Journal of Cleaner Production 10 (2002) 225–235

www.cleanerproduction.net

A uniform definition 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 field, 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 efficiency studies, no single measure is sufficiently 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 significantly advance a
scientific 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 consist-
ent definition 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 “para-
digm shift” [2], a “broad umbrella of concepts, rather
than a unified theoretical construct” [3] and an “aggre-
gation of trends (that) is still being defined by its pro-
ponents” [4]. A broad review of the historical origins of
the term shows that a myriad of definitions, 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
* Corresponding author. Tel.: +1-315-268-3856; fax: +1-315-268-
4291.
E-mail addresses: seagertp@clarkson.edu (T.P. Seager), theist@-
clarkson.edu (T.L. Theis).
be established that reflects the evolution of scientific
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 efficiently and
with fewer environmental impacts if they were modeled
after natural ecosystems wherein “the consumption of
energy and materials is optimized, waste generation min-
imized, and the effluents of one process… serve as the
raw materials for another process”.1 This supposition is
an extension of what Ayres [7] called industrial metab-
olism and characterized as “the energy-and-value-yield-
1
The paper mentions two additional terms that become important
to future discussions. ‘Dematerialization’ is defined as “the use of plas-
tics, composites, and high-strength alloys to reduce the mass of pro-
ducts”, and cited as an important trend in the auto industry wherein
cars are becoming lighter, more fuel efficient, but also increasingly
difficult 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.

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
226 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235
ing process essential to economic development” — anal-
ogous 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 first textbooks in the field 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 indus-
trial civilization with the natural environment and the
aggregate of opportunities for individual industries to
transform their relationships with the natural environ-
ment”, thereby subsuming the research that had been
conducted under a metabolism banner and expanding the
meaning of IE to make a separate term superfluous. In
retrospect this seems unnecessary — the two metaphors
create different perspectives that need not be competi-
tive, 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 per-
spective was adopted, while Commoner [14] has ques-
tioned 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
definition of industrial might lead to the logical con-
clusion 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 field
of study and a new perspective from which to model
industrial processes, the separate but overlapping defi-
nitions offered to date are not adequately resolved by
any author, although articulation of a vocabulary has
been identified as a prerequisite step [16]. Therefore, for
the purposes of this paper, IE shall be defined as a field
of study (or branch of science) concerned with the inter-
relationships of human industrial systems and their
environments. Similarly, industrial metabolism shall be
defined as the process by which mass and energy
(exergy) flows are handled or transformed by the econ-
omy. Lastly, an industrial ecosystem shall be understood
to mean a model of a community or system of firms that
2
See Thomas [8] for comments regarding Ayres [7] and Ayres and
Ayres [9].
is based upon a natural analogue.3 Alternative descrip-
tions need not be entirely supplanted by these, as they
may offer explanatory power for a specialized agenda,
but the definitions offered herein are broad enough for
a wide range of applications and consistent with the bio-
logical and etymological roots that inspired invention of
the terms. If it is not too late to define the nomenclature
of such a young and emergent field, these definitions
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 significant differences between the
two (see Table 1), they are both extremely sensitive to
how the boundaries of study are defined. In fact, one of
the principle motivating hypothesis of IE is the intuitive
sense that as the boundaries expand, supraoptimal sol-
utions 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 difficult to define unambiguously — sys-
Table 1
Summary comparison of LCA and system analysis
Characteristic Life cycle assessment Systems analysis
Purpose Descriptive Prescriptive
Boundaries Cradle to cradle/grave Scalable
Data requirements Broad Focused on
decision
Emphasis Materials cycling Any uniform metric
(e.g. dollars)
Applicability Industrial metabolism Industrial ecology
3
These definitions 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 definitions provided therein. We happened to use Webster’s ninth
new collegiate dictionary, Merriam-Webster Inc., Springfield, MA
1988.
4
O’Rourke et al. [3] have presented a critical review of IE litera-
ture, 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).
 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235
tems analysis is more flexible. 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 optimiz-
ation and decision-making. That is, LCA lends itself to
descriptive models, while systems analysis lends itself
to prescriptive models. For this reason, the data require-
ments of LCA may be more extensive than systems
analysis — at least wherein systems analysis may neg-
lect 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 specific materials
flows and processes, whereas systems analysis is more
applicable to IE, wherein the emphasis is on examin-
ing interrelationships.
