Environmental Toxicology and Chemistry, Vol. 15, No. 9, pp.

1627–1637, 1996
q 1996 SETAC
Printed in the USA
0730-7268/96 $6.00 1 .00

EVALUATING THE ENVIRONMENTAL FATE OF A VARIETY OF TYPES OF

CHEMICALS USING THE EQC MODEL

DONALD MACKAY,*† ANTONIO DI GUARDO† SALLY PATERSON,† AND CHRISTINA E. COWAN‡

†Institute for Environmental Studies, University of Toronto, Toronto, Ontario M5S 3E8, Canada
‡Procter & Gamble Company, Environmental Safety Department, Ivorydale Technical Center, Cincinnati, Ohio 45217, USA

(Received 6 August 1995; Accepted 13 March 1996)

Abstract—The multimedia equilibrium criterion model, which can be used to evaluate the environmental fate of a variety of chemicals,
is described. The model treats chemicals that fall into three categories. In the first the chemicals may partition into all environmental
media, in the second they are involatile, and in the third they are insoluble in water. The structure of the model, the process equations,
and the required input data for each chemical type are described. By undertaking a sequence of level I, II, and III calculations, increasing
information is obtained about the chemical’s partitioning, its susceptibility to transformation and transport, and the environmental
process and the chemical characteristics that most influence chemical fate. Output data, consisting of tables and charts, give a complete
picture of the chemical’s fate in an evaluative or generic environment. The model is illustrated by applying it to two chemicals, pyrene,
which is a chemical of the first type, and lead, which is of a second type. The role of this model as a tool for assessing the fate of
new and existing chemicals is discussed.

Keywords—Model Multimedia Environmental fate Chemical classes

INTRODUCTION 5. Finally, the evaluative risk assessment can be performed by

In a companion paper [1], we described the need to evaluate
the environmental fate of chemicals, suggesting a five-stage
process. Stage 1 involves the classification of chemicals ac-
cording to environmental partitioning properties and thus ac-
quisition of appropriate property data and selection of the ap-
propriate model. In stage 2 discharge data (quantities and media
of discharge) are obtained. Stage 3 is an evaluative assessment
of fate, and stage 4 a regional far-field assessment. Finally, stage
5 is a local or near-field assessment. The evaluation of effects
or risk then follows. This paper provides a detailed account of
models suitable for use in stage 3.
Conducting evaluative assessment can provide invaluable in-
sights into the characteristics of chemical behavior in the en-
vironment. Because the environment considered is purely eval-
uative or hypothetical, there is no possibility of validation, but
the equations used to describe partitioning, transport, and trans-
formation are identical to those that have been used successfully
in validated models of chemical fate in more defined environ-
ments such as ponds and soil plots. The assessor aims to es-
tablish the general features of chemical behavior, namely, into
which media the chemical will tend to partition, the primary
loss mechanisms, its tendency for intermedia transport, and its
persistence. Further, sensitivity analyses can be performed to
identify which parameters most strongly influence chemical fate.
Resources can then be devoted to obtain more accurate values
of the most influential parameters. Evaluative models may pro-
vide sufficient information to show that a proposed use of a
chemical will be risk-free because expected concentrations will
be orders of magnitude below effect levels. In other cases the
assessment will demonstrate the need for, and can help to focus,
the more detailed assessments of fate and risk in stages 4 and
* To whom correspondence may be addressed.
The current address of D. Mackay is Environmental & Resource
Studies, Trent University, Peterborough, ON K9J 7B8, Canada.
an assessor anywhere in the world and the results shared in-
ternationally. This results in considerable economies in re-
sources, allows more chemicals to be evaluated, facilitates in-
ternational communication, and contributes to a wider under-
standing of chemical fate.
THE EQC MODEL
The equilibrium criterion or EQC model is based on an eval-
uative multimedia model described by Mackay et al. [2]. The
major developments described here are the introduction of
chemical classes with corresponding data requirements and
modification of these models to process these class-specific data.
As in the original version, the EQC model allows the user to
progress through the sequence of level I, II, and III (and possibly
IV) models, which have increasing data requirements, introduce
greater complexity, and reveal progressively more about the
nature of the chemical. There is, however, provision to bypass
the first two levels if desired. Figure 1 is a schematic diagram
of the sequence of model calculations. The advantage of this
approach is that the models can treat a greater diversity of
chemicals than conventional models, which are primarily de-
signed for nonpolar organic substances.
In this paper we first describe the generic environment in
which the chemical fate is evaluated, then the data requirements
for various chemical types and the equations used to calculate
partitioning, transport, and transformations. Finally we illustrate
the model for two selected chemicals and discuss the role and
benefits of the evaluative assessment and the EQC models for
evaluating the fate of new and existing chemicals.
Environment
The evaluative environment is an area of 100,000 km2 as
reported in Mackay [3]. This area is regarded as being typical
of a jurisdictional or ecologically homogeneous region of ap-
proximately the size of the state of Ohio in the United States

1627
1628 Environ. Toxicol. Chem. 15, 1996 D. Mackay et al.

