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Monitoring floc formation and breakage

Article  in  Water Science & Technology · February 2004

DOI: 10.2166/wst.2004.0709 · Source: PubMed

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Monitoring floc formation and breakage

Water Science and Technology Vol 50 No 12 pp 163–170 © 2004 IWA Publishing and the authors
J. Gregory
Department of Civil and Environmental Engineering, University College London, Gower Street, London,
WC1E 6BT, UK (E-mail: j.gregory@ucl.ac.uk)

Abstract Monitoring of flocculation processes is of great practical importance and can give very useful
information on the action of different coagulants under various conditions. It is shown that a continuous
optical monitoring technique provides a convenient means of following the formation, break-up and re-
growth of flocs under standard mixing and stirring conditions. Examples of results using this approach are
given, with alum and PACl coagulants as well as a cationic polyelectrolyte. PACl products give larger flocs
than with alum, but they show about the same relative degree of breakage when the shear rate is increased.
With all of these coagulants, floc breakage is not fully reversible; i.e. flocs only re-grow to a limited extent
when the shear rate is reduced. This is in marked contrast to the action of a cationic polyelectrolyte, where
floc breakage is almost completely reversible. Some possible reasons for these observations are discussed,
but, so far, there is no adequate model available.
Keywords Alum; coagulants; floc; monitoring; PACl; polyelectrolyte

Introduction
Because flocculation is such an important process in water treatment, it is desirable to have
convenient methods for monitoring and control. The well-known Jar Test procedure has
been used for many years, mainly to establish optimum coagulant dosages and pH, but also
to investigate variables such as mixing conditions, effects of various additives, temperature
and several others. The jar test is essentially an off-line procedure, which involves standard
mixing and sedimentation conditions, followed by a measure of the degree of removal of
impurities, for instance residual turbidity or colour.
Other techniques are based on measurement of particle charge, since, in many cases, the
optimum flocculation conditions are close to those giving charge neutralisation. The best
known example is the Streaming Current Detector (Dentel and Kingery, 1989), which is
quite widely used to control coagulant dose on-line.
It is often useful to have information on dynamic aspects of floc growth and breakage
under controlled conditions, and the conventional test methods have little to offer in this
regard. In principle, it would be possible to derive information from measurement of parti-
cle (floc) size distribution as a function of time after adding the coagulant. However, this
would involve the generation of large amounts of data, which would have to be analysed.
Also, conventional particle sizing (mostly optical) techniques are mainly intended for sus-
pensions of discrete solid particles, rather than flocs. The optical properties of aggregates
with indeterminate structure are subject to considerable uncertainty, so that interpretation
of floc size data can be quite difficult.
An alternative approach was developed some time ago by Gregory and Nelson (1986),
leading to a simple flow-through monitor that gives a semi-empirical indication of floc
growth and breakage. This method will be described briefly and some examples will be
given of measurements giving some useful information on the dynamics of growth, break-
age and re-growth of flocs, and the mode of action of different coagulants.

163
 Turbidity fluctuations
The monitoring technique is based on measurement of the intensity of light transmitted
through a flowing suspension. This is monitored by a detector (photodiode), the output of
which typically consists of a large d.c. component and a smaller fluctuating (a.c.) part (see
Figure 1). In a typical set-up, the d.c. value might be of the order of volts and the a.c. com-
ponent of the order of millivolts. The d.c. component is simply a measure of the average
transmitted light intensity, which is dependent on the turbidity of the flowing suspension.
J. Gregory

The fluctuations arise from random variations in the number and size of particles in the
light beam. Because the suspension is flowing, the illuminated sample is continuously
renewed. Without flow there is a fixed sample in the beam and the a.c. component becomes
negligibly small.
The a.c. component is separated from the much larger d.c. value and can be amplified by
any desired factor. The root mean square (rms) value of the amplified a.c. signal is then
derived electronically and this value is available as an output, along with the d.c. value. The
ratio of these two quantities (rms/dc) can be shown to be strongly dependent on the state of
aggregation of the particles (Gregory and Nelson, 1986). The ratio value always increases
as aggregation occurs and decreases when aggregates (flocs) are broken. A major benefit of
dividing the rms by the d.c. value is that the ratio is practically unaffected by contamination
(“fouling”) of optical surfaces, which is a significant problem with flow-through turbidity
monitoring. In a commercial version of this technique (Photometric Dispersion Analyzer,
PDA 2000, Rank Brothers Ltd, UK) the ratio value is derived electronically and is provided
as an output in addition to the separate d.c. and rms values. However, when computer data
acquisition is employed, the division can easily be carried out by a software approach, as in
the work reported here. Also, in the present work, the ratio value is referred to as the
Flocculation Index (FI).
Although it is possible to derive more quantitative information from the method (e.g.
Gregory and Chung, 1995) it is more usual to treat the FI value as an empirical index of floc
size. To a rough approximation, FI is proportional to the square of the average aggregation
number (i.e. the mean number of particles per aggregate), but for practical systems,
especially using hydrolyzing coagulants, it is difficult to relate this to the effective floc size.
Most users of the technique (e.g. Ching et al., 1994; Kan et al., 2002) report ratio (FI)
values, without further analysis. This is the approach adopted in the following work.