3. Life cycle assessment
LCA is the principal tool by which IE research is car-
ried 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 advo-
cated, 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 final disposition. The impact assessment is
conducted to relate the inventory data to specific
environmental concerns. Finally, the improvement
assessment (or interpretation phase) identifies 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 environ-
mental benefits. However, current LCA techniques have
been criticized as unreliable scientific tools subject to
quantitative and qualitative errors [21–24]. The limi-
tations identified with current practices include a lack
of adequate inventory data, difficulties in identifying the
boundaries of the system, disparate underlying assump-
tions, 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 difficulties of completing an extensive
227
LCA. The methodology proposed is greatly simplified.
A subjective score (1–4) 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 pub-
lic. However, no matter which methodology is
employed, widely disparate, albeit defensible, con-
clusions can be drawn depending upon what information
is excluded from the study, or which underlying assump-
tions 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 main-
tain little quantitative account. Even when such data do
exist, it is often regarded as proprietary, and therefore
unavailable, unverifiable or unpublishable. Lave et al.
[24] have shown that the boundaries of LCA should be
even greater than suggested by current guidance docu-
ments, especially when the alternatives compared
include significantly different raw materials. However, it
is apparent that no logical beginning or end to a specific
materials cycle may exist, and that establishing the
boundaries of an inventory analysis may rely upon arbi-
trary judgments. This presents a significant obstacle to
producing scientific research that is reproducible by dif-
ferent 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 manage-
ment perspective typical of current practices is rep-
resented by the boxes drawn around manufacturing
activities. The emphasis is on reducing waste and pol-
lution from the source of production. Raw material
requirements and pollutant emissions are benchmarked
to production of ‘finished’ product: for example, photo-
graphic film, 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
228 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235
Fig. 1. Typical (Compliance) vs. life cycle perspective. The typical
compliance perspective (inside boundaries) measures finished product
and residuals at the factory, in terms of material production. The life
cycle perspective (complete figure) measures final product at the end
of the chain, rather than in the middle, in terms of value to the pho-
tographer — excluding unwanted materials like unsatisfactory photo-
graphs.
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 thermodyn-
amic 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 film and paper which is perceived
by the manufacturer to be final product may be wasted.
An improvement assessment might focus on
employing digital technology to make photographic pro-
cesses much more environmentally and economically
efficient. For example, digital cameras typically allow
photographers to delete unsatisfactory exposures by dis-
playing them on a small LCD screen at the back of the
camera. This obviates the need for developing and print-
ing unwanted photographic prints. Other digital techno-
logies operate on the same principle. For example, a film
drive scans photos from a negative directly into com-
puter memory without need for a paper print — allowing
the photographer to preview and select which images or
what information is critical — and may result in signifi-
cant 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 nar-
rowly (e.g. around a single manufacturing facility) or
more broadly (e.g. to include suppliers, partners, cus-
tomers or to encompass wide geographic regions). The
focus of systems analysis is the objective function,
which must be expressed in uniform units of measure-
ment (e.g. dollars). The goal of a systems analyst is to
find a solution which satisfies 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 man-
agement goal. Selection of a unifying objective metric
is an analytical prerequisite. Current environmental man-
agement approaches focus primarily on maximizing pro-
fits (or minimizing manufacturing costs) while main-
taining compliance with emissions regulations or self-
imposed constraints. Revelle et al. [27], Haith [28] and
Ossenbruggen [29] exemplify current analytical
approaches. However, not all business operations are
guided by a profit-maximizing principle. For example,
public utilities may operate under constrained profit mar-
gins and instead attempt to minimize costs while main-
taining a high standard of service and low level of safety
risks. By analogy, a hypothetical manufacturing facility
could conceivably be optimized to generate fixed profits
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 environ-
mental 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 difficult 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 comprehen-
sive, scientific way.
Fig. 2 illustrates a systems model of the silver halide
and digital photographic imaging chains. Three steps are
 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235
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 efficiently serve a variety of pho-
tographer 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 separ-
ate 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 objec-
tive criteria. Because the systems approach is more flex-
ible, it may have advantages as a decision or design tool.
