( 0 1 ) 0 0 0 4 0 - 3

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ing process essential to economic development analogous to the metabolic processes that are essential to life.2 Industrial ecology may be considered a natural broadening of the metabolic analogy [10]. For a brief period, the two terms industrial metabolism and IE coexisted and may have even been used interchangeably [11]. However, the rst textbooks in the eld appeared to almost completely discard metabolism in favor of ecology [9,12,13]. Socolow [13] wrote that IE is intended to mean both the interaction of global industrial civilization with the natural environment and the aggregate of opportunities for individual industries to transform their relationships with the natural environment, thereby subsuming the research that had been conducted under a metabolism banner and expanding the meaning of IE to make a separate term superuous. In retrospect this seems unnecessary the two metaphors create different perspectives that need not be competitive, but complementary. Subsequently, the terms industrial and ecology have also been subject to debate Socolow [13] claimed that industrial held different meanings depending upon whether a metabolism or ecology perspective was adopted, while Commoner [14] has questioned application of the term ecology. Together they have subsequently come to be interpreted broadly to mean practically any anthropogenic function, including agriculture, information technology, etc. not just manufacturing [15]. Extending the argument for a broad denition of industrial might lead to the logical conclusion that the natural and industrial are not separate systems, but inexorably linked and therefore must be considered together. A merging of natural and IE may be the inevitable consequence of a holistic application of the natural analogue, however, a theoretical basis for modeling the linkages has not yet been established. While it is clear that an analogy has led to a new eld of study and a new perspective from which to model industrial processes, the separate but overlapping denitions offered to date are not adequately resolved by any author, although articulation of a vocabulary has been identied as a prerequisite step [16]. Therefore, for the purposes of this paper, IE shall be dened as a eld of study (or branch of science) concerned with the interrelationships of human industrial systems and their environments. Similarly, industrial metabolism shall be dened as the process by which mass and energy (exergy) ows are handled or transformed by the economy. Lastly, an industrial ecosystem shall be understood to mean a model of a community or system of rms that

is based upon a natural analogue.3 Alternative descriptions need not be entirely supplanted by these, as they may offer explanatory power for a specialized agenda, but the denitions offered herein are broad enough for a wide range of applications and consistent with the biological and etymological roots that inspired invention of the terms. If it is not too late to dene the nomenclature of such a young and emergent eld, these denitions would serve to facilitate clarity, understanding and further research if they become more widely adopted.

2. Contrasting analytical perspectives There are principally two perspectives which provide an analytical basis for IE: life cycle assessment (LCA) and systems analysis.4 Each embodies the notion that environmental problems should be examined with an increasingly holistic, rather than reductionist, approach. Although there are signicant differences between the two (see Table 1), they are both extremely sensitive to how the boundaries of study are dened. In fact, one of the principle motivating hypothesis of IE is the intuitive sense that as the boundaries expand, supraoptimal solutions may emerge. That is, the most favorable outcome may be found by coordinating the activities of all system components, rather than by combining the individual best option of each subsystem. Still, LCA and systems analysis approach this synthesis of separate subsystems in different ways. Whereas the LCA approach relies upon the metaphor of a product or process lifetime although this is difcult to dene unambiguously sysTable 1 Summary comparison of LCA and system analysis Characteristic Purpose Boundaries Data requirements Emphasis Applicability Life cycle assessment Systems analysis

Descriptive Prescriptive Cradle to cradle/grave Scalable Broad Focused on decision Materials cycling Any uniform metric (e.g. dollars) Industrial metabolism Industrial ecology

2 See Thomas [8] for comments regarding Ayres [7] and Ayres and Ayres [9].

These denitions are not entirely original. One could obtain nearly the same by looking up the words ecology, metabolism, and ecosystem in the dictionary just substitute the word industry for organism in the denitions provided therein. We happened to use Websters ninth new collegiate dictionary, Merriam-Webster Inc., Springeld, MA 1988. 4 ORourke et al. [3] have presented a critical review of IE literature, research strategies and tools which remains relevant. However, they do not include a detailed discussion of LCA or systems analysis, instead focusing on other methodological and theoretical aspects or weaknesses (e.g. design for environment, ecofeedback, Pigouvian taxes).

