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Coagulation-ﬂocculation processes in water and wastewater treatment. (II)

Fine particles and its removal using electrolytes and polyelectrolytes
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Current topics, concepts and research priorities in environmental chemistry (III)
Chapter 8
Coagulation-flocculation processes in water and wastewater

treatment. (II) Fine particles and its removal using electrolytes
and polyelectrolytes
Carmen Zaharia*
‘Gheorghe Asachi’ Technical University of Iasi, Faculty of Chemical Engineering and
Environmental Protection, Department of Environmental Engineering and Management,
73 Prof.Dr.docent D.Mangeron Blvd, 700050 Iasi, Romania
*
corresponding author e-mail: czah@ch.tuiasi.ro
ABSTRACT
The permanent watercourses nearly industrial sites of cities are known to have contaminated water
bodies with various pollutants such as organics, minerals and heavy metal ions. Some quality
indicators are permanently controlled alongside the length of watercourse (i.e. some general and
specific quality indicators for oxygen regime and solid contents, aquatic fauna), or at least few times
per year (especially for toxic compounds: pesticides, PCBs, total arsen, lead and chrome ions).
Some physical-chemical-biological processes are usually interacting such as chemical
precipitation, colloids’ aggregation by coagulation-flocculation processes, redox processes,
complexation, neutralization (acid-basic process), ionic exchange, adsorption processes at water-
sediment, or water-solid phase interfaces, or in-deep water mass, aerobic and/or anaerobic biological
processes caused by specific metabolism of different aquatic plants or organisms, sedimentation,
filtration/biofiltration, etc.), or other hybrid processes. One of these processes that occurs in natural
state in all surface waters (e.g., river, lake) with differentiated magnitudes is coagulation-flocculation
associated with natural gravity sedimentation, or filtration/biofiltration (or air flotation), which is
presented as mechanism, destabilizing agents and different factors influencing the process efficiency
and stability of formed aggregates. In addition, some laboratory scale set-up tests of coagulation-
flocculation (Jar tests) applied for a Romanian Northern-Eastern river (i.e. Bahlui River, Iasi City
area) were performed and the results summarized, especially for coagulation-flocculation results
working with inorganic coagulants like ferric sulphate - Fe2(SO4)3, aluminium hydroxochlorosulfate
(AHCS), and specific polyelectrolyte (i.e. anionic Ponilit GT-2 polyelectrolyte), respectively, in
different environmental conditions. The best treatment degree (i.e. > 90% for colour and turbidity,
and > 44% for organics expressed by COD) were performed with a individual dose of around 5-30
mg/L Fe2(SO4)3, 50-70 mg/L AHCS, and/or 10-50 mg/L Ponilit GT-2 polyelectrolyte, much lower
(more than 10-100 times lower) if the electrolytes and the polyelectrolyte are acting together for the
same reason (separation of fine turbidity solids). Without Fe3+ ions, the highest efficiency (turbidity
and colour) was performed with a dose of 75 mg/L AHCS, and 10-30 mg/L anionic polyelectrolyte.
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Chapter 8: Coagulation-flocculation processes in water and wastewater treatment (II)
At least one mechanical cleaning treatment (with special mechanical tools) is annually
obvious necessary before the beginning of hot season, more exactly in earlier spring times (March -
April) for elimination of in-excess wastes and aquatic plants/organisms, but also each time necessary
the application of local simple physical-chemical cleaning treatments of surface water. The sediments
must also be removed (i.e. collected, dried, eventually treated), and valorised as soil (in mixture with
existing reference soil in different local area) or ingredient for composites, among others.
Keywords: coagulation, colloids, destabilization agents, flocculation, quality indicator, inorganic

coagulant, polymeric flocculant, sedimentation, solid matter, treatment, turbidity, watercourse
1. INTRODUCTION
The fresh water is not pure and contains different constituents in different proportions
permitting the classification of fresh water in different types of natural aquatic environment
resources. These constituents are consisting of solid particles of inorganic or organic origin,
and different dissolved ionic and molecular species in the whole water mass. Only 0.5 % of
total existing fresh water of Earth is in easely accessible surface forms (i.e. rivers, ponds
and lakes) (van Loon and Duffy, 2005; Zaharia, 2011a; Zaharia and Suteu, 2013).
In quantitative terms, the fresh water is unevenly distributed, and countries that
have available less than 2,000 m3/year per capita of fresh water are considered to be in
chronic water deficit (van Loon and Duffy, 2005; Zaharia and Suteu, 2013). In qualitative
terms, the fresh water is highly variable, and a lot of physical-chemical and microbiological
elements must be considered for determination of its acceptability for different purposes
(Zaharia and Teslaru, 2012; Zaharia and Suteu, 2013).
The dissolved species present in the surface water can participate to simple or
complex homogenous interactions (i.e. reactions of dissolved species with formation of new
dissolved species in aquatic environment) or heterogeneous interactions (i.e. reactions of
dissolved species with formation of new solid or gaseous species), in the presence or
absence of dissolved oxygen or carbon dioxide in water (as dissolved gases in water),
favoured or not by action of some catalysts (e.g., metal ions) and organisms (e.g.,
microorganisms, algae, fungi, etc.), or solar energy. The representative homogenous
interactions for the aquatic environment are exchange interactions of protons (acid-basic
reactions), of different types of cations and anions (ionic exchanges) and exchange of
electrons (redox reactions). In the case of heterogeneous interactions, the representative
ones are precipitation and dissolution interactions in the aquatic environment or at water-
rock/mineral interfaces, and also coordination/complexation/chelatising, coagulation-
floculation, adsorption/sorption/biosorption processes which lead to some gaseous species
formation in-deep surface water and/or water-atmosphere interface. Even if the last three
ones are limited as number in comparison with the precipitation-dissolution processes, the
CO2 and O2 exchanges play an essential role in the superficial processes and also
metabolism of aquatic organisms and plant photosyntesis (Zaharia, 2011a,b; Zaharia and
Surpateanu, 2006; Zaharia and Suteu, 2013).
In ground water, filtered through layers of permeable soil material, water is usually
clear, indicating the presence mostly of dissolved species. In other components of
hydrosphere, the situation is different, and considerable fractions of different inorganic or
organic polluting species exists as suspended particles that requires separation by simple or
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complex processes and/or operations such as natural sedimentation, filtration, or