The data requirements can be less onerous and the sys-
tem boundaries can be defined 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 includ-
ing the paper on which the image is printed, systems
analysis can exclude those factors which remain unin-
fluenced by the decision without altering the con-
clusions. In this way, systems analysis allows a more
specific definition 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 film cameras must contain similar elements: camera
body, a lens, etc. In some instances, these are inter-
changeable. To effect a comparison for the purposes of
229
evaluating relative environmental impact of each tech-
nology, a more focused approach is expedient. Conse-
quently, 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 benefit of the life cycle meta-
phor — 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
Both LCA and systems approaches suffer from the
same shortcoming: the lack of a uniform basis for com-
parison 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 analy-
ses are likely to be incomparable, and environmental sys-
tems analysis to date has primarily been a vehicle for
identifying cost-savings opportunities rather than
environmental improvements. Unfortunately, there is
currently no scientific methodology for answering the
most critical question of IE: which of the technological
alternatives is preferable from an environmental perspec-
tive? There are three metrics that might be applied within
the context of LCA or systems analysis to address the
foregoing question: total financial cost, thermodynamic
(material and energy — i.e. exergy) resource consump-
tion, and environmental impact. The remainder of this
paper is primarily concerned with introducing the ther-
modynamic concept of exergy of mixing as a promising
basis for development of a scientific, objective measure
of the latter quantity, but the first two must also be
addressed briefly to provide a basis for comparison.
6. Total cost assessment
Although accounting, finance and economics are
highly developed disciplines applicable within the con-
text of either LCA or systems analysis, it would be fal-
lacious to take for granted that they may be applied to
determine environmental preferences. Gray [32] exemp-
lifies 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 environ-
mental 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 financial costs
230 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235
such as: contingent liabilities and legal expenses, reme-
diation, employee moral, brand image, and treatment or
disposal costs that are charged to overhead instead of to
specific production activities. Total cost assessment has
been advocated as an alternative which is consistent with
the basic underlying principal of IE: that a more inclus-
ive, 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 financially expedient strategy (even
by holistic measures) is not the environmentally prefer-
able one [35], or the interests of future generations are
denigrated [36], or the most profitable strategy is to irre-
versibly 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 environ-
mental performance”. However, Ayres et al. [39] pro-
pose a unified basis for LCA based upon the thermodyn-
amic 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 first and second laws of thermodyn-
amics 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 per-
form work under ideal conditions. Because all industrial
processes and all material and energetic flows may be
modeled in terms of embodied exergy, thermodynamics
could theoretically provide a common scientific frame-
work 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, refined 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. pressure–volume and heat exchange
type work), for the present purposes the most important
aspect of exergy analysis is chemical, which is anal-
ogous to Gibbs free energy
⌬Bchemical⫽⌬G⫽⌬H⫺T ⌬S (1)
where ⌬Bchemical represents change in chemical exergy,
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 pro-
duction.
⌬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 com-
pounds commonly occur in the environment.
The principal advantage of exergy compared to Gibbs
free energy is a system of environmental reference states
first proposed by Ahrendts [43] which identifies the
chemical characteristics of three different reference
environments for computation of standard chemical
exergies: the atmosphere, the ocean, and the earth’s
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 speci-
fied environmental sink. This is of utmost importance,
as it is well recognized that natural systems are not at
thermodynamic equilibrium, but rather must be approxi-
mated 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 chemi-
cal exergy of any compound are described by Szargut et
al. [44]. Assuming standard pressures and temperatures,
a simplified general formula may be employed
冘冉 冊
ni 0
B0p⫽G0⫹ B (2)
i
np i
where G0 is the free energy of formation (kJ/mole) of
the compound from the elements, ni the number of moles
and B0i the standard chemical exergy (kJ/mole) of the ith
reactant required to form np moles of the product com-
pound; ni and np are determined by the stoichiometric
balancing numbers of the appropriate chemical reaction.
The formation of ammonia gas from nitrogen and hydro-
gen provides a simple example. The chemical reaction
is represented by
1
2 N2(g)⫹112H2(g)→NH3(g) (3)
⫺16.48⫹12(0.72)⫹112(236.1)⫽338 kJ/mole. (4)
 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235 231

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 substitut-
ing 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 exerg-
ies has been compiled by Ayres et al. [39], making
exergy the thermodynamic variable of choice for studies
related to the environment. Exergy analysis has sub-
sequently been employed in LCA [45] and to advance a
scientific 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 difficulties of con-
ducting an environmental impact assessment or con-
structing an environmental objective function. Although
it has been argued that the concept of exergetic optimiz-
ation of industrial processes can be justified on environ-
mental [47,48] or moral [49] grounds, current appli-
cations 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 elec-
tric power generation, refrigeration, distillation, etc. Cur-
rently, 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 qualitat-
Table 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 ⫺RT ln(yi0)
(mol/mol)b (kJ/mol)
N2 0 0.72 0.7479 0.720
H2 0 236.1 – –
NH3 ⫺16.48 337.9 – –
CH4 ⫺50.79 831.65 1.7 ppm 32.9
O2 0 3.97 0.201 3.97
⫺394.37
ive environmental effects. Therefore, a waste exergy (or
exergy emissions) approach could provide only a first
approximation of environmental impact (see Dincer [52]
or Gunnewick and Rosen [53] for a summary of the sali-
ent hypotheses).
