Chemical Engineering Journal 231 (2013) 59–67

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Chemical Engineering Journal

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Coagulation–flocculation treatment of municipal wastewater based

on anionized nanocelluloses
Terhi Suopajärvi a,⇑, Henrikki Liimatainen a, Osmo Hormi b, Jouko Niinimäki a
a
Fiber and Particle Engineering Laboratory, University of Oulu, P.O. Box 4300, FI-90014 Oulu, Finland
b
Department of Chemistry, University of Oulu, P.O. Box 3000, FI-90014 Oulu, Finland

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 We produced nanofibrillar
dicarboxylic acid cellulose samples
with variable charge.
 Anionic nanofibrils were tested in the
flocculation of municipal wastewater.
 Combined coagulation–flocculation
treatment resulted good
performance.
 Results with anionic nanofibrils were
comparable with commercial
reference polymer.
 High charge and nanofibril content
gave the best flocculation
performance.

a r t i c l e i n f o a b s t r a c t

Article history: The synthetic polymers normally used in the coagulation–flocculation treatment of waste water are in
Received 19 April 2013 most cases derived from oil-based, non-renewable raw materials. Consequently, there has been a grow-
Received in revised form 2 July 2013 ing interest in replacing them with more sustainable natural bio-based alternatives. However, derivatives
Accepted 4 July 2013
of cellulose, which is the most abundant biopolymer on earth, are still scarce. In this work dicarboxylic
Available online 15 July 2013
acid nanocellulose (DCC) flocculants were produced by nanofibrillation of periodate and chlorite-oxi-
dized celluloses with a homogenizer. The flocculation performance levels of five such anionic nanocellu-
Keywords:
loses with variable charge densities were examined in the coagulation–flocculation treatment of
Anionic cellulose
Bioflocculant
municipal waste water and the results compared with the performance of a commercial coagulant and
Nanocellulose a synthetic polymeric flocculant. In addition, the aldehyde and carboxyl content, charge density (CD), size
Wastewater treatment and stability of each DCC were determined in an aqueous solution. The results showed that all the DCCs
Turbidity synthesized were able to flocculate waste water very efficiently, and the dosages required were similar to
that of the commercial reference flocculant. The combined coagulation–flocculation treatment of muni-
cipal wastewater resulted in a lower residual turbidity and COD in a settled suspension, with consider-
ably reduced total chemical consumption relative to coagulation with ferric sulphite alone. A high charge
density and high nanofibril content of the DCC flocculant gave the best flocculation performance. The
DCCs showed high stability in aqueous suspensions over a long period of time and good performance
within the chosen pH range.
Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction

Coagulation–flocculation treatment is commonly used to

reduce the turbidity of municipal and industrial waste water, the
⇑ Corresponding author. Tel.: +358 294 482415; fax: +358 855 32405. coagulants in question typically being divalent or trivalent metallic
E-mail address: Terhi.suopajarvi@oulu.fi (T. Suopajärvi).