coagulation-flocculation associated with sedimentation, etc.
A fast-flowing river carrying an abundant sediment load can give a distinct milky
appearance (e.g., the ‚White Amazon’ in northern America, or the ‚White Nile’ in north-
eastern Africa) (vanLoon and Duffy, 2005). In general, the suspended material consists of
typical minerals and organic matters, especially those in fine (nano-, colloidal- and micro-
size) or settleable fraction as illustrated in Table 1. Therefore, the elements usually present
are consisting of high concentrations of silica, clays, fine polymeric solids, alkali and
alkaline earth metals, aluminium, and iron precipitates, along with smaller amounts of other
metals associated, more or least, with the adsorbed species on the fine particle surface.
Table 1 - Estimation of contaminants in different aggregation phases present in various raw waters
(Odegaard, 1987; Zaharia, 2000, 2006)
Indicator/expression mode of Classification of contaminants in water

contaminant (indicator) Soluble Colloidal Supra-colloidal Settleable
Size range, [µm] < 0.025 0.025 - 3 3 - 106 > 106
Inorganic constituents: Clay, silt, 10 43 25 22
silica, etc., [% of total]
Organic constituents:
Grease [% of total] 12 51 24 19
Protein [% of total] 4 25 45 25
Carbohydrates [% of total] 58 7 11 24
BOD5 [% of total] 17 16 46 21
COD [% of total] 12 15 30 43
TOC [% of total] 22 6 36 36
Total P [% of total] 63 3 12 22
Organic N [% of total] 27 15 38 20
k- Biochemical [d-1] 0.39 0.22 0.09 0.08
oxidation rate
The ratio of suspended to dissolved fine substances in rivers is quite variable, with
typically values ranging from less than 0.03 to much greater than 1. Also, metal in
suspended sedimentary material of various origins is considered to be less available for
uptake by organisms than are the dissolved forms of the same element. The elements
associated with iron or manganese (hydr)oxide particles can be remobilized if the particles
participate at reductive dissolution. Suspended organic particles can decompose into
smaller, soluble molecules under oxidizing conditions, and can lead to release of soluble
forms of complexed/coordinated metals. Some organisms (e.g., filter-feeders like clams and
mussels in water bodies) can take up colloid-bound metals and nutrients directly from the
suspended material (sedimentary, or in-deep water flowing solids), and interesting is also
the fact that their excretions may include more soluble forms of rejected elements, thus
contributing to the local alteration/pollution of aquatic environment.
The colloidal particles, considered also as fine turbidity particles, are usual
constituents in natural surface water resources, and cause often taste, odor and color
problems. Therefore, its possibility to be separated from surface waters for use in different
purposes by coagulation-flocculation, or other treatments associated or not with gravity se-
dimentation, or natural barrier filtration/biofiltration, is one of the main goal of this work.
169
These fine particles (both hydrophilic and hydrophobic colloids) possess

