Environ. Sci. Technol.

1986, 20, 187-195

Role of Coagulation in the Kinetics of Sedimentation

Kevin J. Parley! and Frángele . M. Morel*
R. M. Parsons Laboratory, 48-425, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

lations. On this basis a new simplified equation of sedi-

The combined results of analytical, numerical, and
laboratory studies are used in examining the kinetic be-
havior of sedimentation in well-mixed systems. The rate
of mass removal of solids, dC/dt, as a function of mass
concentration C, can be described as the sum of three
power laws, dC/dt = -BdaC2,3 BahCL9 BbC13, each term
- -
mentation kinetics is proposed and tested with laboratory
data, including new data covering a 2 order of magnitude
decrease in mass concentration.
Sedimentation Theory. Since coagulation affects the
distribution of particle settling rates, one must consider

of which corresponds to a particular coagulation mecha-
nism: differential settling, shear, and Brownian motion.
Empirical relationships for the coefficients Bda, Bah, and
Bb as a function of system parameters are provided.
coagulation and settling simultaneously to describe sedi-
mentation kinetics. For a vertically homogeneous water
column of depth h, the dynamic equation for the particle
size distribution has been given by Friedlander (10) as
d n(v) 1 Z· u

)()(
_

Introduction
= -

I ß( , - -

0)
dt 2 Jo
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

Understanding sedimentation kinetics is important for wa(v)

determining the performance of treatment processes and () Jo
ß( , )() do -

-() (1)
assessing the impact of waste disposal in natural waters.
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Sedimentation rates are now typically described by a fixed
distribution of settling velocities, corresponding to the
discrete settling of individual particles. Experimental
results (1-7) however have shown the importance of par-
ticle-particle interactions, most notably coagulation, re-
sulting in the aggregation of smaller particles into larger
ones. According to Stokes law, large particles settle much
faster than smaller ones, and overall sedimentation rates
can thus be dramatically affected by coagulation.
Basic coagulation theory, which is largely attributable
to the work of Smoluchowski (8, 9), is presented elsewhere
where ( ) is the particle size distribution, given as the
number concentration of particles as a function of particle
volume (number mL'1 µ 3), ß( , j) is the collision fre-
quency function, which depends upon the mode of inter-
particle contact (see Table I), and ws(v) is the settling
velocity assumed to be given by Stokes law. Kinetic ex-
pressions for the change in total particle numbers, NT, and
the wet weight of suspended solids, C, are obtained from
integrations of eq 1
dNT
1 r r ß( , )()() du do -

dt 2 Jo Jo
(5-7,10-12). Combining coagulation theory with Stokes
law for gravity settling yields the dynamic equation of wa(u)
n(u) do (2)
sedimentation kinetics. No general analytical solution h
exists for this equation. Investigators have thus relied on
laboratory observations (3-6, 13), simplified analytical dC Wa(v)
=
“Pe v—;—n(v) do (3)
solutions (5, 6,14), and numerical simulations (12,15) to dt h
determine sedimentation behavior. A number of problems
where pe is the effective particle density (floe density) and
are associated with these individual approaches. First,
is dependent on particle density, pp, fluid density, p{, and
extrapolating experimental settling rates to field Conditions
is difficult since dispersion is not represented in laboratory aggregate porosity, e
studies and the appropriate scaling of the laboratory results e)pp + epp
=
Pe (1 -

is unknown. Second, simplified analytical solutions,
namely those developed by Hunt (5, 6) and Morel and
Schiff (14), describe the mass removal of solids by a sec-
ond-order dependency on mass concentration. Although
this second-order rate law appears to be an adequate de-
scription of laboratory data, it has only been tested over
a limited range, encompassing less than an order of mag-
nitude change in suspended mass. Further testing of this
rate law is clearly needed. Finally, numerical simulations
based on the dynamic equation for sedimentation have so
far been performed for case-specific applications-providing
little insight into the general behavior of sedimentation.
Since no systematic comparison of numerical results with
laboratory or field data has been performed, the applica-
bility of the numerical simulations remains questionable.
The goal of this study is to combine results of laboratory,
analytical, and numerical studies for predicting the rate
of solids removal from water. Simplified descriptions of
sedimentation behavior previously hypothesized by Hunt
(5, 6), Morel and Schiff (14), and Farley (16) are used as
a starting point and tested in a series of numerical simu-
+
Present address: Tetra Tech, Inc., 1911 N. Fort Myer Drive,
S-601, Arlington, VA 22209.
(4)
Values for the total particle number, NT, and the wet
weight of suspended solids, C, are related to moments of
the size distribution
Ny =
n(v) do (5)
Jo
C =
Pe vn(v) do (6)
In this description of sedimentation, the following as-
sumptions have been made: (1) particles before and after
each aggregation are spherical; (2) particles approach one
another on rectilinear paths, the path of one particle not
being affected by the presence of another; (3) no force acts
on the particles until they come into physical contact, after
which they adhere. Thus, all possible collisions are suc-
cessful in forming aggregates and the efficiency of particle
collisions is unity. The effects of collision efficiencies that
are less than one (and assumed constant with respect to
particle size) are discussed subsequently; (4) collision
functions for Brownian motion, fluid shear, and differential
settling are additive; (5) the floe density is constant over
the size distribution (see Appendix for limiting case); and
(6) the water column is vertically homogeneous with re-