Flow

. . V0
.
. .
..
. . A.C.
. . V
A . .
.
.. ..
Detector Signal

..
. ..
. . D.C.
Light Source . . Detector
.
.. .
..
. .. ..
..
. ..
..
Time

L
164 Figure 1 Turbidity fluctuations
 All of the work reported here is based on a set-up broadly similar to that in Figure 2,
which is essentially a modified jar test procedure, with continuous monitoring of the
Flocculation Index. The water under test (usually 800 mL of dilute kaolin suspension) is in
a stirred vessel from which sample is pumped through transparent tubing to a monitor. The
transmitted light is monitored directly through the tubing, so there is no need for special,
flow-through optical cells. Typically, coagulant is added to the suspension, under chosen
rapid mix conditions, and the stirring rate is then reduced to a value of 50 rpm or less, to

J. Gregory
allow flocs to form. In some cases, the stirring rate is then increased to a much higher value
(several hundred rpm) to investigate floc break-up. By returning the stirring rate to the
“slow mixing” speed, re-growth of broken flocs can be studied. Variables such as coagulant
type and dosage, suspension concentration, rapid mix conditions and temperature can be
systematically examined using this approach. At various stages, flocs can be allowed to set-
tle and samples taken for residual turbidity measurements. These always show good corre-
spondence with the dynamic monitoring results and only the latter will be given here. All
experiments were conducted at room temperature (22–25°C).
In the following sections, some examples of the use of this monitoring technique will be
given, chosen from a much larger data set. It should be noted that the experimental results
quoted were obtained on different occasions and that the Flocculation Index is given in
arbitrary units, so that the absolute values have no particular significance. However, the
relative changes in FI shown in a graph are directly related to changes in floc size and valid
comparisons can be made.

Floc growth and breakage

Action of hydrolyzing coagulants
Figure 3 (Duan and Gregory, 2003) shows the results of dynamic flocculation monitoring,
using aluminium sulphate (“alum”) as coagulant. In this case, the suspension is kaolin (50
mg/L) in synthetic water (sodium carbonate solution with pH adjusted by adding acid). The
results shown are for two different alum dosages, both at a final pH of 7.0. The lower dose
(10 µmol l–1 Al) is that required to neutralize the charge of the clay particles, by adsorbed

Stirrer

Flow Cell PDA

Beaker

Pump
Interface

Flocculator

Computer

Figure 2 Flocculation monitoring arrangement 165

 hydrolysis products, giving “Zone 2 coagulation”. The higher dose (80 µmol l–1 Al) is sev-
eral times higher than the solubility of amorphous aluminium hydroxide, so that precipita-
tion and “sweep” flocculation occurs (Zone 4). See Duan and Gregory (2003) for a recent
review on the action of hydrolyzing coagulants.
There are very great differences in the dynamics of floc growth between the two coagu-
lant dosages. At the lower dosage the FI value begins to rise slowly almost immediately
after dosing, indicating quite rapid adsorption of the destabilizing species. With the higher
J. Gregory

dosage, there is an appreciable lag time (about 4 minutes) before the FI begins to rise signif-
icantly. However, the value then increases quite rapidly to a much higher value than the low
dosage case. This shows that “sweep” flocculation gives much larger flocs than charge neu-
tralization in the case of alum at pH 7, which is borne out by visual observation and residual
turbidity measurements. The long lag time in the case of sweep flocculation, is associated
with the time needed to form precipitates of sufficient size, although details of the process
are not yet clear. The lag time can be reduced by increasing coagulant dosage or by raising
the pH to around 8 (the isoelectric point of the hydroxide precipitate) (Duan, 1997).