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tems analysis is more exible. The systems approach is amenable to any scale: from single product or process to an entire industry or geographic region. The objective of LCA is principally comparative, whereas in systems analysis the emphasis is explicitly placed upon optimization and decision-making. That is, LCA lends itself to descriptive models, while systems analysis lends itself to prescriptive models. For this reason, the data requirements of LCA may be more extensive than systems analysis at least wherein systems analysis may neglect information that is beyond the boundaries of a focused study or irrelevant to the decision at hand. LCA is therefore more applicable to industrial metabolism, wherein the emphasis is on examining specic materials ows and processes, whereas systems analysis is more applicable to IE, wherein the emphasis is on examining interrelationships.

3. Life cycle assessment LCA is the principal tool by which IE research is carried out. As Allenby [17] argues, virtually all modern approaches to environmental issues begin with the assumption that the appropriate scale of the analysis is the life cycle of the material, product or service at issue. Although a wide variety of approaches have been advocated, LCA researchers typically follow a four-step methodology consisting of scoping, inventory analysis, impact assessment and improvement assessment (see Graedel [18], SETAC [19], or USEPA [20], etc. for further details). Scoping is a process of identifying the goals that motivate the assessment and determining the proper boundaries of study. The inventory analysis is an accounting of the resource requirements of a particular product, process or industry from virgin materials extraction to nal disposition. The impact assessment is conducted to relate the inventory data to specic environmental concerns. Finally, the improvement assessment (or interpretation phase) identies those aspects of the materials life cycle that might be most amenable to mitigation, or evaluates the potential for application of new strategies (e.g. design for environment) that offer the greatest leverage for environmental benets. However, current LCA techniques have been criticized as unreliable scientic tools subject to quantitative and qualitative errors [2124]. The limitations identied with current practices include a lack of adequate inventory data, difculties in identifying the boundaries of the system, disparate underlying assumptions, and impact assessments in terms that are not directly comparable. Nevertheless, LCA is perceived as a useful management tool that is growing in acceptance among industrial practitioners [25]. Graedel [18] suggests streamlining LCA to partially overcome the difculties of completing an extensive

LCA. The methodology proposed is greatly simplied. A subjective score (14) is assigned to each component of a matrix describing the type of impact (e.g. energy consumption, solid waste generation) versus portion of the life cycle. The advantage of this method is the reduced time frame for completion a few days rather than several months and the ease in communicating the results of the analysis to administrators and the public. However, no matter which methodology is employed, widely disparate, albeit defensible, conclusions can be drawn depending upon what information is excluded from the study, or which underlying assumptions are applied [26]. In many instances, a life cycle inventory requires compilation of chemical information for intermediary or by-products for which manufacturers or suppliers maintain little quantitative account. Even when such data do exist, it is often regarded as proprietary, and therefore unavailable, unveriable or unpublishable. Lave et al. [24] have shown that the boundaries of LCA should be even greater than suggested by current guidance documents, especially when the alternatives compared include signicantly different raw materials. However, it is apparent that no logical beginning or end to a specic materials cycle may exist, and that establishing the boundaries of an inventory analysis may rely upon arbitrary judgments. This presents a signicant obstacle to producing scientic research that is reproducible by different investigators. The principal advantage of LCA is that it provides a broad framework for asking questions it guides the investigative process beyond local boundaries, forcing consideration of factors that may have previously been ignored which is informative as a management tool and as a vehicle for exploring an intuitive appreciation of a more holistic approach. The photographic industry provides an illustrative example. In Fig. 1, a management perspective typical of current practices is represented by the boxes drawn around manufacturing activities. The emphasis is on reducing waste and pollution from the source of production. Raw material requirements and pollutant emissions are benchmarked to production of nished product: for example, photographic lm, paper or chemicals. Herein, the principles of waste minimization and pollution prevention may be successfully applied (and are increasingly the focus of traditional environmental engineers), but primarily as a method of meeting stringent emissions goals more cost-effectively. The portions of Fig. 1 outside the boxed boundaries illustrate a more comprehensive view consistent with the product life cycle analogy. Typically, photographers capture extra exposures of critical scenes (i.e. the just in case shots), or take exposures that later prove to be unsatisfactory (e.g. I look fat in that photo), or take additional, unnecessary exposures just to use up the

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what information is critical and may result in signicant economic and environmental savings.