0013-936X/86/0920-0187$01.50/0 © 1986 American Chemical Society Environ. Sci. Technol., Vol. 20, No. 2, 1986 187
Table I. Functional Relationships for Collision Frequency and Stokes Settling Rate11

Brownian Motion
ß( , j) =
XblU/u,·)1/3 + (1/ //3][^/3 + u//3] Kb =
2 /3µ (cm3 s'1)
Fluid Shear
ß( , j) =
^[O;1/3 + O//3]3 K,h =
0/» (S-1)

Differential Settling
d(i, ;') =
Kd8(lV/3 + u//3)3]^1/3 u//3| =
(6/Tr)1/3(g/12y)(pe pf)/pf (cm"1
-

Kd8 s"1)
-

Stokes Settling
wa(i)[h =
(S/h)Vi2/3 S/h =
(l/6ir2)1/s(g/3i'h)(pe
-

pf)/pf (cm"2 s"1)

°Xb, K8h, Kds, and S/h are dimensional constants; k is the Boltzmann constant; T is the absolute temperature; µ and v are the dynamic and
kinematic viscosities, respectively, of the fluid; G is the shearing rate of the fluid; g is the gravitational acceleration; pe is the effective particle
density (floe density); pf is the fluid density; and h is the depth of the vertically homogeneous water column.

spect to particle concentrations, thus vertical mixing of the
water column is fast relative to sedimentation. This is a
useful approximation for many engineering applications
where the depth scale is on the order of meters. As shown
subsequently, the assumption of a vertically homogeneous
water column also appears reasonable for unstirred labo-
ratory columns.
Simplified Analytical Solutions. Through different
approaches, Hunt (5, 6) and Morel and Schiff (14) have
derived a simplified solution that describes the mass re-
moval of solids by a second-order dependency on mass
concentration
f ~BC‘
where B is the rate coefficient. To derive this equation,
Hunt (5, 6) assumed that one coagulation mechanism was
dominant for any given particle size: Brownian coagulation
for the smallest sizes; shear coagulation for intermediate
sizes; and differential settling for the largest particle sizes.
This implies that collisions between similar size particles
are most important. Following Friedlander (17,18), Hunt
also assumed that the volume flux of particles through the
size distribution was constant at any instant in time. (For
a discrete size distribution, the volume flux is equivalent
to the coagulation rate of particles out of a size interval.)
Morel and Schiff (14) considered the extreme case in
which coagulation is the rate-limiting step in the overall
sedimentation process. In this situation, small particles
are assumed to have effectively zero net settling velocity,
but coagulation takes place and large particles are formed
simple case in which the collision frequency function, ß( ,
j), is constant (16).
Similarity solutions derived by this approach for the
separate cases of coagulation by Brownian motion, shear,
and differential settling show that mass removal rates are
expressed by power laws, the exponent of which is de-
pendent on the mode of coagulation (16). For multiple
coagulation mechanisms, similarity transformations are not
successful (19). However, if only one coagulation mecha-
nism is dominant at a given mass concentration (or if eq
1 can be treated as linear), the mass removal rate of solids
can be expressed approximately as the sum of three power
laws
m
^j=-BdsC3-BshC2-BbC1·4
(9)
According to this equation, differential settling should
control the removal kinetics at high solids concentration,
shear at intermediate concentrations, and Brownian
motion at low concentrations.
Materials and Methods
Numerical Simulations. Numerical simulations in-
volving the solution of the dynamic equation for the
particle size distribution (eq 1) are used to examine sed-
imentation behavior. Here the particle size distribution
is expressed as a finite number of size intervals that are
numerically integrated in time. The discrete form of the
governing equation for sedimentation is given by
d nk
^ a(i, })ß( , j)ninj nk ( , )ß( , k)n¡ - -