Pre-hydrolyzed coagulants
Pre-hydrolyzed coagulants such as polyaluminium chloride (PACl) are widely used in
place of traditional coagulants such as alum. They are known to give superior performance,
especially at low temperatures. The mode of action of PACl is still not clear, although most
explanations are in terms of charge neutralization by highly-charged cationic species such
as “Al13” (Al13O4(OH)247+). However, these additives are often used at equivalent Al con-
centrations well above the solubility of the amorphous hydroxide and the role of precipita-
tion and “sweep” flocculation cannot be ignored.
Dynamic testing has shown that commercial PACl products do indeed give larger flocs,
which may be formed more rapidly than those given by alum. However, despite quantita-
tive differences, flocs produced by alum and PACl products show clear qualitative similar-
ities, which indicate similar underlying mechanisms.
Figure 4 shows results for the flocculation of kaolin suspensions (50 mg/L) in London
tap water, using alum and two commercial PACl products (Yukselen and Gregory, 2002).
These samples were kindly provided by Kemira Kemi AB (Helsingborg, Sweden). They
were supplied as concentrated aqueous solutions and had different degrees of neutralisation
r (= OH/Al): XL-1: r = 1.9, 5.1 wt.% Al and XL-9: r = 2.1, 4.6 wt.% Al. These solutions

80 µM Al
3
Flocculation Index

1
10 µM Al

0
0 5 10 15
Time (min)
166 Figure 3 Dynamic flocculation monitoring with kaolin suspensions at two dosages of alum
 2.0
XL-9

Flocculation Index 1.5

XL-1

J. Gregory
1.0

Alum
0.5

0.0
0 200 400 600 800 1000 1200
Time (s)
Figure 4 Dynamic monitoring of kaolin suspensions, after dosing with alum and two PACl samples (all at
3.4 mg/L Al). Floc breakage (10s at 300 rpm) at 660 s

were used directly, without prior dilution. All were used at the same equivalent Al dosage
(3.4 mg/L as Al). This dosage corresponds to about 126 µmol l–1 Al and so is rather higher
than that in Figure 3 and well within the “sweep floc” regime.
The results in Figure 4 were obtained under standard mixing conditions in a semi-auto-
matic jar test device (Flocculator 90, Kemira Kemwater, Helsingborg, Sweden), with con-
tinuous monitoring as shown in Figure 2. After 1 minute of sample flow, coagulant was
added with rapid mixing (300 rpm, corresponding to a mean shear rate, G, of about 340 s–1)
for 10 seconds. The stirring speed was then reduced to 30 rpm (G ≈ 11 s–1) and held at this
value for 10 minutes to allow flocs to form. To show floc breakage and re-growth, the stir-
ring rate was raised to 300 rpm for 10 seconds and then reduced back to 30 rpm.
It is clear from the results in Figure 4 that the three coagulants give different FI values
(and hence different floc sizes) after a short period of slow stirring. The order of floc size is
XL-9 > XL-1 > alum. In all cases floc growth is quite rapid and a plateau FI value is reached
after 2–3 minutes. On increasing the stirring speed to 300 rpm, the FI value shows an imme-
diate and rapid decrease in all cases, indicating rapid floc breakage as a result of increased
shear. On returning the stirring speed to 30 rpm, only limited re-growth of flocs occurs,
since the FI values are not restored to the previous plateau values. Irreversibility of floc
breakage is always found with hydrolyzing coagulants (including PACl) at moderate
dosages, and the effect has been studied in some detail (Yukselen and Gregory, 2004).
The results in Figure 4 show strong qualitative similarities, which are more clearly seen
by re-scaling the FI values for the two PACl products, to give similar plateau values as alum
(see Figure 5). Floc growth and breakage curves are then almost coincident. The two PACl
samples also show very similar floc re-growth behaviour, but in the case of alum, there is
significantly more relative re-growth. However, it must be remembered that the absolute FI
value for alum after floc re-growth is considerably less than those for PACl. These and
other results strongly indicate that there are close similarities between the action of tradi-
tional hydrolyzing coagulants, such as alum and ferric salts, and pre-hydrolyzed forms such
as PACl. It is very likely that hydroxide precipitation plays a significant part in all cases.

Comparison with a polyelectrolyte

It is worth pointing out that the action of the hydrolyzing coagulants discussed so far is
markedly different from the behaviour of polymeric flocculants. As an example, dynamic 167
 0.8

Flocculation Index (Re-scaled)

0.6
J. Gregory

0.4
XL-9 (x 0.40)
XL-1 (x 0.55)
0.2 Alum (x 1)

0.0
0 200 400 600 800 1000 1200
Time (s)
Figure 5 Data from Figure 4, re-scaled by the factors shown

flocculation monitoring results are shown in Figure 6 for a 50 mg/L kaolin suspension in
tap water with alum, XL-9 and polyDADMAC (a high charge, low molecular weight
cationic polyelectrolyte). The latter was a commercial product, Magnafloc 1697, kindly
supplied by Allied Colloids Ltd (now Ciba Specialty Chemicals). The original 40% aque-
ous solution was diluted to give a stock solution of 0.1% or 1 g/L. A dosage of 125 µg/L was
applied, which is well within the optimum range for a 50 mg/L kaolin suspension
(Yukselen and Gregory, 2002).
In this case, mixing, stirring and breakage conditions were different to those used previ-
ously. Coagulant was dosed after monitoring the unflocculated sample for 1 minute and