Table 2. Bulk compartment dimensions and volume fractions for

level III calculations

Com- Volume Volume

partment Subcompartment (m3) fraction

Air Bulk 1014 1

Air phase 1014 ù1
Aerosol 2,000 2 3 10211
Water Bulk 2 3 1011 1
Water phase 2 3 1011 ù1
Suspended sediment phase 10 3 106 5 3 1026
Fish phase 2 3 105 1 3 1026
Soil Bulk 18 3 109 1
Air phase 3.6 3 109 0.2
Water phase 5.4 3 109 0.3
Solid phase 9.0 3 109 0.5
Sediment Bulk 5 3 108 1
Water phase 4 3 108 0.8
Solid phase 1 3 108 0.2
Fig. 1. Block diagram of the different simulations possible with the
EQC program. Level IV calculations are not presently included in the
EQC program.
equations for the calculation of the Z values for a type 1 chemical
are shown in Table 4. The Z value for air ZA is first defined as
or the country of Greece. The compartment dimensions and 1/RT; then Zw for water is defined as ZA/KAW where KAW is the
properties for level I and II calculations are shown in Table 1; dimensionless air–water partition coefficient, which can be de-
Table 2 reports the bulk compartment dimensions and relative duced from solubility and vapor pressure or can be input di-
volume fractions used in the level III calculations. rectly. Partition coefficients to other phases such as soil or fish
The reasons for the differences between Tables 1 and 2 are are deduced from the dimensionless phase-to-water partition
as follows. The total volumes of air and water are identical in coefficient KPW as ZWKPW. The aerosol Z value is deduced from
all cases, but in levels I and II only the solid phases in soil and ZA and the aerosol–air partition coefficient. The Koc or Kd can
sediment are treated; that is, the interstitial air and water are be input directly for the calculation of the Z values in soil,
ignored. Aerosols are treated only in level III. As in other mul- sediment, and suspended sediment. Octanol–water partition co-
timedia models it is assumed that equilibrium exists within the efficients can also be used to deduce partitioning to organic
four bulk compartments of air, water, soil, and sediment; for phases (soil, suspended solids, sediment, fish) as discussed by
example, fish and suspended sediments are at the same fugacity Mackay [3].
as the water.
Type 2 chemicals
Chemical classes, partition coefficients, and Z values
These chemicals are involatile; that is, they do not partition
As discussed previously [1] chemicals can be classified into appreciably into air. The Z values for this type are calculated
five types based on their partitioning characteristics as shown using the aquivalence approach [4]. The difficulty is that PSL,
in Table 3. Partitioning is described by Z values (fugacity ca- and KAW may be zero; therefore if ZW is calculated as for a type
pacities), which express the affinity of a chemical for each en- 1 chemical, it becomes infinite. This necessitates starting the
vironmental phase. When Z is zero for a phase, the chemical calculation of Z values in water rather than in air. The Z value
shows zero or negligible tendency to partition into that phase. in water is first defined as 1.0. All other Z values, including
The mathematical problem is to avoid the use of Z values that that for aerosols, are deduced as KiWZW. Definition of a zero
are zero or equivalently the use of partition coefficients that are partition coefficient for KAW, which results in ZA being zero, is
zero or infinite. As is discussed below and has been reviewed acceptable. The user is interrogated for KAW, but not for solu-
by Mackay [3], Z values can be viewed as being half partition bility or vapor pressure. A suggested value of KQW, the (hy-
coefficients; thus a partition coefficient is a ratio of two Z values. pothetical) aerosol–water partition coefficient of 100, causes all
of the chemical in the atmosphere to be associated with aerosol
Type 1 chemicals particles. Changing this value of 100 has no significant effect
These chemicals partition into all environmental media; thus on chemical fate. The equations for the calculations of Z values
all partition coefficients and Z values must be defined. The are listed in Table 4.

Table 1. Compartment dimensions and properties for level I and II calculations

Suspended
Compartment Air Water Soil Sediment sediment Fish

Volume (m3) 1014 2 3 1011 9 3 109 108 106 2 3 105

Depth (m) 1,000 20 0.1 0.01 — —
Area (m2) 100 3 109 10 3 109 90 3 109 10 3 109 — —
Fraction organic carbon (f) — — 0.02 0.04 0.2 —
Density (kg/m3) 1.2 1,000 2,400 2,400 1,500 1,000
Advection residence time (h) 100 1,000 — 50,000 — —
Advective flow (m3/h) 1012 2 3 108 — 2,000 — —
Evaluating chemical fate Environ. Toxicol. Chem. 15, 1996 1629

Type 3 chemicals
Type 3 chemicals are substances such as long-chain alkanes

Models may not be useful

or silicones that may have negligible or zero solubility in water.