continuously. Above some fixed critical volume size the dt ¿ i+j=k

particles are considered to settle infinitely fast (the Stokes (wk/h)nk (10)
velocity being proportional to u2/3). For particle sizes less
than the critical volume size, the shape of the particle size where a (i, j) = 1 for i j and a (i, j) 2 for i = j. The =

distribution is assumed invariant while the total number
of particles is decreasing due to coagulation and settling.
Farley (16) derived another simplified “similarity” so-
lution assuming that the fraction of particles in a given size
range is a function of two normalizing parameters
n(u, t)
b(t)\l/(v/a(t))
=
(8)
where is the “self-preserving” function and a(f) and b(t)
are normalizing parameters related to moments of the size
distribution. For a continuously depleting size distribution,
the parameter b(t) alone represents a uniform reduction
of particle numbers over the entire distribution and a(t)
represents the faster depletion of larger sized particles.
Solutions using the similarity transformation are ob-
tained by substituting the relationship given by eq 8 into
eq 1-6 and solving these equations simultaneously. So-
lutions found in this way are possible “characteristic” so-
lutions, which are believed to be asymptotically ap-
proached in time; they have been shown to be valid for the
subscripts i, j, and k denote particles of a particular volume
size, and m is the maximum number of size classes con-
sidered in each integration step. The value of m is de-
termined internally in the numerical solution by expanding
and contracting the number of size classes to include all
size classes having particle numbers greater than 10~7
particles mLr1.
Since a wide range of particle sizes is considered in the
numerical solution, it is most convenient to employ a
logarithmic division of particle sizes. With standard
particle sizes that are equally spaced on the basis of the
logarithm of their volumes, the coagulation of particles
does not produce a new particle of standard size. By
following the method of Lawler et al. (15) weighted frac-
tions of the new particle are assigned to standard particle
sizes. This allows particle volume to be conserved. Unless
otherwise stated, initial conditions for the size distribution
were defined by considering all particles to be present in
the three smallest volume sizes.

188 Environ. Sci. Technol., Vol. 20, No. 2, 1986


Figure 1. Simulation results for quiescent sedimentation with different
initial mass concentrations, expressed as mass concentration vs. time
(p, = 2.0 g cm"3, p, = 1.0 g cm'3, h = 3.3 cm, G = 0 s"1, T = 20
°C, µ = 0.01 g cm'1 s"1).
Laboratory Experiments. To test the proposed rate
laws for mass removal, experiments were performed over
a wide concentration range, from a few hundred to a few
milligrams per liter. Small sample volumes were used to
prevent drawdown of the water column. As discussed
subsequently, it was also desirable to employ high-density
particles to minimize the effect of shear coagulation caused
by extraneous sources of turbulence.
Metallic copper particles were obtained from Alfa
Products, Inc., and goethite particles were prepared in our
laboratory. The copper particles have a diameter of ap-
proximately 1 pm and a particle density of 8.9 g cm'3; the
particle density of goethite is approximately 4.5 g cm"3. For
each experiment, particles were added to a mixing tank
containing 20 L of artificial seawater. A 23-cm-diameter,
60-cm-high Plexiglass sedimentation column was then
filled from the mixing tank, with the sedimentation column
initially characterized by a vertically uniform concentration
of particles. Samples were collected over time at two
sampling ports using 5-mL syringes with 15-gauge needles.
Solids concentrations were measured by digesting the
sample suspension in acid and determining the metal
concentration by atomic absorption. For copper particles,
nitric acid was used in the digestion step; digestion of the
goethite particles was performed by using hydrochloric acid
and heating the samples at 70 °C. Since the experiments
were conducted at a pH of approximately 8 (dissolved
metal concentration less than a microgram per liter), total
metal measurements represent the solids concentrations.
Results and Discussion
Numerical Simulations. Results of numerical simu-
lations for quiescent sedimentation with various initial
mass concentrations are presented in Figure 1 as mass
concentration vs. time. For the lower initial concentrations
there is a longer delay before removal of solids. As mass
is reduced below its initial value, solids concentrations at
any given time all approach the same value regardless of
the initial concentration. To examine the reasons for this
behavior, the simulation results are presented in Figure
Numerical Results
Figure 2. Simulation results for quiescent sedimentation with different
Initial mass concentrations, expressed as the mass removal rate of
solids, dC/df, vs. mass concentration (same conditions as in Figure
1).
2 as the mass removal rate of solids, dC/df, vs. mass
concentration. During the initial period of sedimentation,
which corresponds to the development of a characteristic
size distribution, smaller particles are aggregated into
larger ones through coagulation, resulting in an increased
rate of solids removal. Mass concentration remains rela-
tively constant during this time. Since the coagulation
rates are related to particle numbers, the time period is
longer for the lower initial mass concentrations. A
“characteristic” rate of solids removal is then achieved
which is a function of the mass concentration and is not
affected by initial conditions. The characteristic rate of
removal for this particular simulation can be described by
a second-order rate law (slope of 2 on Figure 2) over a
concentration range of 1000-30 mg L"1. However, a better
description for the characteristic removal rate over the
entire range of mass concentration appears to be given by
the summation of two power laws corresponding approx-
imately to the differential settling term and the Brownian
motion term in eq 9.
The evolution of the particle size distribution over time
provides a check on the assumptions of the simplified
derivations. Results of the numerical simulation for the
particle size distribution are presented in Figure 3a as
dV/d(log v) vs. where
dV
—--
= 2.3 2() (11)
d(log y)
is employed since it emphasizes where the particle volume,
and hence mass concentration, is located in the distribu-
tion. The results show that through coagulation the initial
Environ. Sel. Technol., Vol. 20, No. 2, 1986 189