1385-8947/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2013.07.010
60 T. Suopajärvi et al. / Chemical Engineering Journal 231 (2013) 59–67
salts or polymers that have low solubility in the pH range used [1].
Metal salts hydrolyze rapidly in waste water to form cationic spe-
cies, which are adsorbed by negatively charged dirt particles,
resulting in simultaneous surface charge reduction [2]. Polymers
have been used in the coagulation–flocculation process for decades
to reduce coagulant dosages, the volume of sludge and the ionic
load of the waste water (especially the level of aluminium), and
to save overall costs [3].
The polymers used in coagulation–flocculation treatment are
commonly synthetic poly-acrylamides, poly-acrylic acids and
poly-styrene sulphonic acids and their derivatives, which are not
readily biodegradable [4,5]. Moreover, they may also contain unpo-
lymerized monomers and additives that are neurotoxic and carcin-
ogenic [6,7]. Also, synthetic polymers are produced from oil-based
raw materials, which make them non-renewable chemicals. Conse-
quently, there has been a growing interest in replacing oil-based
flocculants with more sustainable natural bio-based alternatives.
Many natural-based flocculants are environmentally friendly
and biodegradable, with good flocculating ability [8,9]. These in-
clude biopolymeric materials such as starch, guar gum, chitin, pec-
tin and algin [4], and some derivatives of natural carbohydrates
such as dextran [10] and pullulan [11] have also been investigated
for these properties. Derivatives of cellulose, which is the most
abundant biopolymer on earth, are nevertheless still scarce. One
potential and environmentally sustainable method of producing
cellulose flocculants is to introduce reactive aldehyde functional-
ities into cellulose by aqueous periodate oxidation, as has been re-
ported earlier [12,13]. The aldehyde groups of 2,3-dialdehyde
cellulose (DAC) can easily be converted further and in a selective
manner to various functional groups such as carboxylic acids
[14], sulphonates [15,16] or imines [17]. Recently Liimatainen
et al. [18] have investigated the use of anionic (ADAC) and cationic
cellulose (CDAC) derivatives [19] in the flocculation of kaolin sus-
pensions, with promising results, showing that anionic cellulose
nanoparticles resulted in better flocculation performance than
the corresponding fully water-soluble derivatives [18]. Also Hok-
kanen et al. [20] used modified nanofibrillated celluloses to remove
heavy metals from aqueous solutions with promising results.
In the present research aldehyde groups of DAC pulp fibres were
converted to carboxylic acids and these anionic cellulose deriva-
tives (DCC) were nanofibrillated with a homogenizer. The floccula-
tion performance of five anionic dicarboxylic acid (DCC)
nanocelluloses produced in this way with variable charge densities
was examined in the context of the coagulation–flocculation treat-
ment of municipal waste water. The effects of DCC dosage and pH
on flocculation were studied by measuring residual turbidity and
COD of the settled suspension and compared the results with the
performance of a commercial coagulant (PIX 105 A) and a commer-
cial combination of a coagulant and a synthetic polymeric floccu-
lant (Fennopol K 1396). In addition, the aldehyde and carboxyl
content, charge density (CD), size and stability of each DCC were
determined in an aqueous solution.
2. Materials and methods
2.1. Raw material and chemicals
Bleached birch (Betula verrucosa and B. pendula) chemical wood
pulp obtained in dry sheets was used as a cellulose raw material
for the synthesis of anionic cellulose derivatives after disintegra-
tion in deionized water. The polysaccharide content of the wood
pulp was determined using high performance anion exchange
chromatography (HPAEC-PAD) [21], the lignin content by the
TAPPI-T 222 om-02 procedure and the extractive content by the
SCAN-CM 49:03 method. The chemical composition of the cellu-
lose material is shown in Table 1.
The average (length–weighted) length and width of the pulp
fibres, as determined with a Metso FiberLab image analyzer, were
0.90 mm and 19.0 lm, respectively. The fines content, as indicated