4. Systems analysis Systems analysis typically requires a mathematical model that characterizes the relationships and constraints governing various systems components. The model is usually the result of a careful analysis of the system in question in which quantitative links among components are established. Boundaries may either be drawn narrowly (e.g. around a single manufacturing facility) or more broadly (e.g. to include suppliers, partners, customers or to encompass wide geographic regions). The focus of systems analysis is the objective function, which must be expressed in uniform units of measurement (e.g. dollars). The goal of a systems analyst is to nd a solution which satises the mathematical model for the maximum (or minimum) value of the objective function. Therefore, systems analysis is a design tool which helps decision-makers focus all the elements of a system towards a single objective. Systems analysis is amenable to any measurable management goal. Selection of a unifying objective metric is an analytical prerequisite. Current environmental management approaches focus primarily on maximizing prots (or minimizing manufacturing costs) while maintaining compliance with emissions regulations or selfimposed constraints. Revelle et al. [27], Haith [28] and Ossenbruggen [29] exemplify current analytical approaches. However, not all business operations are guided by a prot-maximizing principle. For example, public utilities may operate under constrained prot margins and instead attempt to minimize costs while maintaining a high standard of service and low level of safety risks. By analogy, a hypothetical manufacturing facility could conceivably be optimized to generate xed prots at some minimal measure of environmental risk such as toxicity-weighted chemical releases [30]. This kind of approach has yet to be put into practice and may be counter productive to the extent that nontoxic environmental threats like global warming or eutrophication would be ignored it is not obvious that minimal toxic release is synonymous with minimal environmental impact. Because it is difcult to simultaneously optimize for multiple objective functions, the greatest obstacle to the pursuit of a quantitative environmental systems approach for IE remains the fact that no single variable or metric exists which embodies a holistic measure of environmental impact. This in part offers an explanation for why the hypothesis originally articulated by Frosch and Gallapoulos [6] is yet to be tested in any comprehensive, scientic way. Fig. 2 illustrates a systems model of the silver halide and digital photographic imaging chains. Three steps are

Fig. 1. Typical (Compliance) vs. life cycle perspective. The typical compliance perspective (inside boundaries) measures nished product and residuals at the factory, in terms of material production. The life cycle perspective (complete gure) measures nal product at the end of the chain, rather than in the middle, in terms of value to the photographer excluding unwanted materials like unsatisfactory photographs.

roll. Current industry practice is to develop and print all of the exposures, even create double prints, prior to returning the images to the photographer. That is, although not all photographs are equally valued by the photographer they all consume equivalent thermodynamic and environmental resources. The fact that most photographic prints go into long-term storage (the shoe box) without ever being revisited is indicative that a great portion of the lm and paper which is perceived by the manufacturer to be nal product may be wasted. An improvement assessment might focus on employing digital technology to make photographic processes much more environmentally and economically efcient. For example, digital cameras typically allow photographers to delete unsatisfactory exposures by displaying them on a small LCD screen at the back of the camera. This obviates the need for developing and printing unwanted photographic prints. Other digital technologies operate on the same principle. For example, a lm drive scans photos from a negative directly into computer memory without need for a paper print allowing the photographer to preview and select which images or

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evaluating relative environmental impact of each technology, a more focused approach is expedient. Consequently, it is not necessary to complete comprehensive LCAs in order to draw effective comparisons; an abridged or marginal LCA may be adequate. However, this dilutes the principal benet of the life cycle metaphor the notion of expanding the boundaries of study and systems analysis is a more appropriate term for such an approach. Table 1 summarizes the principal differences between the two perspectives.