Particle Volume (/¿m5)
Figure 3. (a) Characteristic volume distributions from simulation results
with different initial mass concentrations (same results obtained for C0
= 50000 mg L'1; 5000 mg L"1, and 500 mg L"1). (b) Coagulation rate
of particles, E(v), out of each particle size Interval.
distribution of small particles is developed into a charac-
teristic shape with a relative depletion in both small and
large particles. Small particlesare depleted due to efficient
Brownian coagulation. Large particles are removed by
settling faster than they are replenished by coagulation as
mass concentration (related to particle numbers) is re-
duced. This results in a nonuniform reduction in the size
distribution. The derivation of second-order removal ki-
netics by Morel and Schiff (14) in which the shape of the
size distribution is assumed invariant over some fixed
volume size is not consistent with these numerical results.
Numerical results, presented in Figure 3b, also show that
at any instant in time the rate of coagulation of particles
out of a size interval roughly follows the volume distri-
bution. This rate is not constant across the size distri-
bution in violation of Hunt’s (5, 6) second assumption.
The contribution of each size class to the coagulation
rate of particles out of a particular size interval (e.g., v =
0.68 1.47 µ 3 in Figure 4) is represented as the differ-
-
ential volume flux rate, cLE(u)/d(log ü), vs. 0, where
cLE(i>)
—--
=
2.3 ß( , ) ( ) ( )
d(log 0)
For the higher solids concentration (C = 360 mg L-1) the
coagulation of 0.68 1.47 µ 3 size particles is controlled
-
by collisions with particles of much larger size and not with
similar size particles as assumed by Hunt (5, 6). Although
it may be argued that collision efficiencies would be ex-
pected to favor the coagulation of similar size particles,
190 Environ. Sci. Technol., Vol. 20, . 2, 1986
10*' 10° I01 !02 I03 I04
v
(jum3)
Figure 4. Differential flux rate of particles, d£(v)/d(log v), coagulating
out of size interval v = 0.68 1.47 µ 3 due to collision with particle
-
of size v (abscissa).
Valioulis (12) has reported that this possibility may be
expected only for the case of shear-induced coagulation.
With the differential flux rate plotted on a linear scale
and particle volume on a logarithmic scale, the relative
importance of each collision mechanism in controlling
coagulation out of a particular size interval (u = 0.68 1.47 -
µ 3, Figure 4) can also be assessed by comparing the areas
under each curve. For the higher solids concentration (C
=
360 mg L"1) differential settling controls the coagulation
of 0.68 1.47 µ 3 size particles. At low solids concen-
-
tration (C = 2.6 mg L-1) Brownian motion controls. These
results contradict the first assumption employed by Hunt
(5, 6) that one coagulation mechanism is dominant at a
given particle size.
Numerical results showing a nonuniform reduction in
the characteristic size distribution (Figure 3) and coagu-
lation of particles out of a particular size interval being
controlled by different collision mechanisms as mass
concentration is reduced (Figure 4) are all consistent with
the simplified description of sedimentation proposed by
Farley (16) and given in eq 9. To test this equation in
greater detail, simulations have been performed for the
separate cases of coagulation by Brownian motion, shear,
and differential settling. Results presented in Figure 5
confirm that the characteristic rates of solids removal can