by an L&W STFI Fibermaster analyzer, was 3.4%. The pulp was
washed and converted in sodium form, as Liimatainen et al. [22]
previously reported, and the f-potential measured in deionized
water (conductivity <5 lS/cm) with a Mütek SZP-06 device was
125 mV. The degree of polymerization (DP) was 3817, as deter-
mined by a similar procedure to that Liimatainen et al. [19] previ-
ously described.
All of the chemicals used in the synthesis and characterization
of DCC were of p.a. grade as obtained from Sigma–Aldrich and were
used without further purification. NaH2PO4 (Sigma), NaCl (Merck),
CH3COOH (Merck), NaCH3COO (Oy FF Chemicals), Na2HPO4 (Fluka),
NaHCO3 (Merck) and Na2CO3 (J.T. Baker), all of which were of p.a.
grade, were used as received to prepare the buffers. Deionized
water (Millipore) was used throughout the work.
PIX-105 A ferric sulphate (Fe2(SO4)3) and Fennopol K1369 (cat-
ionic polyacrylamide) were obtained from Kemira, Finland, and
were used in the experiments as an inorganic coagulant agent
and a reference flocculant. These chemicals are commonly used
in coagulation–flocculation wastewater treatment plants. The mu-
nicipal wastewater samples were obtained on three separate days
from a Finnish activated sludge plant after the screen phase. The
characteristics of wastewater samples are shown in Table 2.
2.2. Synthesis of the nanofibrillar dicarboxyl acid cellulose (DCC)
flocculant
Anionic dicarboxyl acid cellulose (DCC) derivatives with vari-
able charge densities (DCC I–V) were synthesized by the periodate
and chlorite oxidation of cellulose in the manner Liimatainen et al.
[23] reported previously. In brief, dicarboxyl groups were intro-
duced into the cellulose pulp by first oxidizing the vicinal hydroxyl
groups at positions 2 and 3 in the cellulose using sodium metape-
riodate to produce aldehyde groups and subsequently oxidizing
the aldehyde groups to carboxyls using sodium chlorite (Fig. 1).
FTIR spectra of the cellulose samples treated with periodate and
chlorite were recorded using a Bruker FT-IR spectrometer (USA).
The samples were prepared by pressing 2 mg of dry sample into
a pellet with 200 mg of KBr.
The aldehyde content of the periodate oxidized cellulose was
determined using an oxime reaction, as Sirviö et al. [13] previously
reported, while the carboxyl content after the chlorite oxidation
was analyzed by conductometric titration using a procedure de-
scribed by Rattaz et al. [24] and Katz et al. [25]. The mass yields
of the reactions were measured by weighing the products on an
analytical balance. The periodate and chlorite-oxidized celluloses
were suspended in deionized water at a consistency of 0.5%, and
the pH of the suspensions was adjusted to 7.5 using NaOH. The
anionic cellulose fibres were converted to nanofibrils using a
two-chamber high-pressure homogenizer (Invensys APV-2000,
Denmark) with a pressure of 250–950 bar. The suspensions were
passed through the homogenizer one (DCC V), three (DCC II-IV),
or four times (DCC I) until clear, gel-like samples were obtained.
The synthesis route and details of the reaction conditions are pre-
sented in Liimatainen et al. [23].
2.3. Characterization of the nanofibrillar anionic cellulosic flocculants
2.3.1. Size of the flocculants
A fractional size analysis of the nanocellulose flocculants was
conducted with a chromatographic washer based on the continu-
ous water flow within a long tube. The nanocelluloses were
 T. Suopajärvi et al. / Chemical Engineering Journal 231 (2013) 59–67
Table 1
The chemical composition of the cellulose material that was used in the experiments.
Cellulose material Polysaccharides
Cellulose (%) Xylan (%)
Birch pulp 74.8 23.6
Table 2
Characteristics of the samples from the municipal wastewater treatment plant.
Waste water TSSa (mg/l) TSb (mg/l)
Sample I 333 700
Sample II 368 865
Sample III 404 897
a
Total suspended solids (SFS-EN 872).
b
Total solids (SFS 3008:1990).
c
Chemical oxygen demand (ISO 15705:2002).
Fig. 1. Periodate and chlorite oxidation of cellulose.
washed in a long plastic tube (diameter 4 mm) with 1000 ml of
deionized water for 108 s at a flow rate of 7.5 ml/s. The particles
flowed in this tube at different average velocities according to their
size, the largest particles tending to remain in it longer at faster