5. Introduction to quantitative metrics for LCA and systems analysis

Fig. 2. Which is the optimum image pathway?

common to both: capture, processing, and output (or printing), and the feasible or hypothetical links between each step on each chain create a myriad of technological possibilities that may efciently serve a variety of photographer preferences. Both LCA and systems approaches may be adapted to provide contrasting interpretations of the photographic industry model depicted in Fig. 3. An LCA approach would entail separate assessments of each imaging step or link to determine the comparative environmental characteristics of each pathway or identify any opportunities for improvement along any particular pathway. The systems approach would model the functional relationships at each box and link to determine which pathway best meets the objective criteria. Because the systems approach is more exible, it may have advantages as a decision or design tool. The data requirements can be less onerous and the system boundaries can be dened unambiguously. The photographic industry again provides illustrative examples. Suppose the focus of one aspect of study is the environmental impact of two methods of printing: ink jet and silver halide photographic. As far as each is printed on identical paper base, the environmental impact of the base is irrelevant to comparison. Only the different coatings, consumable chemicals and energy requirements need be studied. Whereas an LCA approach requires consideration of every aspect including the paper on which the image is printed, systems analysis can exclude those factors which remain uninuenced by the decision without altering the conclusions. In this way, systems analysis allows a more specic denition of system boundries which partially overcomes one of the primary obstacles to LCA: the extensive data requirements called for by the life cycle inventory. This principle is applicable to other aspects of the imaging chains as well. For example, both digital and lm cameras must contain similar elements: camera body, a lens, etc. In some instances, these are interchangeable. To effect a comparison for the purposes of

Both LCA and systems approaches suffer from the same shortcoming: the lack of a uniform basis for comparison or expression of disparate material and energy requirements, emissions or environmental impacts [31]. LCA is severely limited in its applicability to complex problems (such as technology replacement) in which the resources and pollutants resulting from alternative analyses are likely to be incomparable, and environmental systems analysis to date has primarily been a vehicle for identifying cost-savings opportunities rather than environmental improvements. Unfortunately, there is currently no scientic methodology for answering the most critical question of IE: which of the technological alternatives is preferable from an environmental perspective? There are three metrics that might be applied within the context of LCA or systems analysis to address the foregoing question: total nancial cost, thermodynamic (material and energy i.e. exergy) resource consumption, and environmental impact. The remainder of this paper is primarily concerned with introducing the thermodynamic concept of exergy of mixing as a promising basis for development of a scientic, objective measure of the latter quantity, but the rst two must also be addressed briey to provide a basis for comparison.

6. Total cost assessment Although accounting, nance and economics are highly developed disciplines applicable within the context of either LCA or systems analysis, it would be fallacious to take for granted that they may be applied to determine environmental preferences. Gray [32] exemplies the criticisms that have been levied against current accounting practices essentially arguing that these are too narrowly focused to provide accurate or objective information to decision-makers regarding the environmental implications of industrial activities. For example, in addition to the classic economic problem of external costs, there are several instances wherein it is common practice to neglect or misallocate internal nancial costs

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such as: contingent liabilities and legal expenses, remediation, employee moral, brand image, and treatment or disposal costs that are charged to overhead instead of to specic production activities. Total cost assessment has been advocated as an alternative which is consistent with the basic underlying principal of IE: that a more inclusive, holistic treatment will lead to better decisions [33,34]. However, TCA approaches have rarely been employed within the context of LCA to determine environmental preferences. There may be circumstances in which the most nancially expedient strategy (even by holistic measures) is not the environmentally preferable one [35], or the interests of future generations are denigrated [36], or the most protable strategy is to irreversibly exploit natural resources to exhaustion (or in the case of biological resources, extinction) [37].