be described by power law dependencies on mass concen-
tration and that the exponent is dependent on the mode
(12) of coagulation. For Brownian motion, solids removal is
proportional to C1·3, for shear proportional to C1·9, and for
differential settling proportional to C2·3. These exponents
correspond reasonably well with those of eq 9, the greatest
difference (2.3 vs. 3.0) being observed for the case of co-
agulation by differential settling.
The explanation for differences in the rate laws derived
by similarity (16) and those obtained from numerical
Figure 5. Simulation results for the mass removal of solids for the
10 10
V ponents of the three power laws obtained from the nu-
Figure 6. Simulation results for the particle size distribution as ex-
pressed in terms of similarity parameters for the separate cases of
coagulation by Brownian motion, shear, and differential settling.
simulations is found by examining the dynamics of the
particle size distribution. One may express the numerical
results in terms of two normalizing parameters: the nor-
malizing volume size = v/a(t) and the self-preserving size
distribution 2 ( ) (see eq 8). The resulting graph of the
self-preserving size distribution vs. shown in Figure 6 is
analogous to Figure 3a and indicates the relative contri-
bution of each size class to the total mass. The results
show that some variation in the self-preserving function
occurs as mass concentration is reduced, particularly for
the case of coagulation by differential settling. Clearly a
simple similarity transform is not strictly applicable. It
has been shown to work when the collision frequency
Figure 7. Simulation results for the mass removal rate for a case in
which all coagulation mechanisms (Including shear) are considered (/>„
= 2.0 g cm'3, p, = 1.0 g cm-3, h = 3.3 cm, G = 10.0 s'1, 7 = 20
°C, µ = 0.01 g cm"1 s"1).
function is constant (16). For more complex forms of the
collision frequency function, the transform can only ap-
proximate the dynamics of the size distribution. In ad-
dition, for the hypothetical cases of coagulation by shear
and differential settling, the contribution of smaller par-
ticles to mass concentrations does not necessarily approach
zero. This results in a similarity prediction that continually
creates mass at the very small particle sizes. For the case
of coagulation by differential settling, these very small
particle sizes make a significant contribution to the pre-
dicted mass concentration. The characteristic removal rate
given by eq 9 can thus only be viewed as a first approxi-
mation. We now propose instead a semi-empirical kinetic
equation that has the form of eq 9 and includes the ex-
merical simulation:
=
-BdaC2·3
-
B^C1·9- BbCL3 (13)
The dimensions for the rate coefficients are given as Bda
(mg'1·3 L1·3 s'1), Bah (mg'0·9 L0·9 s"1) and Bb (mg~°·3 L0·3 s"1).
This equation has been employed in fitting the charac-
teristic rate of solids removal presented in Figure 2. For
this case of quiescent sedimentation, the following rate
coefficients were used: Bda =
10"617; Bb =
10"4·35; and Bah
= 0. As shown in Figure 2, solids removal is controlled by
differential settling at high solids concentrations and by
Brownian motion at low concentrations. For the inter-
mediate concentration range, solids removal is determined
by the addition of the two terms in accordance with eq 13.
Numerical simulations have also been performed for
cases in which shear coagulation is important. Results of
Environ. Sci. Technol., Vol. 20, No. 2, 1986 191