electrokinetic property causing double layer formation, and consequently surface charges.
Hydrophilic colloids are in principal of biological origin (such as proteins,
bacteria) and usually consist of water-soluble functional groups like –NH2, -COOH, -OH, -
SO3H, and –OPO3H2 (e.g., a protein particle: HOOC – R – NH3+ formed at high pH level,
or –OOC – R – NH2 formed at low pH level). In practice, the Zeta potential (determined
from the electrophoretic mobility measurements, and expressed by relation: Me = ε ⋅ Z ,
K ⋅η
where: Me – electrophoretic mobility, [m2/s. V]; ε - dielectric constant of aquatic medium,
[F/m]; η - dynamic viscosity, [Poisse]; K – factor depending on colloid type and dimension
(usually it has the value of 4); Z – Zeta potential, [V]) is important being implicated in
many environmental applications, but an essential factor it has in the transport of organics,
bacteria in porous media as shown in table 2. In general, a zeta potential of 100 mV in
water at 25⁰C is equivalent with a field of about 1500 V/cm created by electrodes to
produce a velocity of 1 cm/s of air bubbles in the capillary at the return path (Yen, 2007).
Table 2 - Zeta potential of Bacillus subtilis and Pseudonomas putida (Jang and Yen, 1985)
Species Culture age, [h] Suspending medium Zeta potential, [mV]
18 Electrolyte solution (A)* 33.6
Bacillus subtilis - 18 Buffer solution (B)** 27.1
18 Buffer solution (C)*** 37.8
a spore-forming Gram 72 Buffer solution (B) 47.0
positive facultative 72 Culture growth medium with 51.8
anaerobe bacteria remained cells without separation
72 Buffer solution (C) 63.28
12 Electrolyte solution (A) 53.9
Pseudomonas putida - 12 Buffer solution (C) 52.4
15 Culture growth medium with 58.3
a non-spore forming remained cells without separation
Gram negative aerobe 15 Buffer solution (B) 58.7
bacteria 72 Buffer solution (B) 56.7
*
1,000 ppm NaCl-containing electrolyte solution; ** 0.0663 M KH2PO4 and 0.0267 M NaOH-containing buffer
solution (pH=7.00); *** 0.0127 M KH2PO4 and 0.0054 M NaOH-containing buffer solution (pH=7.00).
The hydrophobic colloids are especial of inorganic or mineral origin (such as clay,
silt, and silica), being charged at face boundaries of particle surfaces as result of different
ionic exchanges or isomorphous replacements within the lattice due to lattice imperfections.
Most metal oxides and hydroxides are amphoteric, but can adsorb H+ and HO- ions or its
complexes, and are changing their surface charges passing through zero (isoelectric point-
IEP), fact expressed mainly by pHZPC (pH of zero point of charge). Some values of pHZPC
for fine inorganic turbidity particles (i.e. clay minerals - phyllosilicates as kaolinite;
montmorillonite - smectite as muscovite, vermiculite, chlorite; feldspar, quartz), present in
fresh water are given in table 3 (Yen, 2007; Zaharia, 2013; Zaharia and Suteu, 2013).
The colloidal and near-colloidal-size particles have an ‚apparent’ surface charge,
but its magnitude and sign is dependent of pH value. Because fine particle in-deep surface
water is generally neutral (no net charge), a double ionic layer (consisting of a Stern layer
covering the external colloidal particle surface, and also a diffuse layer at a specific distance
from colloidal particle surface, with multiple co-ions and counter ions present) is developed
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(Haller, 1995; Schroeder, 1977; Yen, 2007; Zaharia, 2006, 2013; Zaharia et al., 2007):
- ions with the same charge as the particle are rare near the particle surface, but
gradually increase in number as the distance from particle increases (present in the
diffuse layer as co-ions).
- unlike ions or counter ions predominate near the particle surface, but gradually
decrease in number with increasing distance (present in the Stern layer but in a
decreasing number in the diffuse layer).
Table 3. The pHZPC values of different fine turbidity particles (adapted after Yen, 2007;
Zaharia, 2011a, 2013; Zaharia and Suteu, 2013)
Fine particles pHZPC Fine particles pHZPC Fine particles pHZPC
α-Al2O3 9.1 γ−Fe2O3 6.7 ZrSiO4 5.0
α-Al(OH)3 5.0 Fe(OH)3 amorf 8.5 Feldspars 2-2.4
γ-AlOOH 8.2 MgO 12.4 Kaolinite 4.6
CuO 9.5 δ-MnO2 2.8 Montmorillonite 2.5
Fe2O3 6.5 b-MnO2 7.2 Albite 2.0
α−FeOOH 7.8 SiO2 2.0 Chrysolite > 12
Repulsive (coulombic repulsive forces) and attractive forces (van der Waals
attraction forces) analogous to gravitational forces exist between particles, and regulate the
distance between colloidal turbidity particles. Increasing ionic strength is produced by
adding electrolytes (coagulants), termed as compression of double layer, which is
significant in coagulation of colloidal clay particles moving from fresh water rivers into
estuaries. Coagulation is induced also by simple electrostatic adsorption of counterions that
effectively neutralize the turbidity particles and decrease the surface potential. The
effectiveness of a counter ion in coagulation increases with charge; e.g., in the increasing
order of Na+, Ca2+ (Fe2+), Al3+ as measured by ionic concentrations necessary to coagulate
the fine turbidity particles which are usually of 1: 10-2: 10-3.
In addition, the colloidal turbidity particles can be separated by chemical-
mechanical interactions, in principal by coagulation and flocculation processes in natural
self-purification systems of fresh surface water, or induced in situ treatments of fresh water
bodies that are normally carried out prior to sedimentation and filtration.
In general, the fresh water utilization for different human consumption demands
such as drinking purposes is based on ex situ treatments (as production and population
supply with potable/drinkable water, preparation of alcoholic or non-alcoholic, aromatic or
refreshing drinkings, food conservation, etc.), or irrigation, or sportive activities, among
others, which imposes some obligatory steps of water treatment in a plant in order to
respect the strict requirements of water quality and safe, such as coagulation-flocculation,
gravity sedimentation, rapid filtration, adsorption on activated carbon, disinfection, etc.
2. THEORETICAL PART ON THE IN / EX SITU COAGULATION AND

FLOCCULATION PROCESSES IN NATURAL WATERS AND WASTEWATERS
In general, it is considering that coagulation is the process by which the colloidal systems
are destabilized, and particles are allowed to aggregate and flocculate to higher sizes that
settle with high, or most satisfactory velocities (Haller, 1995; Yen, 2007). The existing
turbidity particles in natural surface waters are within colloidal sizes possessing
171
electrokinetic properties which cause double layer formation, and their stabilities are
governed by colloidal chemistry charges. The electrokinetic properties are caused by
different field effects, such as electricity and so forth, at a different solid surface. The main
electrokinetic phenomena for colloidal surface are divided in four types as (Yen, 2007):
• electrophoresis, due to electric field on colloidal particles with motion of disperse
phase;
• sedimentation potential, due to gravitational field on particles with potential gradient;
• electroosmosis, due to electric field on tube wall or packed bed with motion of the
aquatic medium;
• streaming potential, due to motion of aquatic medium (e.g., on tube wall or packed
bed) with potential gradient.
Some examples of charged colloidal particles (mineral particles) are illustrated in
Fig. 1, and also define below as:
- colloidal particles having on its surface groups of silanol, i.e. ≡SiOH acting as
≡Si – OH2+ ↔ (K1)/-H+ Si – OH ↔ (K2)/-H+ Si – O- (1)