7. Exergy as a measure of material and energetic resource consumption Hocking [38] suggests that net energy expenditure may be the most useful measure for judging environmental performance. However, Ayres et al. [39] propose a unied basis for LCA based upon the thermodynamic concept of exergy which is an improvement upon energetic measures to create a more complete resource and waste accounting. A term invented by Rant [40], exergy combines the rst and second laws of thermodynamics in a manner analogous to Gibbs free energy, Helmholtz energy or availability. It is a thermodynamic property that expresses the capacity of a system to perform work under ideal conditions. Because all industrial processes and all material and energetic ows may be modeled in terms of embodied exergy, thermodynamics could theoretically provide a common scientic framework for both LCA and systems analysis, merging the two perspectives into complementary tools. A general relationship can be drawn between exergy and the material life cycle wherein high exergy (low entropy) resources are extracted from the environment, rened by the economy, and returned to the environment as low exergy (high entropy) wastes.5 Although exergy may be found in four basic forms, kinetic, potential, chemical and physical (i.e. pressurevolume and heat exchange type work), for the present purposes the most important aspect of exergy analysis is chemical, which is analogous to Gibbs free energy BchemicalGHT S (1) where Bchemical represents change in chemical exergy,

G change in Gibbs free energy, H change in enthalpy, T absolute temperature and S change in entropy between two thermodynamic states. Computation of Gibbs free energies of formation has been the subject of extensive research. Standard tables are available as supplements or appendices to textbooks that describe the general principles in application to environmental problems [42]. The standard reference state is most commonly taken to be a pure elemental, zero valence form (e.g. O2 (g), Cl2 (g), Ag(metal)) and the free energies of formation of all other compounds may be computed by comparison to these. Unfortunately, the highly reactive state of some standard forms (chlorine, hydrogen, etc.) makes them an inappropriate reference state for exergetic analyses incorporating environmental considerations. Moreover, pure reference conditions are not representative of the state in which chemical compounds commonly occur in the environment. The principal advantage of exergy compared to Gibbs free energy is a system of environmental reference states rst proposed by Ahrendts [43] which identies the chemical characteristics of three different reference environments for computation of standard chemical exergies: the atmosphere, the ocean, and the earths crust. In many cases the most oxidized form of an element serves as the appropriate reference state in each environment, however consideration must also be given to the molar concentration of a compound in the specied environmental sink. This is of utmost importance, as it is well recognized that natural systems are not at thermodynamic equilibrium, but rather must be approximated as ongoing, quasi-steady-state reactions limited by both kinetic and energetic considerations, and that pure substances released into the environment will eventually become dissipated to background concentration levels. The principles for computation of the standard chemical exergy of any compound are described by Szargut et al. [44]. Assuming standard pressures and temperatures, a simplied general formula may be employed
0 B0 pG

ni 0 B np i

(2)

where G0 is the free energy of formation (kJ/mole) of the compound from the elements, ni the number of moles and B0 i the standard chemical exergy (kJ/mole) of the ith reactant required to form np moles of the product compound; ni and np are determined by the stoichiometric balancing numbers of the appropriate chemical reaction. The formation of ammonia gas from nitrogen and hydrogen provides a simple example. The chemical reaction is represented by
1 2

N2(g)11 2H2(g)NH3(g)

(3) (4)

5 See Ayres [41] for a critical review of the role of thermodynamics in economic theory and further treatment of exergy as a factor of production.

1 16.481 2(0.72)12(236.1)338 kJ/mole.

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The Gibbs free energy of formation of ammonia gas is given as 16.48 kJ/mol [42]. However, the standard chemical exergy is found to be 338 kJ/mol by substituting thermodynamic data from Table 2 into Eq. (2). Whereas the Gibbs free energy is representative of the ideal thermodynamic work required to sythesize pure ammonia from pure elements, the standard chemical exergy is representative of the maximum work that could be obtained under ideal conditions from pure ammonia gas. An extensive tabulation of standard chemical exergies has been compiled by Ayres et al. [39], making exergy the thermodynamic variable of choice for studies related to the environment. Exergy analysis has subsequently been employed in LCA [45] and to advance a scientic basis for sustainability [46].