Equilibrium criterion

Probably aquivalence
Fugacity is the preferred equilibrium criterion and calculation
follows the same approach as for the type 1 chemicals, first
defining Z in air. All the other Z values are deduced using

Aquivalence
Fugacity partition coefficients with respect to air, that is, KiA; thus Zi is

Fugacity
KiAZA. However, for this type of chemical the water–air partition
coefficient is usually zero, resulting in a Z value for water of
zero. Table 4 lists the equations.
A problem inherent with these chemicals is that certain par-
long-chain hydrocarbons, silicones, tition coefficients may be impossible to determine experimen-
Cations, anions, and involatile organ-
Most organic chemicals, e.g., chloro-

tally. An example is the fish–air partition coefficient KFA. Such

polymers, many elemental metals,

Organo-metals, phenols of low pKa

Large molecular weight substances,
Very hydrophobic compounds, e.g.,

and inorganic substances such as

chemicals may accumulate in fish from dietary exposure, but
benzene, hexachlorobenzene,

the negligible solubility in water will preclude experimental

determination of bioconcentration factors. Field observations or
Examples

monitoring may possibly be the only way to infer certain ef-

fective partition coefficients such as KFA. The science of mod-
eling the fate of such chemicals is still in its infancy; thus the
and polymers
ic chemicals

approach proposed here should be viewed as a preliminary sug-

PCBs, etc.

gestion for quantifying the fate of these sparingly soluble chem-

minerals

icals.
Table 3. Type of chemicals and their classification

Type 4 chemicals
These chemicals are essentially insoluble in both air and water,
the two fluid media with regard to which virtually all partition
ry’s law constant, and octanol–water partition coeffi-

Sorptive properties from a pure phase to various solids

coefficients are measured. In the environment these chemicals

Water and fat or lipid solubility, vapor pressure, Hen-

Partition coefficient to solids from air or from a pure

Partition coefficients to solid surfaces and to organic

will most likely exist either as a pure phase (possibly associated

with another organic solvent such as an oil) or sorbed to solid
surfaces in aerosols, soils, and sediment. Conceiving of how
these chemicals can be transported environmentally except by
Partitioning data required

particle transport is difficult. The role of models in such cases

carbon, solubility in water and fat

is not yet clear. For example, a chemical discharged to soil may

remain there, being subject only to transport by solids runoff.
Partitioning data for all species

Calculation of degradation rates may, however, be useful. One

possible approach is to define for each solid medium a relative
solubility, that is, a concentration that will be in equilibrium
with the pure chemical phase. The ratio of this concentration
to that of the pure chemical (i.e., the chemical density) is then
a partition coefficient Kic where i is a solid phase. Again, this
should be regarded as only a tentative suggestion.
phase
cient

Type 5 chemicals
This category includes chemicals that can exist as several
reversibly interchangeable species. Examples are mercury and
acids that may be present in ionized form at environmental pHs.
Zero or near zero in air, measur-

Zero or near zero in water, mea-

Zero or near zero in air and wa-

Relevant Z values required for

Modeling of speciating or type 5 chemicals presents consid-

surable in all other phases

erable challenges because definition of inter species conversion

all species in all phases
able in all other phases
Measurable in all phases

rates may be necessary. A tractable approach is to define con-

stant species fractions in each medium; however, Z values must
Z values

still be defined for all species in all phases. This problem has
been discussed by Diamond et al. [5]. As with type 4 chemicals,
multimedia, multispecies evaluative models for predicting fate
are less developed. Development of such models in view of the
ter

environmental importance of substances such as mercury, phe-

nols, amines, and carboxylic acids is needed. Type 3, 4, or 5
chemicals are not discussed further in this paper.

Bulk Z values
Chemical
category

The bulk Z values for the level III calculations are calculated
Type 1

Type 2

Type 3

Type 4

Type 5

for all chemical types using the Z values for the pure phases
and the volume fractions of the subcompartments (Table 2):
1630 Environ. Toxicol. Chem. 15, 1996 D. Mackay et al.