- colloidal particles of metal oxides and hydroxides both amphoteric, with possibility of
adsorbing H+, or HO- ions, or its complexes. Surface charges can originate from a
mineral particle, or hydrous metal (Fe or Al) oxide layer as solute coordinated to bind to
a specific solid mineral surface (Kam and Gregory, 2001; Yen, 2007); e.g.:
Cu (s) + 2H2S ↔ Cu(SH)22- (surface) + 2H+ (2)

MnO2 H2O (s) + Zn2+ ↔ MnOOHOZn+ (surface) + H+ (3)
- colloidal particles adsorbing surfactant ions.
Fig. 1. The surface charges of a mineral colloid particle Fig. 2. Representation of a negative colloidal
with adsorbed humic substances and surface complexed particle with its electrostatic field
divalent cations and also counter ions in diffuse double (adapted from Preisting, 1962)
layer (Yen, 2007)
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The charges of colloidal particles are essential to the understanding of colloidal

agglomeration, or stabilization by coagulation-flocculation, but also the formed flocs
destabilization (break-up). The stages of a coagulation process are summarized in table 4.
A colloidal system, like a lake or river containing suspended clay particles, is stable
because the small charged particles repeal each other. As they move in the aquatic
environment due to thermal motion, these are able to come suficiently close in order to
overcome the repulsive forces of the surface charge and aggregate into larger, settleable
units. The result is a long-lasting suspension of colloids (vanLoon and Duffy, 2005).
Table 4 - The stages of a coagulation-flocculation process (Zaharia, 2006; Zaharia et al., 2006b)
Stage Phenomenon Defined term
Addition of Processes of ionization, hydrolysis, polymerization in Hydrolysis
coagulant water or aquatic medium
Destabilization Compression of double electric layer. Coagulation
Specific adsorption of coagulant ions at the surface of
colloidal particles.
Specific binding of ions sau species at particle surface.
Colloid inclussion in a precipitate of hydroxide.
Bridging between particles due to polymeric species. (or flocculation)
Transport Brownian motion Perikinetic flocculation
Dissipated energy (velocity gradient) Orthokinetic flocculation
There are known four major coagulation mechanisms explaining the agglomeration
of colloidal particles at higher particle-size dimensions, and consequently ease separation
by gravity sedimentation or filtration (Odegaard, 1987;Walldal, 2001;Zaharia, 2006, 2013):
(i) double-layer compression. The DLVO (Derjaguin-Lindau-Verney-Overbeek) model is
considering that the space charge density of ions in water decreases rapidly with
distance from the surface, and potential declines exponentially as function of distance
(Figs. 2-3) (Yen, 2007). For water and monovalent electrolyte (i.e. ordinary salt, NaCl),
the reciprocal double layer thickness is about 11 Å at 0.1 M, and 101 Å for 1.10-3 M.
Some salt concentrations may be small enough for two particles to approach each other
and result in aggregation. Also, the higher valence of counter ions is shorten the double
layer thickness (i.e. Hardy rule: coagulation efficiency of counter ions increases mark-
edly with valency). The interaction energy is a simple additive term (ET), defines as:
ET = ER + EA ≤ 0 (4)
where: EA is van der Waals attraction energy, and ER is coulombic repulsive energy of
double layer. Some agglomeration behaviours for different destabilizing agents (coagu-
lants or flocculants) are illustrated in Fig. 4 (Yen, 2007; Zaharia, 2000, 2006, 2013).
ER = ε ⋅ a ⋅ψ δ ⋅ exp(− χ ⋅ u )
2
EA = - A =- A (5) (6)
12 ⋅ π ⋅ H 2 12 ⋅ u u+2
where: A – Hamaker constant; H – distance between colloid particles, [m]; u = x , x – distance
a
between the separation surfaces, [m]; a – radium of spheric particle, [m]; ε - water dielectric
constant, [F/m]; ψδ - superficial potential, equal to Zeta potential (ψδ=Z), [V]; χ - reversal of
thickness of double electric layer (H), [m].
173
The exact concentration of electrolyte (monovalent, divalent, or trivalent metal

salt) required to coagulate the colloidal particles depends on the co-ions rather than
counter ions (phenomenon known as salting-out). In addition, some anions can be added
to complete for charged particles for bound water formation. The effectiveness for
coagulation of added anions respects the Hofmeister series rule which considers the
following order: SO42- > Cl- > NO3- > I-.
(ii) charge neutralization and adsorption. The coulombic electrostatic energy involved
across the diffusion layer (potential of about 100 mV) of a typical colloidal particle and
a monovalent counter ion is only around 2 kcal/mole, being quite weak in comparison
with covalent, coordinative, or even hydrogen bonds (Yen, 2007). The colloid-
coagulant, coagulant-solvent (water), and colloid-solvent (water) interactions are
important when compared with the coulombic energy (i.e. colloids - surfactant-like
molecules such as dodecylammonium chloride). When a sufficient number of counter
ions is adsorbed, charge reversal occurs, and restabilization is acting.
Fig. 3. Representation of a double Fig. 4. Particles’ agglomeration behaviour for different