To remedy this theoretical deficiency, many manufac-
turing 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 techno-
logies, materials alternatives or material and energetic
trade-offs. However, of the wide variety of approaches
currently employed, none are appropriate for develop-
ment 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 compo-
sition. This is referred to as the exergy of mixing, and it
is a measure of the potential chemical change attribu-
table to introduction of any pollutant into the environ-
ment.
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 first of these is manifested in the
chemical bond and released during reaction (e.g. com-
bustion of fossil fuels to form carbon dioxide and water),
and the second in dilution or dissipation of reaction end-
products throughout the environment (e.g. the
atmosphere). Whereas matter and energy are conserved
throughout the process, exergy is not. Assuming iso-
thermal 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-depen-
dent component’ of chemical exergy [44]) is computed
for the ith chemical species of any system as

再冎
CO2 19.87 0.000331 19.87
H2O ⫺228.57 9.49 0.0217 9.49 yi
NO2 51.3 55.6 1 ppb (est.) 51.4 i ⫽niRT0 ln
Bm (5)
SO2 ⫺330.2 313.4 35 ppb (est.) 42.6 y0i
C(graphite) 0 410.26 – –
where Bmi is exergy of mixing in joules, ni the total num-
a
From [42]. ber of moles of the species, yi the acitivity in the thermo-
b
From [44]. dynamic system under consideration, and y0i the refer-
232 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235

ence activity in the appropriate environmental sink. R is Table 3

the universal gas constant, taken to be 8.314 J/mol/K; Properties typical of bituminous coal [44]
T0 is standard temperature, 298.15 K. Because the work Mass m.w. (g/mol) Molal ni
available in chemical reaction (i.e. heat transfer) is gen- fraction fraction (mol/35.3 g)
erally much larger than that of mixing (i.e. mass (kg/kg) (mol/kg)
transfer), researchers have to date nearly uniformly
ignored dissipative considerations ([58]; an exception is C 0.577 12 48.1 1.70
H2 0.041 2 20.5 0.724
Edgerton [59]). H2O(l) 0.10 18 5.56 0.200
For example, consider the chemical reaction rep- O2 0.112 32 3.50 0.124
resenting methane combustion S 0.013 32 0.406 0.015
N2 0.007 28 0.250 0.009
CH4⫹2O2→CO2⫹2H2O (6) Ash 0.15 – – –
⌬G0⫽⫺[(⫺50.79)⫺2(0)]⫹[⫺394.37⫹2( (7)
⫺228.57)]⫽⫺800.72 kJ/mol.
(1.70 C⫹0.724 H2⫹0.200 H2O(l)⫹0.124 O2
The change in Gibbs free energy for the reaction is ⫹0.015 S⫹0.009 N2)coal⫹1.862 O2(g)→1.70 CO2 (8)
given in Eq. (7) and is computed from the thermodyn- ⫹0.924 H2O(g)⫹0.009 NO2(g)⫹0.015 SO2(g)
amic data in Table 2 by subtracting the stoichiometric
equivalent standard free energies of formation of the
reactants from those of the products. The standard The exergy of mixing of the exhaust gases may be com-
chemical exergy is computed with Eq. (2) as puted from Eq. (5). These total 43.65 kJ for coal, com-
831.7 kJ/mol from the formation reaction as in the pared to 38.85 kJ for an exergetic equivalent amount
ammonia example. The difference of 31.0 kJ/mol of methane.
between the standard chemical exergy and the negative Although exergy of mixing of the exhaust gases is
Gibbs free energy is entirely due to the net exergy avail- very small (and uneconomical) compared to total exergy,
able from dissipation of the products (taken as pure car- from an environmental impact standpoint the waste
bon dioxide and pure water vapor in accordance with exergy of mixing is an objective measure of the chemical
the Gibbs standard states) throughout the environment, change engendered in the environment by release of the
minus the exergy required to concentrate pure oxygen at combustion products to the atmosphere. Excluding oxy-
the site of the reaction. From this example it is clear gen (which is extracted from rather than wasted to the
that the standard chemical exergies B° of the reference atmosphere) the sum of the exergies of mixing of the
compounds O2, CO2, and H2O may be determined solely coal exhaust gases is 12% higher than those of methane,
by their exergies of mixing computed from Eq. (5), indicating that coal combustion is likely to have a greater
assuming reference activities y0i shown in Table 2, and atmospheric environmental impact (due to increased
that the results are consistent with those given by Eq. (2). CO2 emissions from carbon) than methane combustion.6
From an energetic standpoint, the net exergy of mixing is Furthermore, it is possible to relate exergy of mixing to
negligible, being in the order of 1/25th the net work other measures of environmental impact. Fig. 3 (adapted
available from combustion. Nevertheless, it embodies from [53]) compares the exergy of mixing of five atmos-
the thermodynamics of the final step wherein waste pro- pheric pollutants to estimates of environmental pol-
ducts are introduced into and dispersed throughout the lution costs.