Figure 8. Rate coefficient relationships determined from numerical
results for Sb, Ssh, and Bds.
one simulation are presented in Figure 7. By use of values
of £da and £b obtained for quiescent sedimentation and
a value of £ah of 10'4·91, the characteristic removal can
adequately be described by the summation of power laws
given in eq 13. Comparison of the mass removal rate with
the rate obtained for quiescent sedimentation (dotted line
on Figure 7) shows that shear coagulation primarily affects
the removal rate for an intermediate range of mass con-
centration.
Values for the sedimentation rate coefficients (Bb, Bsb,
B^) obtained from all our numerical simulations were used
in developing functional relationships describing the de-
pendency of the rate coefficients (given in eq 13) on system
parameters. Parameters that are involved in the dynamics
of solids removal can be represented by five independent
groupings: the four dimensional constants in Table I (S/h,
Kb, Kah, Kds) plus the floe density, pe. (Note that the
parameter h is included since it is important in defining
the suspension time of each particle size and also in de-
termining the likelihood of coagulation prior to removal.)
For solids removal controlled by Brownian motion, the
coefficient Bb is expected to depend on three parameter
groupings (S/h, pe, Kb). A relationship for Bb (mg'9·3 L0,3
s'1) is then obtained directly by dimensional analysis
Bb cx
(S/h)oeKbMpi°·3 (14)
As shown by the solid line in Figure 8a, this relationship
agrees well with the rate coefficients obtained from nu-
merical simulations. Kab and Kda have not been included
in this relationship since coagulation by shear and dif-
ferential settling would only be important when larger
192 Environ. Sci. Technol., Vol. 20, No. 2, 1986
Table II. Final Results for the Proposed Power Law
Removal Relationship"
dC/di =
-£daC2·3 fiahClsl BbC'·3
- -
=
Sda 3.12(S//i)-0'32pe"1’3ab0'I7Ab<l'I7ada1,15AdaLi5
fi.h =
ío.ocs/h^V'V^b0·1^·75^0·76
fi„ =
l^íS/h)0·6^-0'8^0·4/^0·-1
“Kda, Ktb, and Kb are dimensional parameters for the collision
frequency functions; ab, ash, and ada are the collision efficiencies;
(S/h) is the dimensional parameter for Stokes settling in a verti-
cally homogeneous water column; and pe is the floe density (see
Table I for details).
particles present in the size distribution-a condition
are
that does not occur at low concentrations where the
Brownian motion term controls the rate of mass removal.
The coefficient for removal by shear coagulation £ah is
expected to depend on four parameter groupings (S/h, pe,
Kb, Kah). Kb is included since its value is important in
determining the coagulation of small particles present in
the size distribution. With dimensions as a constraint, the
relationship for Bah (mg'0·9 L0·9 s'1) has one degree of
freedom
Bsh -
(S/h)0-e^Kb°^Ksbape^ (15)
The final relationship for Bsh obtained by regression of
numerical data is shown in Figure 8b.
A similar procedure is taken in determining a relation-
ship for Bds (mg'1,3 L1·3 s'1). For the case of quiescent
sedimentation, £da is expected to depend on four param-
eter groups (S/h, pe, Kb, Kda) as follows:
Bds (S/h)^-^Kb0^>Kdaape-L3
«
(16)
With one degree of freedom, a final relationship for Bda
is obtained by regression (Figure 8c). For cases in which
shear coagulation was also considered, any possible effects
of Kab on the rate coefficient Bda could not be detected in
the simulation results. The relationship for Bda given in
Figure 8c is therefore assumed to hold.
As shown in Figure 8, similar relationships can be ob-
tained for cases where collision efficiencies for Brownian
motion, fluid shear, and differential settling (ab, aab, ads)
are less than unity. General expressions for the sedi-
mentation rate coefficients, including the effects of collision
efficiencies, are presented in Table II.
In fitting the numerical results for mass removal kinetics
(with collision efficiencies of 1), we included an initial lag
time prior to the establishment of characteristic removal
(Figure 1). This lag time, which corresponds to the time
required by the coagulation mechanisms to transform the
initial size distribution into its characteristic shape, was
found to be dependent on the initial mass concentration
(C0
= 50000 mg L'1, f0 = 15 s; C0 = 5000 mg L™1, tb = 180
s; C0 =
500 mg L'1, í0 = 2300 s). Since the initial size
distributions included only small particles (ca. 10"6 pm3),
the values presented are indicative of maximum lag times.
A comparison of the characteristic removal, assuming no
initial lag time, and simulation results for various initial
size distributions are presented in Figure 9. For several
initial distributions, the assumption that characteristic
removal is established almost instantaneously is a good
approximation.
Laboratory Experiments. Since an idealized de-
scription of sedimentation behavior is considered in the
numerical simulations, laboratory data were analyzed to
test the applicability of the proposed power law removal
equation and rate coefficient relationships given in Table
II. (Note that all laboratory results for mass concentrations
and sedimentation rate coefficients are based on dry weight