flow rates, so that they were the first particles to emerge at the
end of the long tube [26]. 5 ml of sample at a consistency of 0.1%
was injected into a constant water flow in a washer and four size
categories were obtained by taking samples after 60, 77, 86 and
95 s of separation. The largest particles in the washed particle-
water suspension was visualized with a CCD camera (resolution
1.6 lm) in a small cuvette, and the amounts of material in the var-
ious categories were measured by filtration on a membrane (reten-
tion 0.2 lm) followed by weighing. Fractions were also collected
for subsequent FESEM analysis.
2.3.2. Imaging by field emission scanned electron microscopy (FESEM)
An FESEM device (Zeiss Ultra Plus) was used to study the mor-
phology and size of the chromatographically washed fibrils in the
different fractions. As a pretreatment, the samples were filtered
using a polycarbonate membrane with a pore size of 0.2 lm fol-
lowed by rapid freezing with liquid nitrogen and freeze-drying in
a vacuum overnight. The dried samples were sputter-coated with
platinum and imaged using a voltage of 10 kV and a working dis-
tance of 5 mm.
2.3.3. Atomic force microscopy (AFM)
AFM (Nanoscope IIIA, Veeco Instruments, Santa Barbara, USA)
was performed to reveal the morphology of DCC nanofibers. As a
pretreatment, the nanofiber suspension of 0.001% was sonicated
for 1 min to enable complete disentanglement and dispersion of
nanofibers. A fresh mica surface, which was pretreated with
cationic polyelectrolyte (polylysine, Sigma–Aldrich, Germany),
was used as substrate for nanofibers. The dilute DCC nanofiber
suspension was cast on the pretreated mica surface and air
dried. AFM images were captured in a tapping mode using
8 nm steel tip.
61
Lignin Extractives
Glucomannan (%) Total (%) Acetone soluble (%)
1.1 0.4 0.08
pH Conductivity (lS/cm) CODc (mg/l) Turbidity (NTU)
7.37 663 395 175
6.97 810 435 158
6.92 1600 727 156
2.3.4. Determination of charge density (CD) by polyelectrolyte titration
The pH buffers (pH 3–5: CH3COOH/NaCH3COO; pH 7–8: NaH2-
PO4/Na2HPO4 and pH 9–10: NaHCO3/Na2CO3) for the analysis were
prepared by diluting an appropriate amount of the Na-salt of the
respective base to approximately 80% of the final volume, adjusting
the pH (as measured with a combination electrode, Mettler Toledo)
with 0.1/1M HCl (or NaOH), and finally diluting the buffer to the
appropriate volume in volumetric flasks. These buffers were used
for all the experiments in the pH-range 3–10.
The polyelectrolyte titrations were conducted at a solids con-
tent of 0.1%. For these experiments, 9 ml of the appropriate buffer
and 1 ml of DCC suspension were mixed and titrated with a cat-
ionic polyelectrolyte (poly DADMAC) in a Mütek PCD 03 particle
charge detector while monitoring the sign of the charge.
2.4. Coagulation–flocculation experiments
2.4.1. Coagulation–flocculation treatment procedure
The flocculation performance of the DCCs was evaluated by
measuring the residual turbidity and COD of the settled waste
water after coagulation–flocculation treatment using procedure
similar to that employed in standard jar testing. The waste water
(100 ml) was treated using only ferric coagulant or using both
ferric coagulant and DCCs. The experiments were conducted by
adding a constant dose of ferric coagulant (37.5 mg/dm3 or
25 mg/dm3 after optimization of the dosage) to the waste water
in a beaker and stirring the suspension with a magnetic stirring
bar at 200 rpm for 3 min at room temperature. After the coagula-
tion treatment, the DCC solution (2.5–50 mg/dm3) was added to
the waste water and the suspension was stirred at 40 rpm for
15 min. Finally, the suspension was allowed to settle for 30 min
at room temperature and the turbidity of the supernatant was
measured with a Hach Ratio XR turbidimeter (model 43900) and
the COD from standardized (ISO 15705:2002) test tubes (Hach)
by means of a Hach Lange DR 2800 spectrophotometer.
To characterize the flocculation performance of the DCCs at
different pH values, experiments were conducted at pH values
ranging from 6 to 8, corresponding to a typical pH range for a
62 T. Suopajärvi et al. / Chemical Engineering Journal 231 (2013) 59–67