Table 4. Equations for the calculation of the pure phase Z values for chemical types 1, 2, and 3

Phase Z Type 1 Type 2 Type 3

Air Z1 1/RT Z1 5 Z2KAW (probably zero) Z1 5 1/RT

Water Z2 Z1/KAW 5 1/H 5 CS/PS Z2 5 1 Z2 5 Z1/KAW (probably zero)
Soil Z3 Z2r3f3KOC/1,000 or Z2r3KD3/1,000 Z3 5 Z2r3KD3/1,000 Z3 5 Z1KSA
Sediment solids Z4 Z2r4f4KOC/1,000 or Z2r4KD4/1,000 Z4 5 Z2r4KD4/1,000 Z4 5 Z1KSedA
Suspended sediment Z5 Z2r5f5KOC/1,000 or Z2r5KD5/1,000 Z5 5 Z2r5KD5/1,000 Z5 5 Z1KSsA
Fish Z6 Z2r6LKOW/1,000 or Z2r6KFW/1,000 Z6 5 Z2KFW Z6 5 Z1KFA
Aerosol Z7 Z1KQA Z7 5 Z2KQW Z7 5 Z1KQA

Notes: R 5 gas constant (8.314 J/mol·K); T 5 absolute temperature (K); KAW 5 air–water partition coefficient; H 5 Henry’s law constant (Pa·m3/
mol); PS 5 vapor pressure of solid or liquid (Pa); CS 5 solubility in water of solid or liquid (mol/m3); PSL 5 vapor pressure of liquid (Pa): for solids
PSL 5 PSS/exp[6.79(1 2 TM/T)], where PSS is the vapor pressure of the solid state, TM is the melting point (K) of the chemical, and T is the environmental
temperature (K); ri 5 density of phase (kg/m3); fi 5 mass fraction organic carbon for phase i (g/g); Koc 5 organic carbon partition coefficient
(L/kg); Kd 5 solids–water partition coefficient (L/kg); Kow 5 octanol–water partition coefficient; L 5 lipid content of fish (g/g); KFW 5 fish–water
bioconcentration factor (L/kg); KQA 5 6 3 106/PSL 5 aerosol particle–air partition coefficient; KQW 5 aerosol particle–water partition coefficient; KSA
5 soil–air partition coefficient; KSedA 5 sediment–air partition coefficient; KSsA 5 suspended solids–air partition coefficient; KFA 5 fish–air partition
coefficient.

Air ZB1 5 Z1 1 2 3 10211Z 7 Level II calculation

Water ZB2 5 Z2 1 5 3 1026Z5 1 1 3 1026Z6
Soil ZB3 5 0.2Z1 1 0.3Z 2 1 0.5Z 3
Sediment ZB4 5 0.8Z 2 1 0.2Z4
Level I calculation
This level describes a situation in which a fixed quantity of
chemical, namely an illustrative 100,000 kg, is introduced in a
closed system, under steady-state and equilibrium conditions.
The level I calculation is performed in a six-compartment en-
vironment, according to either the fugacity approach (type 1
and 3 chemicals) or the aquivalence approach (type 2 chemi-
cals). In general we refer to fugacity and aquivalence as the
‘‘equilibrium criteria,’’ designated Q, which are related to con-
centration C mol/m3 by the equation
C 5 QZ
The chemical distribution is calculated from the equation:
Q 5 M/S Vi Zi
where
Q 5 equilibrium criterion (fugacity, Pa) for types 1 and 3,
and aquivalence (mol/m3) for type 2
M 5 amount of chemical introduced into the system (mol)
Vi 5 volume of the environmental compartment i (m3)
Zi 5 capacity of the compartment i (mol/m3·Pa for fugacity,
dimensionless for aquivalence)
The molar concentration C (mol/m ) can be deduced as ZQ
3
mol/m3 or as WZQ g/m3 or 1,000 WZQ/r mg/g, where W is the
molecular weight (g/mol) and r is the phase density (kg/m3).
The amount in each medium is CV mol, which total to M mol.
This calculation gives a general impression of the likely me-
dia into which the chemical will tend to partition and an in-
dication of relative concentrations in each medium. These re-
sults are not always intuitively obvious because, for example,
a fairly involatile chemical (such as DDT) may partition ap-
preciably into the atmosphere by virtue of its low solubility in
water, which causes KAW to be relatively large compared to other
substances of similar vapor pressures. The tendency to biocon-
centrate is also quantified.
The level II calculation is also performed in a six-compart-
ment environment, as for the level I calculation, and describes
a situation in which a chemical is continuously discharged at a
constant rate E mol/h of, for example 1,000 kg/h, and achieves
a steady-state and equilibrium condition at which input and
output rates are equal. This involves calculating the rates of
degradation and advection, from half-lives or rate constants k
(h21) and advective flow rates G (m3/h), and considering the
emission E (mol/h). The calculation is performed using deg-
radation and advection D values [2,3,6].
DRi 5 Vi Zi ki (3)
DAi 5 Gi Zi (4)
where DRi is the degradation D value for the compartment i and
DAi is the corresponding advection D value. The D values have
dimensions of mol/Pa·h for fugacity calculations and m3/h for
aquivalence. The rate of the process is then DQ mol/h in both
(1) cases. There are no advective losses from soil or sediment. The
equilibrium criterion is then calculated as
Q 5 E/(S DAi 1 S DRi) (5)
(2)
from which amounts and concentrations are calculated.
Additional information deriving from a level II calculation
is the overall persistence or residence time, calculated as
t0 5 M/E (6)
where M is the amount of moles present in the system. The
reaction and advection persistences are
tR 5 M/S DRiQ and tA 5 M/S DAiQ (7)
where tR and tA are reaction and advection persistences (h),
respectively. Clearly
1/t0 5 1/tR 1 1/tA (8)
where 1/t0 is the overall persistence.
This calculation provides a first estimate of overall environ-
mental persistence, which is a critical property of the chemical.
It also shows which loss processes are likely to be most im-
portant. A fast reaction or short half-life may not be significant
if relatively little of the chemical is subject to this reaction by
virtue of its partitioning. The potential for the chemical to be
subject to long-range atmospheric transport is also indicated by
the magnitude of the air advection loss. The global chemical
Evaluating chemical fate Environ. Toxicol. Chem. 15, 1996 1631