8. The problem of quantifying environmental impact As a common basis for resource accounting, exergy is an improvement upon mass or energy-based measures, but it is far from a panacea for the difculties of conducting an environmental impact assessment or constructing an environmental objective function. Although it has been argued that the concept of exergetic optimization of industrial processes can be justied on environmental [47,48] or moral [49] grounds, current applications are for the most part limited to those industries wherein thermodynamic and economic criteria are closely aligned. Bejan [50] and Brodyansky et al. [51] exemplify current approaches in industries such as electric power generation, refrigeration, distillation, etc. Currently, no methodology exists whereby exergy may be reliably related to environmental impact or ecosystem function. This is primarily because waste exergy that which is released to the environment in the form of chemical pollutants and waste heat comes in different forms that may have different quantitative and qualitatTable 2 Thermodynamic data (R=8.314 J/mol/K, T=298.15 K, P=101.325 kPa) G0 (kJ/mol)a B0 (kJ/mol)b yi0 (mol/mol)b N2 H2 NH3 CH4 O2 CO2 H2O NO2 SO2 C(graphite)
a b

ive environmental effects. Therefore, a waste exergy (or exergy emissions) approach could provide only a rst approximation of environmental impact (see Dincer [52] or Gunnewick and Rosen [53] for a summary of the salient hypotheses). To remedy this theoretical deciency, many manufacturing companies have developed empirical metrics to gauge improvements in environmental performance [54 57]. Typically, these apply subjective value judgments regarding the importance of various characteristic impacts allowing cross-comparison of different technologies, materials alternatives or material and energetic trade-offs. However, of the wide variety of approaches currently employed, none are appropriate for development of a broad-based quantitative framework for IE. They may be too narrowly focused (e.g. on human toxicity), rely on economic rather than environmental measures (e.g. externalities), fail to capture the disparate qualitative characteristics of various materials (e.g. materials intensity indices), or be applicable only to a narrow set of products, industries or single company. Consequently, the need for a universal, broad-based environmental metric has increasingly been recognized as a high priority for research. A better approach may be to focus on the portion of the chemical exergy which is due solely to material transfers or changes in composition. This is referred to as the exergy of mixing, and it is a measure of the potential chemical change attributable to introduction of any pollutant into the environment.

9. Calculation of exergy of mixing There are two mechanisms by which chemical exergy may be converted into work or entropy: heat transfer and mass transfer. The rst of these is manifested in the chemical bond and released during reaction (e.g. combustion of fossil fuels to form carbon dioxide and water), and the second in dilution or dissipation of reaction endproducts throughout the environment (e.g. the atmosphere). Whereas matter and energy are conserved throughout the process, exergy is not. Assuming isothermal and isobaric conditions, the net chemical exergy of heat transfer for a reaction is approximated by the change in Gibbs free energy in accordance with Eq. (1), whereas the exergy of mixing (or composition-dependent component of chemical exergy [44]) is computed for the ith chemical species of any system as Bm i niRT0 ln

RT ln(yi0) (kJ/mol) 0.720 32.9 3.97 19.87 9.49 51.4 42.6

0 0 16.48 50.79 0 394.37 228.57 51.3 330.2 0

0.72 236.1 337.9 831.65 3.97 19.87 9.49 55.6 313.4 410.26

0.7479 1.7 ppm 0.201 0.000331 0.0217 1 ppb (est.) 35 ppb (est.)

yi y0 i

(5)

From [42]. From [44].

where Bm i is exergy of mixing in joules, ni the total number of moles of the species, yi the acitivity in the thermodynamic system under consideration, and y0 i the refer-

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ence activity in the appropriate environmental sink. R is the universal gas constant, taken to be 8.314 J/mol/K; T0 is standard temperature, 298.15 K. Because the work available in chemical reaction (i.e. heat transfer) is generally much larger than that of mixing (i.e. mass transfer), researchers have to date nearly uniformly ignored dissipative considerations ([58]; an exception is Edgerton [59]). For example, consider the chemical reaction representing methane combustion CH42O2CO22H2O G [(50.79)2(0)][394.372(
0

Table 3 Properties typical of bituminous coal [44] Mass fraction (kg/kg) C H2 H2O(l) O2 S N2 Ash 0.577 0.041 0.10 0.112 0.013 0.007 0.15 m.w. (g/mol) Molal fraction (mol/kg) 12 2 18 32 32 28 48.1 20.5 5.56 3.50 0.406 0.250 ni (mol/35.3 g)