Table 3 forms of carboxyl groups, which indicate the formation of dicarb-

Aldehyde and carboxyl content of cellulose after periodate and chloride oxidation, oxyl-containing celluloses.
and the yield after chlorite oxidation.

Sample Aldehyde content Carboxyl content Yield after chlorite 3.1.2. Amount of anionic groups and size of nanofibrils
(mmol/g) (mmol/g) oxidation (%)
The aldehyde and carboxyl contents of the cellulose after perio-
DCC I 0.36 ± 0.03 0.38 ± 0.02 100 date and chlorite oxidation and the mass yield of the samples after
DCC II 0.61 ± 0.06 0.69 ± 0.03 84
chlorite oxidation are shown in Table 3. The carboxyl content re-
DCC III 0.95 ± 0.09 0.75 ± 0.03 83
DCC IV 1.31 ± 0.12 1.20 ± 0.05 73 sults indicate that a major proportion of the aldehyde groups were
DCC V 1.68 ± 0.15 1.75 ± 0.07 66 converted to dicarboxyl groups during chlorite oxidation. The mass
yield of the samples after chlorite oxidation was from 100% to 66%.
As found previously [23], the dissolution losses during oxidation
pretreatments are closely associated with the carboxyl content of
municipal wastewater treatment plant. The doses of ferric coagu-
the cellulose. Thus, the yield would improve if a cellulose pulp with
lant and DCC used in these experiments were 37.5 mg/dm3 and
a lower hemicelluloses content were used.
5 mg/dm3, respectively.
The mass proportions of the various fractions in the chromato-
graphic washer for the DCC samples and the types of particles pres-
2.4.2. Zeta potential measurements ent in the fractions are shown in Fig. 2. Fraction 1 (FR 1) contained
Zeta potential was measured as a function of pH from untreated mainly non-fibrillated material, and therefore had the largest par-
wastewater, after coagulation (25 mg/dm3 (Fe2(SO4)3)) and after ticles, while the second fraction (FR 2) contained fibrillated mate-
coagulation (25 mg/dm3 (Fe2(SO4)3))-flocculation (5 mg/dm3 DCC) rial, but still with some bunches of fibrils remaining. The widths of
treatments. Measurements were conducted by Zeta-potential the particles in FR 2 as measured from the FESEM images were
apparatus Beckman Coulter DELSA Nano C (USA) from the settled from 80 nm to 20 nm, while the lengths were assumed to be
suspensions. The pH of the suspensions was adjusted from 2 to some tens of micrometres. FR 3 contained highly fibrillated mate-
10 using HCl and NaOH solutions. rial with widths from 20 nm to 6 nm and lengths of several
micrometres, and FR 4 contained the finest material, with more
3. Results and discussion rounded particles having a lower aspect ratio than in FR 2 or FR 3.
The highest non-fibrillated material content was found in the
3.1. Characteristics of the DCCs DCC II sample, and DCC II was oxidized more than DCC I, even
though it had had one homogenizer pass less than DCC I. DCC III
3.1.1. Characteristics of the oxidation reactions and IV had passed through the homogenizer as many times as
The IR spectrums of the periodate oxidized (DAC) and of the DCC II, but because of their higher degree of oxidation they unrav-
chlorite oxidized (DCC) samples are shown in Supplementary data elled more easily to nanofibrils in the homogenizer than did DCC II.
in Fig. S1. The spectrum for DAC shows characteristic bands at The high anionic charge density of DCC V promoted efficient nano-
1640 and 895 cm 1, which are assigned to the aldehyde carbonyl fibrillation and consequently this sample had the highest nanofibr-
group, hemiacetals, and the hydrated forms of aldehyde groups, illated material content (FR 3), even though it had had only one
respectively [27]. The functionality of the chlorite-oxidized cellu- pass through the homogenizer. DCC I had similar mass proportions
lose was confirmed by the disappearance of the aldehyde bands to DCC V after four passes through the homogenizer, while DCC IV
and the appearance of new bands at 1735 and 1620 cm 1. These had the highest amount of fraction 2 and thus contained more
new bands are associated with the protonated and dissociated bunches of fibrils than DCC I or DCC V.