3
Flocculation Index

PolyDADMAC
2

XL-9
1

Alum
0
0 1000 2000 3000
Time (s)
Figure 6 Dynamic flocculation monitoring after dosing kaolin suspensions with alum, PACl and
168 polyDADMAC (see text)
rapid mixing was achieved by 10 seconds stirring at 400 rpm (G ≈ 520 s–1). Slow stirring at
50 rpm (G ≈ 23 s–1) was then applied for 10 minutes in the case of Al-based coagulants and
30 minutes for polyDADMAC. Floc breakage was induced by 10 seconds of stirring at 400
rpm and the stirrer speed was finally reduced to 50 rpm.
There are very clear differences between the action of the polyelectrolyte and the Al-
based coagulants. The latter show similar behaviour to that shown in Figure 4. With
polyDADMAC the FI does not begin to rise appreciably until a few minutes after dosing,

J. Gregory
but then reaches a much higher value than with the other coagulants (about 4 times higher
than with alum). The slow onset of flocculation is a result of the relatively slow polymer
adsorption under these conditions and the higher plateau FI value indicates significantly
larger (and hence stronger) flocs.
Another striking feature of these results is that floc breakage is almost completely
reversible in the case of polyDADMAC, since the FI rises almost back to the original
plateau value after breakage. This is in marked contrast to the irreversible floc breakage
observed with the other coagulants.

Discussion and conclusions

It is evident that continuous monitoring of flocculation, during floc formation, breakage
and re-growth, gives very useful information on the nature of the processes involved –
much more than can be derived from simple jar test experiments. A simple, flow-through
optical technique is well suited to such monitoring. The results shown here, and other data
reported elsewhere, reveal some important aspects of the action of hydrolyzing coagulants,
which have not received much attention previously.
At very low dosages, metal salts such as alum can destabilize negatively charged parti-
cles by adsorption of cationic species and charge neutralization. It is clear from Figure 3
that the adsorption is rapid, since aggregates begin to form almost immediately after dos-
ing. This is quite different to the case of charge neutralization by a cationic polyelectrolyte,
where adsorption of sufficient polymer takes several minutes, under comparable condi-
tions (Figure 6). The polyelectrolyte used has a rather low molecular weight (about 15,000)
and the adsorption rate might be controlled by diffusion or shear (Gregory, 1988). The
apparently much more rapid adsorption of hydrolyzed Al species implies that these are of
much lower molecular weight and diffuse much more rapidly. This is consistent with the
adsorption of monomeric species, perhaps followed by some form of surface precipitation.
Under conditions where hydroxide precipitation and “sweep flocculation” are domi-
nant, flocs can grow appreciably larger than in the charge neutralization case, but there may
be a significant lag time before flocculation begins (Figure 3). This must have to do with the
time required for precipitate particles of sufficient size to be formed, although details are
not yet clear. The lag time is much less apparent in Figure 4, probably because of a higher
alum dose, but perhaps also due to different chemical conditions (especially pH).
Comparison of alum with pre-hydrolyzed coagulants (PACl) shows that the latter can
give larger flocs for an equivalent Al dose, but it is likely that hydroxide precipitation plays
a part in all cases. There are broad similarities in the dynamics of floc growth and breakage
between these additives (Figures 4 and 5) and the most noteworthy feature is that floc
breakage cannot be completely reversed by reducing the applied shear. There is no ade-
quate model to explain this observation, but it is likely that the nature of the binding within
the amorphous hydroxide precipitate plays a role. Explanations of the better performance
of PACl products simply in terms of more effective charge neutralization do not seem to be
realistic.
The flocculation with a cationic polyelectrolyte differs markedly from the behaviour of
the Al-based coagulants. The long lag time is a result of relatively slow adsorption, as 169
 already mentioned. The fact that much larger flocs are formed under the same shear condi-
tions means that the binding forces between particles must be much stronger than in the
case of “sweep” flocculation. Since the molecular weight is quite low, it is unlikely that
bridging interactions play a significant role. However, because of the high polyelectrolyte
charge density, fairly strong attraction between particles could arise because of “electro-
static patch” effects (Gregory, 1996). Reversible floc breakage would be expected in such a
case. Since it has been shown (Figure 3) that charge neutralization by cationic hydrolysis
J. Gregory

products of alum gives smaller flocs than in the case of “sweep” flocculation, it is unlikely
that the cationic species are large enough to give patchwise adsorption.
Further investigations along these lines will be needed before a satisfactory understand-
ing of the action of water treatment coagulants is achieved.

Acknowledgements
Some of the work reported here was supported by EPSRC Grant No. R40944/01 and by
INTAS Grants 99-0510 and 00-0493.

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