(6) (7)

1.70 0.724 0.200 0.124 0.015 0.009

228.57)]800.72 kJ/mol. The change in Gibbs free energy for the reaction is given in Eq. (7) and is computed from the thermodynamic data in Table 2 by subtracting the stoichiometric equivalent standard free energies of formation of the reactants from those of the products. The standard chemical exergy is computed with Eq. (2) as 831.7 kJ/mol from the formation reaction as in the ammonia example. The difference of 31.0 kJ/mol between the standard chemical exergy and the negative Gibbs free energy is entirely due to the net exergy available from dissipation of the products (taken as pure carbon dioxide and pure water vapor in accordance with the Gibbs standard states) throughout the environment, minus the exergy required to concentrate pure oxygen at the site of the reaction. From this example it is clear that the standard chemical exergies B of the reference compounds O2, CO2, and H2O may be determined solely by their exergies of mixing computed from Eq. (5), assuming reference activities y0 i shown in Table 2, and that the results are consistent with those given by Eq. (2). From an energetic standpoint, the net exergy of mixing is negligible, being in the order of 1/25th the net work available from combustion. Nevertheless, it embodies the thermodynamics of the nal step wherein waste products are introduced into and dispersed throughout the environment, and may provide a specic link between exergetic LCA and a holistic measure of the potential for unintended or adverse environmental consequences. The case of coal, which is a mixture of hydrocarbons, oxygen, sulfur, nitrogen, moisture, ash and trace elements, provides a basis for comparison. Mass fractions typical of moist coal are given in Table 3. The total chemical exergy is estimated as 23,583 kJ/kg [44]. Therefore, approximately 35.3 g of coal is required to provide the same 831.7 kJ exergy as one mole of pure methane gas. A simplied chemical reaction (ignoring trace elements and ash) is shown below. The stoichiometric balancing numbers represent the number of moles of each substance involved in the reaction of 35.3 g coal (see Table 3):

(1.70 C0.724 H20.200 H2O(l)0.124 O2 0.015 S0.009 N2)coal1.862 O2(g)1.70 CO2 0.924 H2O(g)0.009 NO2(g)0.015 SO2(g) The exergy of mixing of the exhaust gases may be computed from Eq. (5). These total 43.65 kJ for coal, compared to 38.85 kJ for an exergetic equivalent amount of methane. Although exergy of mixing of the exhaust gases is very small (and uneconomical) compared to total exergy, from an environmental impact standpoint the waste exergy of mixing is an objective measure of the chemical change engendered in the environment by release of the combustion products to the atmosphere. Excluding oxygen (which is extracted from rather than wasted to the atmosphere) the sum of the exergies of mixing of the coal exhaust gases is 12% higher than those of methane, indicating that coal combustion is likely to have a greater atmospheric environmental impact (due to increased CO2 emissions from carbon) than methane combustion.6 Furthermore, it is possible to relate exergy of mixing to other measures of environmental impact. Fig. 3 (adapted from [53]) compares the exergy of mixing of ve atmospheric pollutants to estimates of environmental pollution costs. In general, those chemical species which appear with the greatest frequency in the environmental sink of interest are those with the lowest exergy of mixing and least potential for harm. Conversely, organisms and ecosystems have little evolutionary experience with chemical species which occur only rarely in nature and introduction of these (having greater exergy of mixing) may be particularly disturbing. Chemical species which do not occur at all in nature (e.g. chlorinated hydrocarbons such as CFCs or PCBs)
6 Additional environmental considerations have not been included in this analysis and may make coal even less attractive: e.g. the presence of mercury increases the loading of pollutants to the atmosphere and ash disposal may present a problematic land impact.