Fig. 2. Mass proportions of the four fractions (FR 1–4) in DCC samples from the chromatographic washer and images illustrating the particles of different fractions. Left: CCD
camera images of FR 1, centre: FESEM images of FR 2, and right: FESEM images of FR 3. The scaling bar in the FESEM images is 1 lm.
 T. Suopajärvi et al. / Chemical Engineering Journal 231 (2013) 59–67
Fig. 3. AFM image from the DCC sample. The scaling bar in the image is 500 nm.
The size of nanofibrils were also confirmed by AFM from sam-
ples without fractionating and the results are shown in Fig. 3. Typ-
ical lateral dimensions of used DCC nanofibers ranged from 3 to
5 nm, while their length was up to micrometre-scale. The NFC sus-
pension was used directly after preparation with homogenizer
without any purification steps, and consequently it also contained
some larger fibril bundles of diameter below 200 nm.
3.1.3. Apparent charge density as a function of pH of the solution
The apparent CDs of DCCs I–V in the pH range 3–10, as
determined by polyelectrolyte titration, are shown in Fig. 4a. The
Fig. 4. Apparent CDs of DCCs I–V as a function of pH (a), and the CD of DCC I as a function of time (b). The titration data points are averages from 2–4 titrations.
Fig. 5. Turbidityreduction and COD removal in wastewater samples I-III after coagulation treatment as a function of the dose of coagulant (ferric sulphate). The settling time
was 30 min.
63
apparent anionic charge density of the DCCs increased towards
neutral conditions and remained quite constant after a pH of about
7. DCCs IV and V, with higher numbers of carboxyl groups, showed
greater charge density changes from acidic to neutral conditions
than did the other DCCs, but all the DCC flocculants showed con-
stant CDs below pH 6–8, i.e. in the range that normally prevails
in activated sludge wastewater treatment. The CDs obtained by
polyelectrolyte titration under neutral conditions were substan-
tially lower than the carboxyl group content values obtained by
conductometric titration (Table 3), probably as a consequence of
the high Mw of the titrant polymer, which sterically restricted
the availability of carboxyl groups in the cellulose. The same effect
has been observed previously with sulphonated cellulose nanopar-
ticles [18].
The apparent charge density for DCC I is shown as a function of
time under neutral conditions in Fig. 4b. CD was found to be con-
stant for at least nine days, which indicates that particulate DCC
flocculants remain quite stable in aqueous solutions without losing
anionicity.
3.2. coagulation–flocculation treatment
3.2.1. Optimization of coagulant dosage
The coagulation performance of ferric sulphate in terms of the
reduction achieved in the turbidity of wastewater samples I–III
(Fig. 5a) and the removal of COD from samples I–II (Fig. 5b) as a
function of coagulant dosage are shown in Fig. 5. Turbidity reduc-
tion starts after the addition of about 50 mg/dm3 of ferric sulphate
(120 mg/dm3 for sample I) and increases up to a dosage of 250 mg/
dm3. The same trend with the dosage of ferric coagulant is seen in
64 T. Suopajärvi et al. / Chemical Engineering Journal 231 (2013) 59–67

Fig. 6. Turbidity (a) and COD (b) of waste water after coagulation as a function of the pH of the suspension. The doses of coagulant (ferric sulphate) were 37.5 and 62.5 mg/
dm3 for wastewater samples I and II, respectively. The settling time was 30 min.

COD removal, although the process is not as efficient as in turbidity
reduction.
3.2.2. Influence of pH on coagulation
The coagulation performance of ferric sulphate at different pHs
was also tested with water samples I and II. The pH range used was
from 6 to 8, representing the typical pH of an activated sludge
wastewater treatment plant. The doses of ferric coagulant were
62.5 mg/dm3 for sample I and 37.5 mg/dm3 for sample II. Turbidity
and COD both increase slightly towards neutral conditions (Fig. 6),
but decrease again slightly towards an alkaline pH. These results
are well in accordance with previous reports of optimum pH values
of 3.5 to 7.0 and above 9.0 for ferric sulphate in coagulation [1] and
show that the ferric sulphate coagulant was working properly at
the pH of the present wastewater samples.
3.2.3. Influence of the nanofibril DCC flocculant dose on coagulation–
flocculation treatment
The coagulation–flocculation treatments were performed by
adding a constant dose of ferric sulphate (25 mg/dm3 for samples
I and II and 37.5 mg/dm3 for sample III) to stirred waste water,
after which nanofibrillar DCC was added to the coagulated product.
The flocculation performance of the DCCs in terms of the reduction
in turbidity and removal of COD as a function of DCC dosage is
shown in Figs. 7 and 8. The results indicate that all the DCCs
synthesized here were able to flocculate waste water efficiently
(turbidity reduction of 40–80% and COD removal of 40–60%). The
effective doses of the DCCs were similar to those of the commercial
cationic polymer used as a reference flocculent. The reference
polymer showed 14–40% higher turbidity reduction efficiency than
the DCCs (Fig. 7), but the DCC flocculants showed as good a