electric layer (mainly the diffuse layer) electrolytes (inorganic cations – Al3+, Ca2+, Na+
species, organic species) and polyelectrolytes
(hydrolyzed polyacrylamide)
If long-chain counter ions are attached to the colloid within the Stern layer, the effective
charge outside the shear layer is reduced, in contrast to the double layer repression
(double layer compression), which alters the charge distributions within diffuse layer.
(iii) entrapment in a precipitate (co-precipitation) and adsorption. The addition of coagu-
lants (i.e. Fe3+ and Al3+ salts) in colloids-containing water leads to formation of
polynuclear hydrolysis products – M(OH)nz+ which are adsorbed at particle-water
interfaces (e.g., hydrous metal oxide inferfaces). Moreover, the adsorption of cations
and anions at hydrous colloid interfaces can lead to surface complex formation and
ligand exchange equilibrium; e.g., amphoteric hydrous metal oxides reacting with
cations and anions in coodination reaction (Fig. 5; Yen, 2007) such as:
≡MOH2+ ↔ ≡MOH + H+ (Ka1) (7) ≡MOH ↔ ≡MO- + H+ (Ka2) (8)
174
≡MOH + Mz+ ↔ ≡MOMz-1 + H+ (*k1) (9) 2≡MOH + Mz+ ↔ (≡MO)2Mz-2 +2H+ (10)
≡MOH + A ↔ ≡MA
z- z-1 -
+ OH (k1) (11) 2≡MOH + Az- ↔(≡MO)2Az-2+2OH- (β2) (12)
E.g., ≡MOH + HPO4 ↔ ≡MHPO4- + OH- ↔ ≡MPO42- + H2O
2-
(13)
The adsorption of cations by hydrous metal oxides will lower the pHZPC, and
adsorption of anions will increase the pHZPC. The adsorption at the hydrous metal
oxides sites will modify the net electric charges. The maximum settling velocities of
particles are predicted at zero charge (at point which is at pH of isoelectric point - IEP).
Other charged particles are similarly enmeshed in colloids.
Fig. 5. Interactions of hydrous oxides with cations Fig. 6. Representation of turbidity and color
and anions in terms of surface complex formation removal by mineral coagulants based on
and ligand exchange equlibria (Stumm, 1978) magnetite (Yen, 2007)
(i) interparticles bridging. The polyelectrolytes (i.e. polymer or macromolecular

compounds with multiple ionizable functional groups on its chain, soluble in water,
cationic, anionic, or ampholytic in nature, and having macromolecular structures with
flexible chains and charges spreading over extensive areas) can modify the surface of
mineral particles leading to floc formation (Fig. 6). Restabilization can occur, not
throught charge inversal, but with excess of polymer, or prolonged agitation, or no
particle available and intramolecular adsorption by folding (Figs. 4, 6).
In practice, all four mechanisms are involved but latter two ones are implicated in
particle-size growth and/or aggregation known as flocculation process. Consequently,
coagulation-flocculation can be produced by (Zaharia, 2000, 2006, 2011, 2013):
- the attraction forces which will decrease the surface charge for permitting the
aggregation of particles in distinct flocs of higher sizes easely separable by
sedimentation (coagulation process);
- the simple electrostatic adsorption of counter ions that effectively neutralize the
particles, and decrease the surface potential (depending of particular simple cation or
anion; e.g., efectiveness of Na+, Ca2+ and Al3+ in coagulation process measured by
ionic concentrations which is of 1:10-2:10-3, or depending of large, complex molecules
used as coagulants or flocculants, and implicitly ordinary adsorption). Overdosage
with coagulant can result in particle-charge reversal due to adsorption of excess ions
175
(resulting stable colloids) (coagulation-flocculation process) (Zaharia, 2006; Zaharia

and Suteu, 2013; Zaharia et al., 2006 a,b, 2007);
- formation of precipitates (hydrated-metal hydroxides with low solubility limits) which
can adsorb on its particle surface other existing colloids, and act through charge
neutralization (pH effect is important; especially, the value of isoelectric point of
metal hydroxide) (coagulation-flocculation process) (Haller, 1995; Yen, 2007);
- enmeshment in a agglomerate-precipitate and adsorption, mainly when are used as
coagulant aids/flocculants the organic polymers (cationic, anionic and nonionic ones).
The ions presented in water interact with the polymer, and particle-aggregates are
formed, even in suprising situation when an anionic polymer is the most suitable
coagulant-flocculant for a negatively charged colloid (flocculation) (Schroeder, 1977;
Haller, 1995; Zaharia, 2000; Zaharia and Suteu, 2013; Zaharia et al., 2006 a,b, 2007).
Flocculation usually refers to the postdestabilization process in which
aggregations and large flocs are formed, as result of particle or small floc collision due to a
rapid stirring either by Brownian motion (perikinetic flocculation) or by velocity gradients
(orthokinetic flocculation). Both rapid and slow stirring are needed for a good and complete
flocculation. A schematic representation of the bridging model for the destabilization of
colloids by polymers is illustrated in Fig. 7 (O’Melia, 1972; Leu and Ghosh, 1988;
Kawamura, 1991; Tanaka and Pirbazari, 1986; Yen, 2007). As general agreed definition,
flocculation is the actual accumulation of the particles into settleable mass.
Bridging between polymers (polelectrolytes) and colloid particles
Fig. 7. Flocculation by bridging model of colloids with polymers (O’Melia, 1972; Zaharia, 2006)
The separation of dense formed agglomerates or flocs from surface water is