Table 5. Intermedia transport parameters (U)

U m/h m/year

1 Air side, air–water MTC, kA or U1 5 43,800

2 Water side, air–water MTC, kW or U2 0.05 438
3 Rain rate, UR or U3 1024 0.876
4 Aerosol wet and dry depositiona 6 3 10210 5.256 3 1026
5 Soil–air phase diffusion MTC, kSA or U5 0.02 175.2
6 Soil–water phase transport MTC, kSW or U6 1025 0.0876
7 Soil–air boundary layer MTC, kS or U7 5 43,800
8 Sediment-water MTC, kT or U8 1024 0.876
9 Sediment deposition, UD or U9a 5.0 3 1027 0.00438
10 Sediment resuspension, URE or U10a 2.0 3 1027 0.00175
11 Soil–water runoff, USW or U11 5 3 1025 0.438
12 Soil–solids runoff, USS or U12 1028 0.0000876

Note: MTC is mass transfer coefficient.

a
Velocities U4, U9, and U10 are the volumetric rate of particle transport, for example, m3 of particles per
hour divided by the horizontal area. They are not the actual particle deposition velocities.

persistence is best indicated by the reaction persistence, whereas to levels I, II, and III, and displays and prints the results in
the local persistence is indicated by the overall persistence. tabular and graphic format.

Level III calculation Illustration

In this case the environment comprises four bulk or major
compartments (air, water, soil, and sediments) with subcom-
partments defined in Table 2. The additional parameters required
by the level III calculation are the intermedia transport param-
eters (U, m/h), used to calculate seven intermedia transport D
values. The intermedia transport parameters and D values, cal-
culated as reported in Mackay et al. [2], are listed in Tables 5
and 6. The four mass balance equations (one for each major
compartment) and the solutions are listed in Table 7.
Computing procedure
The program is written in Visual Basicy for Windowsy and
runs as a standard compiled Windows application. This pro-
gramming language was chosen because it is capable of creating
a full-featured application, with user-friendly interface while
retaining relative ease of coding. The program can access a
database of chemical properties, from which data can be re-
trieved and used. New chemical records can be added. The
program calculates the fate of chemicals (types 1–3) according
The EQC model was run for a type 1 chemical (pyrene) and
a type 2 chemical (lead). The input physical–chemical data are
given in Table 8.
Level I. Figures 2 and 3 are the level I diagrams, which show
that the soil compartment holds more than 96% of the chemical
in both cases. Much smaller amounts can be found in sediment,
particles, water, and fish. About 0.1% of pyrene partitions into
air. No lead partitions into air, because this compartment consists
of pure air with no aerosols and the air–water partition coef-
ficient is zero. The steady-state and equilibrium conditions in
a closed and conservative system, as applies to level I, give a
picture of the general affinity of the chemicals for the various
pure phases present in the environment. Tabulated data are also
available but are not shown.
Level II. Figures 4 and 5 give the level II diagrams, which
show the same distribution characteristics as level I. The ad-
ditional information provided by the level II calculation is the
importance of advection and degradation or reaction phenom-
ena, indicated with different arrows in the figures. The results