Figure 9. Comparison of the characteristic power law removal
equation (assuming no initial time lag) with simulation results for various
Initial size distributions (p„ = 2.0 g cm-3, p, = 1.0 g cm-3, h = 33 cm,
G = 0 s'1, T = 20 °C, µ = 0.01 g cirr1 s"1).
Time (seconds)
Figure 10. Laboratory results for the quiescent sedimentation of
metallic copper particles in seawater (pp = 8.9 g cm"3, p, = 1.025
g cm"3, hmax = 44 cm, T= 20 °C).
measurements.) Results for the quiescent sedimentation
of metallic copper particles (pp = 8.9 g cm"3) are presented
in Figure 10. Although there exists a vertical gradient in
the solids concentration during part of the experiment, the
water column is considered vertically homogeneous for
data analysis, The assumption that characteristic removal
is established almost instantaneously is also employed. A
good agreement of the experimental data with the pro-
posed power law equation is obtained by using values of
10"6·2 and 10"s·8 for the sedimentation rate coefficients Bds
and Bb, respectively. As shown in Figure 10, the differ-
ential settling term controls the removal kinetics for the
Time (seconds)
Figure 11. Laboratory results for quiescent sedimentation of goethite
particles in seawater (pp m 4.5 g cm"3, p, = 1.025 g cm"3, hmax =
44 cm, T = 20 °C).
higher concentration range. At low solids concentration
(less than 10 mg L"1), solids removal begins to be influ-
enced by the Brownian motion term.
In conducting “quiescent” sedimentation experiments,
it is nearly impossible to eliminate all extraneous sources
of turbulence (due to convection, sampling, etc.). Although
some low level of turbulence may exist in the sedimenta-
tion column, from analysis of numerical results we have
concluded that for high-density particles such as copper
a relatively high shearing rate of 0.2 s"1 would be necessary
for shear coagulation to have any effect on the removal
rate. Low turbulence levels however may inhibit the
settling of very small particles. This would result in a
decreasing rate of solids removal at very low concentrations
and is offered as a possible explanation for the last few data
points shown in Figure 10.
Results of a similar experiment for goethite particles (p„
ai 4.5
g cm"3) are presented in Figure 11. The power law
removal equation was fitted to the data by considering only
the differential settling term to be important (Bds = 10"5·86).
As shown, the removal equation provides a good descrip-
tion of the data after approximately 2 h of sedimentation.
Prior to this time, solids removal is probably affected by
initial conditions. For instance, if the initial size distri-
bution contains large particles we would expect solids re-
moval to be initially fast due to settling and coagulation
of the large particles. It should be noted that these ex-
perimental data, as well as the copper data (Figure 10),
cannot be described adequately by a second-order rate law.
To examine the effect of shear coagulation on mass
removal kinetics, we have analyzed the laboratory data of
Hunt and Pandya (13). Comparison of their data with the
power law removal equation is presented in Figure 12. In
fitting the data, the Brownian motion term was considered
not to be important in determining solids removal over the
observed range of concentration. For all shearing rates,
the removal equation provides a good description of the
data.
Comparisons of sedimentation rate coefficients obtained
from analysis of laboratory data (based on dry weight) with
the rate coefficient relationships determined from nu-
merical results (based on wet weight) are performed for
Bsb and B^ with the conversion factor relating dry weight
to wet weight given as
e Pt
/ 1 + (17)
"(1
-
e) pp
Environ. Sci. Technol., Vol. 20, No. 2, 1986 193
 Time (seconds)
Figure 12. Analysis of laboratory results for the sedimentation of
sludge for various fluid shearing rates. Data are from Hunt and Pandya
U3).