achieved by sedimentation or filtration/biofiltration. Sedimentation usually refers to settling
of the formed flocs without stirring for quiescence settling. Filtration usually refers to
separation of the formed flocs by free, vacuum or under pressure passing through a granular
solid layer of varying porosity and density (graded sand, garnet, coal, resins) supported by
176
gravel layers and/or porous underdrains (depth filters) or precoat filters. In natural aquatic
environment, the separation of fine particles is in majority of cases achieved by
sedimentation with or without coagulation-flocculation processes, but for specific water
bodies different filtration/biofiltration also occur by passing throught different solid layers
(rocks, aquatic trees, or other aquatic flora etc.).
Some particularities of orthokinetic flocculation related to perikinetic flocculation
are summarized in table 5, but both leads to reduction of potential for the double layer of
colloidal particle.
The collision efficiency for different colloidal particles-coagulant/flocculant
systems are presented in table 6, and some comparisons between coagulation-sedimentation
and filtration (as final separation after coagulation, flocculation and/or sedimentation) in
tables 7-9, and Figs. 8 and 8 (Strumm, 1978; Yen, 2007; Zaharia, 2006).
Table 5 - Orthokinetic flocculation versus perikinetic flocculation

Characteristics Orthokinetic flocculation Perikinetic flocculation
Interparticle process involved Hydrodynamic fluid motion or agitation Brownian interparticle contact (Boltman
(velocity gradient - G) constant - k, and temperature - T)
Energy regulation,  dN   2αGd 3  2  dN   4αGφ   dN   4αkT 
 ⋅N  ⋅ N
2
  = −  ⋅N   = −   = −
  dt ok  π   dt  pk  3µ 
i.e. Maxwell-Boltzman distri-  dt ok  3  , , , or
bution, associated with ln N/N0 = -4afGt / π,
sedimentation G=
P
=k⋅
P N = N0 / [1 + (4αkTN0 / 3μ)t] , or
V ⋅η V t1/2 = 3μ/(4αkTN0) = 1.6.1011/(αN0)
(Zaharia, 2006)
tF = 2 / k1N0, or tA= -ln(1-α)k12N0,
where: tF - flocculation time; tA - where: α - fraction of collision leading
adsorption time; α- fraction of colli- to agglomeration; D - Brownian
sion leading to agglomeration; G - diffusion coefficient (D= kT/(3πμd)); d
velocity gradient; P – real dissipated - particle diameter; k - Boltzman
power, [m2 Kg/s3, or W]; V – volume constant; T - temperature; μ –absolute
occupied of water, [m3]; η - dynamic viscosity.
viscosity, [Kg/m.s]; φ - volume fraction
of colloidal particles (φ = πd3N/6); d -
particle diameter; k1, k12 - appropiate
rate const.
Energy regulation,  dN  3 1 − f 
−  =  αηN
i.e. Maxwell-Boltzman For packed-bed filtration:  dl  2 d 
distribution, associated with where: f - porosity; 1-f - the volume of filter media per unit volume of filter bed; l -
filtration bed depth, η - a single collector efficiency, reflecting the rate at which particle
contacts occur between suspended particles and filter bed.
The overall rate of diminution dN  kT Gφ 
− = 4αN  N +
of particles is expressed as: dt  3µ π  , usually G = 10/s, φ = 10-4, α = 10-1, and t = 103 s.
Overall flocculation process Step: Effect of: Typical time scale:
(Gregory, 1987; Particle concentration Mixing rate
Gregory and Lee, 1990) - Mixing - + Seconds
- Adsorption ++ + 0.5 s to minutes
- Reconformation - ? 1 s to hours (?)
- Flocculation ++ + 0.1 s to minutes
- Floc break-up +? +++ Seconds
where: ‚-‚ sign indicates little or no effect expected; ‚+’ sign - estimated importance
of the step effect; ‚++’ - both important adsorption and flocculation steps; ‚?’ -
some incertainties; ‚+++’ - three important steps.
Example of different values of For a 0.1 µm particle, G is 104/s, whereas For a poor destabilized system (low
coagulation-flocculation for a particle of 10 µm, G is 102/s. Small α), t1/2 becomes large.
177
parameters or measures particles are not sufficient for separation,

but they should be aggregated into larger If a virus of 104/mL is completely
ones (of >1 µm). In general, G values destabilized (α=1), t1/2 still requires
varies as 400 – 1000 s-1 (in coagulation), 200 days.
and around 100 s-1 (in flocculation).
Table 6 - Collision efficiency for some colloidal systems treated by coagulation-flocculation (O’Melia, 1972)
Colloid Coagulant / Flocculant Type of G [s-1] η [Poisse]
flocculation
Polystyrene latex spheres NaCl Orthokinetic 11 0.448
Polystyrene latex spheres NaCl Orthokinetic 45 0.344
Polystyrene latex spheres Polyethylenimine Orthokinetic 11 0.217
Polystyrene latex spheres Polyethylenimine Orthokinetic 45 0.063
Silica Al3+ Perikinetic - 0.010
Silica Al3+ Orthokinetic 10 0.011
Oil Ca(NO3)2 Perikinetic - 0.355
Polystyrene latex spheres NaCl Perikinetic - 0.375
Polystyrene latex spheres NaCl Orthokinetic 1-80 0.364
Table 7 - Comparison between coagulation/flocculation-sedimentation, flotation and filtration