Table 6. Intermedia transport D values for chemical types 1, 2, and 3

Environmental media

From To Process Equation

Air Water Total D12 5 DVW 1 DRW 1 DQW

Absorption DVW 5 AW/(1/U1Z1 1 1/U2Z2)
Rain dissolution DRW 5 U3AWZ2
Aerosol deposition DQW 5 U4AwZ7
Water Air Volatilization D21 5 DVW
Air Soil Total D13 5 DVS 1 DRS 1 DQS
Absorption DVS 5 1/[1/DS 1 1/(DW 1 DA)]
Air boundary layer D S 5 U 7A S Z 1
Air phase diffusion in soil DA 5 U5ASZ1
Water phase diffusion in soil DW 5 U6ASZ2
Rain dissolution DRS 5 U3ASZ2
Deposition DQS 5 U4ASZ7
Soil Air Volatilization D31 5 DVS
Water Sediment Diffusion plus deposition D24 5 DWS 1 DD 5 U8AWZ2 1 U9AWZ5
Sediment Water Diffusion plus resuspension D42 5 DWS 1 DR 5 U8AWZ2 1 U10AWZ4
Soil Water Runoff of water and solids D32 5 DSW 1 DSS 5 U11ASZ2 1 U12ASZ3

Notes: for a type 2 chemical (Z1 5 0), DVW, DS, DA, and DVS are zero; for a type 3 chemical (Z2 5 0),
DRW, DRS, and DW are zero.
1632 Environ. Toxicol. Chem. 15, 1996 D. Mackay et al.

Table 7. Level III mass balance equations in units of mol/h and relative solutions for chemical types 1, 2, and 3

Compartment Mass balance equations Comment

Air E1 1 Q2D21 1 Q3D31 5 Q1DT1 Q2D21 and Q3D31 5 0, for type 2

Water E2 1 Q1D12 1 Q3D32 1 Q4D42 5 Q2DT2 E is discharge rate, E4 is usually
zero
Soil E3 1 Q1D13 5 Q3DT3
Sediment E4 1 Q2D24 5 Q4DT4
where DT1 5 DR1 1 DA1 1 D12 1 D13
DT2 5 DR2 1 DA2 1 D21 1 D24 D21 5 0 for type 2
DT3 5 DR3 1 DA3 1 D31 1 D32 DA3 5 0; D31 5 0 for type 2
DT4 5 DR4 1 DA4 1 D42
Solution
Water Q2 5 (E2 1 J1J4/J3 1 E3D32 1 E4D42/DT4)/(DT2 2 J2J4/J3 2 D24D42/DT4)
Air Q1 5 (J1 1 Q2J2)J3
Soil Q3 5 (E3 1 Q1D13)/DT3
Sediment Q4 5 (E4 1 Q2D24)/DT4
where J1 5 E1/DT1 1 E3D31/(DT3DT1)
J2 5 D21/DT1
J3 5 1 2 D31D13/(DT1DT3)
J4 5 D12 1 D32D13/DT3

show that the relative importance of the various removal mech-
anisms for pyrene are: reaction in soil, 57%; advection in air,
19%; advection in water, 10%; reaction in air, 8%; reaction in
water, 4%; with sediment loss processes contributing about 1%.
The overall persistence is 14,400 h or 600 days with a reaction
persistence of 20,750 h and advection persistence of 47,460 h.
For lead the only removal processes are advection in sediment
(i.e., sediment burial; 89%) and in water by particle flow (11%).
There is no advective loss from air because it is a pure phase.
The program calculates a negligible reaction rate from the as-
sumed half-life of 1011 h but this should be interpreted as zero.
In both cases (pyrene and lead) the level II diagram reports only
the four major compartments. The simulation is, however, con-
ducted on a six-compartment scenario.
Level III. Figures 6 and 7 give the more complex level III
diagrams, which show intermedia transport when 1,000 kg/h is
discharged into each of air, water, and soil. In these nonequi-
librium conditions, steady-state conditions for different equi-
librium criteria are deduced for the four main compartments.
The values reported in the diagrams refer to the bulk phases
and therefore include the subcompartments.
The percent distribution for both chemicals in level III is fairly
similar to those of levels I and II. Soil retains most of the chemical
introduced in the system (82.4% for pyrene and 99.4% for lead).
For pyrene, 15.4% is present in the sediment. Note that partitioning
in a level III scenario is strongly affected by which compartments
receive the emissions. We recommend that the level III model be
run for emissions of 1,000 kg/h into air, water, and soil individually,
then in total. The fourth (total) case is the sum of the first three
cases because the equations are linear. Running the model for
individual then total emission shows which emission is primarily
responsible for the chemical present in each compartment. For
example in the case of pyrene, the total 597,900 kg in water (ob-
tained in the emission scenario of 1,000 kg/h in air, water, and
soil) can be obtained adding the amounts obtained by emissions
(1,000 kg/h) in the single media: air emissions (20,300 kg), water

Table 8. Physical–chemical data, half-lives, and emission for pyrene and lead. Data for pyrene are from
Mackay et al. [8]; data for lead are from Ling et al. [9] except for arbitrarily selected aerosol–water and
fish–water partition coefficients. The half-lives for lead (1011 h) represent infinite persistence, that is,
zero reaction