(8)

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Degradation of the pollutant over time. Passing of the material beyond the geographic boundaries of interest. Sorption, deposition, or partitioning of the pollutant into a different media of interest. Therefore computation under actual, rather than ideal, conditions in the environment must necessarily include scalar and kinetic considerations, as well as thermodynamic. Actual exergies of mixing for any particular pollutant could conceivably be computed for any reference environment provided the environmental fate and mixing kinetics (i.e. chemodynamics) within a particularly dened geographic boundary can be approximated. It may be hypothesized that the results of a general methodology would show that those pollutants that occur most rarely in nature, that mix quickly, and that are the most long-lived may intuitively be suspected of embodying the greatest exergy of mixing and of being the most dangerous to the environment. In these instances, a precautionary or preventative approach may be justied to prevent future environmental surprises [61].

Fig. 3. Comparison of Environmental Pollutant Cost (EPC) with exergy of mixing (adapted from [53]).

would have an innite exergy of mixing in accordance with Eq. (3) wherein the standard mole fraction in the environmental reference sink is taken as zero. However, this treatment contradicts common sense. (How can innite exergy emerge from a nite system?) The conventional thermodynamic assumption is to treat the environment as an innite sink with immutable properties and for many cases, the impact of mixing a small amount of pollutant results in a negligible change in the mole fraction of the reference environment. However, for exceedingly rare chemical species, or for massive anthropogenic release (e.g. carbon dioxide), the reference condition may change over time. In these cases, the earth must be treated as a nite system. In the case of chemicals with no natural sources, the reference condition (for the purposes of computing exergy of mixing) may be taken as some arbitrarily small gure such as that which would be found in the environmental sink of interest after complete dissipation of the pollutant of interest. Exergy of mixing computations are very sensitive to the choice of an ideal reference environment, and some subjectivity may be introduced in deciding what reference mole fractions are to be employed. In some instances, globally and/or annually averaged values would be inappropriate, and reference conditions that vary temporally or geographically are likely to be called for. When mixing is instantaneous, the exergy of mixing per mole of material is analogous to that portion of Gibbs chemical potential which is solely due to mixing (or the free energy of mixing [42,60]) albeit with reference to environmental rather than standard states. However, under environmental conditions, the actual exergy of mixing may be signicantly less than the ideal for several reasons:

10. Conclusions Either LCA or systems optimization approaches may be feasible on the basis of any of the three criteria described: TCA, exergetic efciency, or chemical exergy of mixing. In the case of LCA, it is conceivable that life cycle inventories could be condensed into common units of total nancial cost, total exergetic resources consumed or total waste exergy of mixing, and comparative assessments conducted on these bases. In the case of systems analysis, any of the three metrics may be cast in terms of an objective function, allowing maximization of the objective criteria (or multi-objective criteria) under constraints expressed in terms of the other two. Each measure is applicable to all conceivable industrial processes and may synthesize widely disparate attributes. However, the recommendations of otherwise identical studies conducted under different criteria may vary. Except in instances wherein nancial, thermodynamic and environmental considerations are all aligned, there is no basis within IE to select a strategy or design which involves trade-offs among the three. The rst measure may be most amenable to cost/benet or rate of return studies; the second may be central to studies related to sustainability; the last might be a comprehensive method for managing the disparate impacts of chemical contamination. As a eld of science, IE should uphold no other goal other than a further understanding of human industrial systems and the environmental implications concomitant to them and not be called upon to make value judgments

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or advocate a principled agenda. Environmental managers, on the contrary, may have less philosophical motivations. They may be charged with the responsibility of meeting increasingly prohibitive environmental constraints or corporate goals, of reducing environmental treatment and disposal costs, or of managing environmental risks or liabilities. Just as forest management may be characterized as an application of forest ecology, so might the environmental management of industrial processes be characterized as an application of IE. The distinction till date has been blurred, if it has existed at all. However, through the development of more reliable analytical tools, IE will mature into a science of its own that furthers understanding of the ramications of industrial strategies that at present are judged subjectively.

Acknowledgements This research was supported by the National Science Foundation through the Lucent Technologies Industrial Ecology Research Fellowship Program (BES-9873589) and the Environmental Manufacturing Management Program (DGE-9870646) at Clarkson University. Jeffrey Mathews (Eastman Kodak Co. Inc.) and Randy Brown (Clarkson University) have provided helpful comments regarding various sections of this paper.

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