Fig. 7. Reduction in the turbidity of waste water after coagulation–flocculation treatment as a function of the dose of nanofibril DCC flocculant. The coagulant (ferric sulphate)
dose was 25 mg/dm3 for wastewater samples I and II (a and b) and 37.5 mg/dm3 for sample III (c). The settling time was 30 min.
 T. Suopajärvi et al. / Chemical Engineering Journal 231 (2013) 59–67 65

Fig. 8. COD removal from waste water after coagulation–flocculation treatment as a function of the flocculant (DCC) dose. The coagulant (ferric sulphate) dose was 25 mg/
dm3 with wastewater sample I (a) and 37.5 mg/dm3 with sample III (b). The settling time was 30 min.

performance as the commercial reference polymer in COD removal
(Fig. 8). The optimum improvements were achieved with moder-
ately low doses of DCC flocculants (2.5–5 mg/dm3).
The flocculant performance of the DCCs was found to correlate
with the charge density and nanofibril content of the samples, the
best flocculation performance being observed with DCCs IV and V.
These DCCs had the highest anionicity and contained highly nano-
fibrillated material. Even though DCC II and III had a higher charge
density than DCC I (Table 3 and Fig. 4), DCC I showed a better floc-
culation performance. This effect may be explained by the amounts
of the nanofibrillated material in the samples. As seen in Fig. 2, DCC
I, which was homogenized four times, contained more nanofibrillar
material in fractions 2 and 3 than did DCCs II and III, which were
passed through the homogenizer three times. It should be noted
in particular that DCC I worked best at lower coagulant doses.
Compared with the coagulant treatment in which ferric sul-
phate alone was used (Fig. 5), combined coagulation–flocculation
with DCCs (Fig. 7) resulted in a similar degree of turbidity reduc-
tion with a significantly lower coagulant dose (25 mg/dm3 vs.
250 mg/dm3), while higher coagulant doses seemed to attenuate
turbidity reduction (Fig. 7). COD removal was as good in this coag-
ulation–flocculation treatment (Fig. 8) as in coagulation alone. As
the optimum dose of DCCs was only 2.5–5 mg/dm3, the combined
process resulted in considerably lower levels of total chemical
consumption.
3.2.4. Influence of pH on coagulation–flocculation treatment
The flocculation performance of the combinations of ferric sul-
phate with DCCs I and IV in the pH range 6–8 is shown in Fig. 9.
Turbidity reduction (Fig. 9a) declined from the pH 6 to 6.5 and
started to improve again towards alkaline conditions, while COD
removal (Fig. 9b) improved slightly towards alkaline conditions,
although no significant changes were observed. Also the charge
density as a function of pH (Fig. 4) showed that anionicity of the
DCCs remained quite constant from the pH 5 to pH 10. These re-
sults indicate that DCC flocculants are effective for the coagula-
tion–flocculation treatment of waste water in the pH range used
here and that no inactivation of the flocculants occurred.
3.2.5. Mechanism of flocculation with nanofibrillar DCCs
As shown in Fig. 10, the DCCs formed flocs of a different mor-
phology from that obtained with the commercial cationic reference
polymer. Where the reference polymer yielded large floats of airy
flocs which were drifting in the water, the DCCs formed small, tight
flocks which slowly settled on the bottom of the container.
The anionic DCCs were unable to flocculate anionic dirt material
from the municipal waste water without assistance from a cationic
coagulant, so that the right coagulant dose for charge neutraliza-
tion was important. It is also significant that the size of the DCC
flocculants plays a major role in flocculation performance, since
DCC I, which had the lowest charge, gave similar flocculation re-
sults to DCC V, which had the highest charge.
The zeta potential of initial wastewater, after coagulation and
after coagulation–flocculation treatment in the pH range 2–10,
are shown in Fig. 11. The zeta potential of the suspensions
remained during the whole coagulation–flocculation treatment
on a negative side (the operating pH was from 6 to 8). The
dosage of cationic ferric coagulant was so low that the charge