Pyrene Lead

Molecular mass (g/mol) 202.3 207.2

Melting point (8C) 156 —
Water solubility (g/m3) 0.132 —
Vapor pressure (Pa) 0.0006 —
Log KOW 5.18 —
Air–water partition coefficient (dimensionless) — 0
Soil–water partition coefficient (dimensionless) — 500,000
Sediment–water partition coefficient (dimensionless) — 800,000
Suspended solids–water partition coefficient (dimensionless) — 1,600,000
Fish–water partition coefficient (dimensionless) — 100
Aerosol–water partition coefficient (dimensionless) — 100
Half-life in air (h) 170 1011
Half-life in water (h) 1,700 1011
Half-life in soil (h) 17,000 1011
Half-life in sediment (h) 55,000 1011
Emission for level I (kg) 100,000 100,000
Emission for level II (kg/h) 1,000 1,000
Emission into air for level III (kg/h) 1,000 1,000
Emission into water for level III (kg/h) 1,000 1,000
Emission into soil for level III (kg/h) 1,000 1,000
Evaluating chemical fate Environ. Toxicol. Chem. 15, 1996 1633

Fig. 2. Level I results for pyrene.

emissions (573,800 kg), and soil emissions (3,800 kg); thus, the
quantity in water is primarily a result of emissions directly to water.
Alternatively, the amount in water of 597,900 kg can be obtained
by varying the individual emissions, that is, from air-only emissions
of 29,770 kg/h, or water-only emissions of 1,042 kg/h, or soil-
only emissions of 158,750 kg/h. This demonstrates that large emis-
sions to air or soil are necessary to match the amount in water.
Most pyrene found in water is the result of direct emission in water.
Table 9 reports the amounts in the four compartments derived from
single and total emissions.
The additional information provided by the level III simu-
lation is the susceptibility of the chemical to intermedia trans-
port which, combined with user-specified emissions, gives a
more realistic picture of the fate in the generic environment.
The pyrene level III diagram (Fig. 6) shows a net transfer of
chemical from air to soil and water to sediment, whereas the
transfer from soil to water is negligible. Net air–water transfer
is small. Reaction in soil is the main removal mechanism, and
advection and reaction are of similar order of magnitude in the
other compartments. The steady-state buildup of pyrene in the
system is about 3 3 107 kg. The overall persistence is 10,000
h or about 1.1 years. The important transport and transformation
parameters for pyrene are those responsible for the principal
processes, namely the half-lives in soil, air, water, and sediment,
and the intermedia processes of deposition from the atmosphere,
sediment–water exchange, and volatilization.

Fig. 3. Level I results for lead.

1634 Environ. Toxicol. Chem. 15, 1996 D. Mackay et al.

Fig. 4. Level II results for pyrene. Advection and reaction rates are in kg/h.

The level III diagram for lead (Fig. 7) shows the importance
of deposition from the air compartment to soil and water, at a
rate that exceeds the advection rate. These phenomena obviously
apply to the chemical associated with particles in air, because
no lead is present in the pure air phase. The main removal
mechanism in this case is advection (burial) in sediment, fol-
lowed by soil runoff and advection in water. The buildup of the
chemical is about 1.7 3 1010 kg and the overall persistence is
5.6 3 106 h or 634 years, which is essentially infinite in duration.
Of the 3,000 kg/h discharged, 1,896 are buried in sediment, 854
advect from water, and 250 advect from air. There is a net
transfer from air to soil of 675 kg/h, from air to water of 75
kg/h, and from water to sediment of 1,856 kg/h, that is, the
difference between deposition of 3,794 and resuspension of

Fig. 5. Level II results for lead. Advection and reaction rates are in kg/h. The reaction rates should be interpreted as zero.
Evaluating chemical fate Environ. Toxicol. Chem. 15, 1996 1635

Fig. 6. Level III results for pyrene. Advection, reaction, and intermedia rates are in kg/h.

1,898 kg/h. For lead the important transport parameters are those
controlling atmospheric deposition and sediment–water ex-
change.
DISCUSSION
As has been demonstrated for pyrene and lead, the model is
capable of identifying the dominant media of accumulation, the
dominant reactions, the role of advective losses, and the inter-
media transport characteristics. A fairly complete profile of
chemical fate has been obtained, permitting more detailed fur-
ther assessment using models of ‘‘real systems.’’
The EQC model is designed to be an easy-to-use and reliable
tool for conducting an evaluative fate assessment of chemicals,
with the goal of determining the general features of a substance’s
behavior in the environment. This is possible for a variety of
chemical types having different partitioning properties. The