Design and Chemicals Coagulation aids, media Energy input, Residence time,
operational size, sludge recirculation mass transport filter lengths,
variables media diameter
Coagulation- α φ G t
Flocculation / Collision efficiency Volumetric concentration of Velocity gradient Time
Sedimentation suspended particles
Flocculation / α φ G t
Flotation Collision efficiency Volumetric concentration of Velocity gradient / Time
suspended particles Fair - air disperse flow,
d- air bubble diameter
Coagulation- α 1-f η L/d
Flocculation / Volumetric concentration Single collector Number of
Filtration of filter medium efficiency (ν, d) collectors
contact opportunities
REMARKS for separation of formed aggregates by coagulation-flocculation at daily design flow (Jiang et al., 1994):
Separation process Chemicals G, [s-1] Tcoag/flocc, [min] Overflow rate,
1st Intermed. Last vf, [m/h]
comp.* Comps.** comp.
Coagulation- Al3+ / Fe3+ 40-50 15-20 ≤ 10 25−35 0.8-1.0
Flocculation/ Ca(OH)2 30-40 15-20 ≤ 10 15−20 1.0-1.2
Sedimentation Fe2+ + Ca(OH)2 25-35 10-20 ≤ 10 15−20 0.8-1.0
Al3+/Fe3+ + polymer 50-70 30-40 ≤ 10 10−15 1.5-2.0
Flocculation/ Al3+ / Fe3+ 70-90 70-90 70-90 15−25 5.0-7.5
Flotation
Flocculation / direct Al3+ / Fe3+ > 100 >100 >100 5−15 5.0-10.0
Filtration + polymer
* 1st comp. - means the first settlement compartment; ** Intermed. Comps - means the intermediate settlement
compartment.
178
.
Tabel 8 – Characteristics of destabilization processes by coagulation-flocculation
Parameters Coagulation Coagulation by adsorption Flocculation
Destabilization agent Non-hydrolysing conter - Hydrolysing salts (of iron or Polymers and/or
ions aluminium); poyelectrolytes
- Superficial active conter ions,
soluble polynuclear compounds
Electrostatic effects Predominant Important Subordonated
Chemical and Do not take place usually Important Predominant
adsorption effects
Zeta aggregation Almost zero Almost zero In general different of zero
potential
Physical proprieties Dense and resistent Dense, filtrable, easy Easely breakable, volumeous,
of formed aggregates coagulation deshydrated coagulation tridimensional, easy filtrable
flocs
Addition of agent Without effect Restabilization because of Restabilization because of
charge exchange complete covering of surface
Relative covering of Not observable 0<φ<1 φ = 0.5
surface for optimal
destabilization
Necessary quantity of Independent of disperse Stoichiometric towards Stoichiometric
destabilization and phase concentration. It superficial concentration of
restabilization agent follows the Schultze – disperse phase
Hardy rule.
Fig. 9. Typical variables in coagulation-flocculation Fig. 10. Most suitable ranges for various applications for
in natural waters and wastewaters (Yen, 2007) particle removal in water and wastewater treatments
(Yen, 2007)
The efficiency of coagulation-floculation process in sedimentation of natural

surface water is important, the removal of suspended solids must be higher than 70%,
ideally of 100%.
In practice, the effect of coagulation-flocculation on sedimentation performance is
beneficial, being improved the suspended solids and turbidity removal (28-82 %) as
presented in tables 9 and 10 (Bolto, 1994; Zaharia, 2006).
179
Tabel 9 – Effect of coagulation-flocculation in primary sedimentation of a surface water (Zaharia, 2006)

Treatment Suspended solids, [mg/L] BOD5, [mg/L] Effective
Inffluent Effluent Removal, Inffluent Effluent Removal, removal,
[%] [%] [%]
Without 111 49 56 117 60 49 51
75 mg/LFe3++
0,6 mg/L HYPAM* 160 23 86 95 20 79
Without 110-280 45-80 56 110-145 42-72 54 52
150 mg/L Al3++
0,5 mg/L HYPAM 110-260 14-50 81 116-145 13-29 82
Without - - 50 - - 36 53
1 mg/L HYPAM - - 63 - - 45
Without 201 133 34 158 121 18 36
0,25 mg/L HYPAM 172 58 66 147 114 28
Without chemicals - - 45 - - 38 -
- - 70 - - 56
*
HYPAM – hydrolyzed polyacrylamide.
Tabel 10 – Application (in Australia) of organic polyelectrolytes in wastewater treatments (Barkacs et al.,
2000; Bolto, 1994; Bolto et al., 2001; Zaharia, 2006)
Stage Aplications Suspended Polyelectrolyte Polyelectro- Observa-
load, [mg/L] characteristics lyte dose, tions
[mg/L]
Preliminary Initial cleaning 125 – 400 - - -
High solids removal;
Pre-aeration
Primary Removal of organic 100 – 400 - Moderate and high charges; 0.1 – 6 Cationic
and inorganic - HYPAM* with with high polyelec-
matters by physical macromolecular mass used trolytes are
operations with/without inorganic /organic used when
coagulant separated
- AMPAMS** cationic with solid is
high-medium charge recycling.
Secondary Reduction of CBO 0.1 – 1.5 - moderate and high charge 0.2 –10 Dense flocs
leading to biological - cationic polymers for
attack settlement
Sludge Improvement of 0.1 – 5 - High and moderate charge 2 –10 -
concentra- water elimination - Cationic polymers
tion process
Sludge Reduction of sludge 2 – 10 % - high charge 0.5 - 35 Unitary
deshydra- humidity content - cationic polymers with mode- operations
tation rate-high molecular mass of high
torsions
*
HYPAM – hydrolyzed polyacrylamide; ** AMPAMS – cationic polyacrylamide.
3. COMMON ELECTROLYTES AND POLYELECTROLYTES ACTING AS