Fig. 9. Turbidity reduction (a) and COD (b) removal in wastewater sample III after coagulation–flocculation treatment as a function of the pH of the suspension. The coagulant
(ferric sulphate) and flocculant (DCC) doses were 37.5 mg/dm3 and 5 mg/dm3, respectively.
66 T. Suopajärvi et al. / Chemical Engineering Journal 231 (2013) 59–67
Fig. 10. Images showing the differences in floc morphology between the cationic
reference flocculant and the nanofibrillar DCC flocculants.
Fig. 11. Zeta potential of the initial wastewater, after coagulation (25 mg/dm3 ferric
sulphate) and after Coagulation (25 mg/dm3 ferric sulphate) -flocculation (5 mg/
dm3 DCC) as a function of pH.
of wastewater colloidal particles remained highly anionic and
they did not approaches the point of electrical neutrality. The
anionic flocculant increased the negatively charged zeta potential
additionally.
It is likely that the positively charged ferric species provided
cationic patches on the surface of the dirt particles and the anionic
DCC nanofibrils were coagulated aggregates connected via these
cationic patches. It is generally found that the most effective poly-
mers for bridging are linear chains of high molecular weight, but
the charge density can also have a considerable influence on bridg-
ing effectiveness [3]. In the case of the DCCs, the influence of the
CD was not so obvious, and Bolto and Gregory [3] have also ob-
served that the presence of multivalent metal ions such as Fe3+
may promote complexation of the metal with carboxylate groups
on the polymer chain and cause an effective reduction in CD. Any-
how, there may be an optimum salt concentration for bridging
flocculation with DCCs, as it was seen in Fig. 7 that lower coagulant
doses improved turbidity reduction. The configuration of the poly-
mer also affects the mechanism of flocculation. Nanofibrillar DCCs
have a high aspect ratio and a negatively charged backbone. Since,
as stated by Ho et al. [6], the negatively charged carboxyl group
(COO ) and hydroxyl group (OH ) on the molecular chain of bio-
polymeric flocculants make the chain stretch out under alkaline
conditions because of electrostatic repulsion, allowing the polymer
molecules to be extended and to produce loops and tails to pro-
mote bridging. It may be presumed that the nanofibrillar DCCs
were in this stretched configuration under the present experimen-
tal conditions, enabling the DCCs to form large flocs with an open
structure.
4. Conclusions
The anionic nanofibrillated dicarboxylated cellulose (DCC)
bioflocculants synthesized here showed good performance in the
coagulation–flocculation treatment of municipal waste water.
Their turbidity reduction efficiency fell short of that of the syn-
thetic reference polymer, but their COD removal performance
was as good as the latter. Combined treatment resulted in a lower
residual turbidity and COD in settled suspension with highly re-
duced total chemical consumption relative to coagulation with fer-
ric sulphite alone. DCC flocculants with a high charge density and
high nanofibril content gave the best flocculation performance. The
DCCs showed good stability over a long period of time in aqueous
suspensions and good performance in the pH range chosen here.
Acknowledgements
We thank M.Sc. Ngesa Ezekiel at the Royal Institute of
Technology (KTH, Sweden) for AFM imaging. The authors also
acknowledge with gratitude the funding provided by the European
Regional Development Fund project ‘‘Nano- and Microcellulose
Based Materials for Water Treatment Applications’’, the European
Union and the Future Biorefinery Programme of Forestcluster Ltd.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2013.07.010.
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