Fig. 7. Level III results for lead. Advection, reaction, and intermedia rates are in kg/h. The reaction rates should be interpreted as zero.
1636 Environ. Toxicol. Chem. 15, 1996
Table 9. Amounts of pyrene in air, water, soil, and sediment depending on
single and multiple emissions
Emission medium and rate
of emissions (kg/h) Air
Air (1,000) 66,060
Water (1,000) 3,075
Soil (1,000) 113
All three (1,000 1 1,000 1 1,000) 69,250
model has the advantage of being capable of treating involatile
and insoluble chemicals. It must be recognized that few quan-
titative structure–property relationships (QSPRs) are available
for predicting partition coefficients for type 2 and type 3 chem-
icals. Thus, measurement of these properties for each chemical
is necessary in order to conduct a fate assessment. For example,
the soil–water partition coefficient for type 2 chemicals cannot
be generalized to other soil systems, being specific to the com-
position of the soil tested. A standardized soil (or a set of stan-
dardized soils) could be selected for the measurement of the
partition coefficient in order to facilitate the comparison. Ad-
ditional difficulties are encountered with type 3 chemicals,
where some of the partition coefficients (sediment–air, sus-
pended sediment–air, and fish–air) are difficult or impossible to
measure in practice, even if they are valid theoretically. Ap-
proaches for evaluating the fate of type 3 and 4 chemicals de-
serve more attention.
Care must be taken when interpreting the concentrations in
these diagrams. In levels I and II the concentrations (g/m3) are
obtained by dividing the total mass of the chemical (g) by the
total volume of the compartment (m3). The concentration in
solid phases (mg/g) is the concentration in g/m3 divided by the
solid phase density of 2.4 g/cm3 and is thus on a dry-weight
basis. The concentration in fish is on a wet-weight basis. In
level III the concentration (g/m3) is obtained similarly and thus
refers to the bulk compartment (i.e., containing all subcom-
partments). The concentration in soil and sediments (mg/g) is
calculated using the bulk-phase density and is thus essentially
on a wet-weight basis. The concentration in soil on a dry-weight
basis will be approximately a factor of 1.25 higher and that on
the sediment will be a factor of approximately 2.67 higher,
assuming that all the chemical dissolved in the associated water
becomes sorbed to the solids during drying prior to analysis.
An important advantage of the EQC model is its ease of use.
It includes the capability of accessing and adding to a database
of chemical properties, the ability to obtain graphic represen-
tations of a chemical’s fate (Figs. 2 to 7), and charts for the
comparison of the results. Such information is an essential com-
ponent of the first screening stage of evaluating the behavior
of a new chemical in the environment, where the emphasis is
on the factors and properties influencing the fate. An evaluative
assessment conducted with this model can demonstrate that a
chemical poses no harm to specified environmental targets. Al-
ternatively, it can show that more detailed studies are needed
to clarify its behavior, and it can help focus these studies.
The EQC model does not give information about the response
times to a change in emission scenario (e.g., the time required
to reach a certain concentration after the emission has ceased).
This can be performed by using an unsteady-state, nonequilib-
rium (level IV) model. Additional work is needed to reach this
goal, as well as the assessment of type 4 and 5 chemicals.
As was discussed in a companion paper [1], an obvious need
D. Mackay et al.
Amount at steady state (kg)
Water Soil Sediment
20,350 887,900 160,300
573,800 41,320 4,519,000
3,768 24,340,000 29,680
597,900 25,257,000 4,709,000
exists for extending this assessment by conducting an analysis
of the sensitivity of the results to variance in the input param-
eters. The present model can be used to generate such an analysis
manually, that is, by varying each desired parameter individ-
ually or in combination with others. Work is underway to build
a ‘‘sensitivity analysis engine’’ into the model to facilitate this
process. An example of sensitivity analysis on the input param-
eters of the ChemCAN model is reported in a companion paper
[7].
CONCLUSIONS
The model presented here facilitates the evaluation of the fate
of chemicals in a generic regional environment, and allows for
comparison and ranking of chemicals. It is stage 3, an evaluative
or generic assessment of fate of chemicals, of the five-stage
evaluation process described by Mackay et al. [1]. The sequence
of increasingly complex calculations, from level I to III, sys-
tematically reveals the general features of chemical behavior in
the generic environment. The model can treat three chemical
types, namely type 1 (chemicals that partition into all phases),
type 2 (involatile chemicals), and type 3 (water-insoluble chem-
icals), thus enlarging the spectrum of chemicals that can be
assessed by multimedia models. It is hoped that the model will
contribute to improved environmental stewardship by revealing
the important properties and processes affecting chemicals in
the environment and by facilitating international communication
about chemical fate.
The EQC program is available from the Trent University
Environmental Modelling Centre by the Internet at http://
www.trentu.ca/envmodel. It requires DOS 3.3 or higher and
Windows 3.1xy, 4MB RAM and about 2MB of hard disk space.
Acknowledgement—We are grateful to NSERC, Health Canada, and the
Procter & Gamble Company for financial support.
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