environment, and may provide a specific link between In general, those chemical species which appear with
exergetic LCA and a holistic measure of the potential the greatest frequency in the environmental sink of inter-
for unintended or adverse environmental consequences. est are those with the lowest exergy of mixing and least
The case of coal, which is a mixture of hydrocarbons, potential for harm. Conversely, organisms and ecosys-
oxygen, sulfur, nitrogen, moisture, ash and trace tems have little evolutionary experience with chemical
elements, provides a basis for comparison. Mass frac- species which occur only rarely in nature and introduc-
tions typical of moist coal are given in Table 3. The tion of these (having greater exergy of mixing) may be
total chemical exergy is estimated as 23,583 kJ/kg [44]. particularly disturbing.
Therefore, approximately 35.3 g of coal is required to Chemical species which do not occur at all in nature
provide the same 831.7 kJ exergy as one mole of pure (e.g. chlorinated hydrocarbons such as CFCs or PCBs)
methane gas. A simplified chemical reaction (ignoring
trace elements and ash) is shown below. The stoichio- 6
Additional environmental considerations have not been included
metric balancing numbers represent the number of moles in this analysis and may make coal even less attractive: e.g. the pres-
of each substance involved in the reaction of 35.3 g coal ence of mercury increases the loading of pollutants to the atmosphere
(see Table 3): and ash disposal may present a problematic land impact.
 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235
Fig. 3. Comparison of Environmental Pollutant Cost (EPC) with
exergy of mixing (adapted from [53]).
would have an infinite 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
infinite exergy emerge from a finite system?) The con-
ventional thermodynamic assumption is to treat the
environment as an infinite sink with immutable proper-
ties 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 refer-
ence condition may change over time. In these cases, the
earth must be treated as a finite system. In the case of
chemicals with no natural sources, the reference con-
dition (for the purposes of computing exergy of mixing)
may be taken as some arbitrarily small figure 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 refer-
ence 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 refer-
ence to environmental rather than standard states. How-
ever, under environmental conditions, the actual exergy
of mixing may be significantly less than the ideal for
several reasons:
233
앫 Degradation of the pollutant over time.
앫 Passing of the material beyond the geographic bound-
aries of interest.
앫 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 thermodyn-
amic. Actual exergies of mixing for any particular pol-
lutant could conceivably be computed for any reference
environment provided the environmental fate and mixing
kinetics (i.e. chemodynamics) within a particularly
defined geographic boundary can be approximated. It
may be hypothesized that the results of a general meth-
odology 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 justified to prevent future environmental ‘surprises’
[61].
10. Conclusions
Either LCA or systems optimization approaches may
be feasible on the basis of any of the three criteria
described: TCA, exergetic efficiency, 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 financial cost, total exergetic resources consumed
or total waste exergy of mixing, and comparative assess-
ments 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 con-
straints expressed in terms of the other two. Each meas-
ure is applicable to all conceivable industrial processes
and may synthesize widely disparate attributes. How-
ever, the recommendations of otherwise identical studies
conducted under different criteria may vary. Except in
instances wherein financial, 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 first measure
may be most amenable to cost/benefit 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 contami-
nation.
As a field 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
234 T.P. Seager, T.L. Theis / Journal of Cleaner Production 10 (2002) 225–235
or advocate a principled agenda. Environmental man-
agers, on the contrary, may have less philosophical
motivations. They may be charged with the responsi-
bility of meeting increasingly prohibitive environmental
constraints or corporate goals, of reducing environmental
treatment and disposal costs, or of managing environ-
mental risks or liabilities. Just as forest management may
be characterized as an application of forest ecology, so
might the environmental management of industrial pro-
cesses be characterized as an application of IE. The dis-
tinction 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 ramifications of indus-
trial 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 Pro-
gram (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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