Laboratory rate coefficients are then expressed as equiv-

alent wet weight values
Bsh(wet weight) =
/"°-9Bsh(dry weight) (18)

Bds(wet weight) =
/~L3Bds(dry weight) (19)
For the comparisons presented in Figure 13, a value of the
vertically homogeneous water column depth was taken over
a range corresponding to the sample depth and the total
water column height. The floe porosity was estimated to
be 0.8 (see Appendix). Since the particle density for the
sludge experiments was not reported, a value of 1.5 g cm"3 Figure 13. Comparison of laboratory rate coefficients (in equivalent
was assumed based on the range 1.37-1.69 g cm"3 previ- wet weight values) with the rate coefficient relationships determined
from numerical results for 8sh and 8ds.
ously reported by Faisst (4). As shown in Figure 13, lab-
oratory coefficients for the copper, goethite, and sludge
data previously presented and for fly ash data (7) corre-
spond reasonably well with our rate coefficient relation-
ships for collision efficiencies ranging from 0.2 to 1.0. A
similar range of collision efficiencies has been reported by
Gibbs (20) for coagulation in seawater solutions.
With the exception of the copper data (Figure 10), it was
not possible to determine a laboratory value for the rate
coefficient Bb. The value of Bb obtained from the copper
experiment is approximately an order of magnitude lower
than what would be expected based on numerical results.
Since metallic particles typically exhibit a relatively high
IO"' I0°
surface charge, it is possible that even in seawater, dou-
Aggregate size ( am )
ble-layer effects could be important in reducing the éffi-
ciency of particle collision. Although further laboratory Figure 14. Laboratory results (from transmission-electron micro-
study is needed, we have concluded from simulation results graphs) for two-dimensional projections of gold colloid aggregates.
Colloids are uniformly sized, spherical particles approximately 14.5 nm
that, for field applications where mixing typically occurs in diameter. Data are from Weltz and Oliveria (21).
over depths much larger than those in a laboratory column,
the Brownian motion term in the power law removal coefficients (Bb, Bah, Bds) have been determined as func-
equation would not be significant for mass concentrations tions of system parameters. Laboratory rate coefficients
greater than 1 mg L"1. for seawater experiments compare reasonably well with our
rate coefficient relationships for collision efficiencies
Conclusions ranging from 0.2 to 1.0. Additional work on floe porosity
The results of the analytical, numerical, and laboratory and collision efficiencies however is needed.
studies presented in this paper appear to be consistent and In applying the proposed power law removal equation
their combination provides insight into the kinetic behavior to field conditions, only the differential settling term and
of sedimentation. A semiempirical approximate solution the shear term are expected to be important. Removal
to the dynamic equation for sedimentation describes the rates could therefore be approximated reasonably well by
mass removal of solids as a simple summation of power a second-order expression. However, it should be em-
laws (Table II). Relationships for sedimentation rate phasized that (whether by direct calculations from system

194 Environ. Sci. Technol., Vol. 20, No. 2, 1986

 Environ. Sci. Technol. 1986, 20, 195-200
parameters or by extrapolation from laboratory observa-
tions) the proposed power law relationship provides a
better estimation of removal rates. Finally, in applying
these results, particularly for the case of ocean disposal,
questions concerning initial sedimentation behavior,
mixing depths, and vertical mass concentration gradients
should be addressed.
Acknowledgments
We extend thanks to K. Stolzenbach, R. Mercier,
our
J. Hunt, J. Connolly, D. Dzombak, and B. Hanrahan for
their various contributions.
Appendix
In our description of sedimentation, the effective particle
density (floe density) is considered constant over the size
distribution. It is realized that this assumption is not
appropriate for the initial aggregation of primary particles.
However, as larger aggregates are formed, the porosity of
the floes is expected to reach a limiting values (resulting
in a constant floe density). Such behavior is demonstrated
in Figure 14 where a slope of 2 is indicative of constant
porosity. From the experimental data, a value in the range
0.7-0.8 is obtained for the aggregate porosity.
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Airborne Dioxins and Dibenzofurans: Sources and Fates
Jean M. Czuczwa and Ronald A. Hites*
School of Public and Environmental Affairs and Department of Chemistry, Indiana University, Bloomington, Indiana 47405
Polychlorinated dibenzo-p-dioxins (PCDD) and di-
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furans.
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Received for review July 9,1984. Revised manuscript received
May 23, 1985. Accepted September 23, 1985. This work was
supported in part by NOAA Grant NA79AA-D-00077 and EPA
Grant CR-811181-01-01 and a combined grant from American
Electric Power Service Corp., Duke Power Co., Northeast Utilities
Service Co., and PS&G Research Corp.
Introduction
Polychlorinated dibenzo-p-dioxins (PCDD) have become
an issue of national importance. This has probably re-
sulted from two facts: First, 2,3,7,8-tetrachlorodibenzo-
p-dioxin (2378-TCDD) kills guinea pigs at a dose of 0.6
Mg/kg, thus making it the most toxic anthropogenic com-
pound yet known (1). Second, Agent Orange, which was
used as a defoliant in the Vietnam War, was contaminated
with an average of 2 ppm of 2378-TCDD (2). Other in-
cidents such as the explosion of a trichlorophenol reactor
near Seveso, Italy (3), and the contamination of Times
Beach, MO (4), have reinforced the public’s perception that
dioxins are threats to its health.
More recently, it has been learned that the incineration
of municipal and chemical wastes produces dioxins, some
of which are released into the atmosphere. This infor-
Environ. Sci. Technol., Vol. 20, No. 2, 1986 195