EFFICIENT COAGULANTS AND FLOCCULANTS
Turbidity in water is due mainly to different collection of solids having a range of particle
sizes (nano-, colloidal-, micro-size), shapes (sphere, tube, rod), and densities. The
coagulants and flocculants serve mainly to assist and aggregate particles in coagulation and
flocculation processes, in order to maximize removal of very small solid particles of
180
various compositions, but also to react with and remove some potential chemical polluting
species such as phosphorus species from the water (vanLoon and Duffy, 2005).
Direct addition of metal salts as iron salts to the water to be treated may cause
extremely rapid and uncontrolled hydrolysis process, and frequently, very rapid
precipitation (Jiang et al., 1994). In contrast, a controlled hydrolysis process may produce a
range of ferric hydrolysis products which may adsorb to colloidal surfaces to neutralize
their charge or may chemically interact with dissolved components in the raw water.
Therefore, the rate of coagulant interaction with colloidal and dissolved substances must be
faster than the rate of hydrolysis to low charge species and hydroxyde precipitate.
There are many organic and inorganic compounds that possess the ability to retard
the hydrolysis and polymerization processes of Fe(III), and the main criteria mostly
considered are: (i) appropriate affinity to Fe(III) comparable to OH; (ii) non-toxic and un-
treablesome/unproblematic in water and wastewater, and (iii) cheap and capable of being
produced industrially, or existing in sufficient amount in natural water (at interface
rocks/minerals-water, or in-deep water mass).
One example of coagulation process using ferric salts studied by many authors and
useful in removal of polluting species from water as phosphates (important role in
promoting water eutrophication) is illustrated below. The following known information is
mentioned considering the affinity of Fe(III) for phosphate that is inferior to that for the
hydroxy ion but much stronger than that for other anions such as: HO- > PO43- > F- > SO42-
> Cl- > NO3- > ClO4-.
The interactions of phosphate and hydroxy ion with Fe(III) species can lead also to
formation of fresh precipitates, composite complexes, or polymers following some possible
known mechanisms as (Gillberg, 1994; Tang et al., 1994; Zaharia, 2006):
- The precipitation reaction as the formation of ferric sulphate (Fe2(SO4)3), or inert part
of fresh precipitates like FexOz(OH)y(3z-2z-y)+ and high hydroxy ferric polymers
xFeOOH, xFe(OH)3 (mixtures) or Fex(OH)y(3x-y)+, where x is an order equal with 103
and/or 104:
Fe3+ (aq) + PO43- (aq) → FePO4 (s) (14)
Fe3+ (aq) + 3HO- (aq) → Fe(OH)3 (s) (15)
This reaction is completed sometimes with formation of complex precipitate if it was
present or added lime (calcium hydroxyde) in the water as:
5Ca(OH)2 (aq) + 3HPO42- (aq) → Ca5OH(PO4)3 (s) + 6HO- (aq) + 3H2O (16)
- The composite complex formation:
Fe3+ + H2O + H2PO4- ↔ [Fe(OH)(PO4)]- (17)
- The ligand exchange:
FeO(OH)...Fe...OH + HOPO3H2 ↔ FeO(OH)...Fe...OPO3H + H2O (18)
- Phosphate bridging:
Fe.O(OH).Fe.(OH)2.Fe.(PO4)2.Fe.(OH)(PO4).Fe. (19)
All these mechanisms lead to inclusion of phosphate groups in composite structures
of Fe(III), and also substitution of a part of hydroxyl groups. Important contribution of
181
phosphate stabilizer is improving of Fe3+ ion presence together with the active and effective
action for coagulation and flocculation.
Coagulation agents. The most used coagulants in current practice are still considering
aluminium salts (aluminium sulfate or chloride, sodium aluminate), iron salts (ferric
chloride or sulfate, ferrous sulfate, ferric chloro-sulfate), lime, mixed coagulants (based on
Al3+/Fe3+, polyaluminium chloride, polyferric sulphate etc.).
A schematic classification of some well-known coagulants and flocculants based
on origin of the compounds and their ionic characters is given in tables 11 (for coagulants)
and 12 (for flocculants), additionally being claimed in different patents (Jiang et al., 1994;
Kitchener, 1972; Lee et al., 2000; Morlay et al., 2000; Tang et al., 1994; Walker and Bob,
2001; Zaharia and Macoveanu, 1992, 1994; Zaharia, 2006). In addition to the sign of
charge (i.e. polyanion, or polycation), the relative charge density has an important influence
in the coagulation and/or flocculation performance together with the molecular weight of
the polymer (i.e. polyelectrolytes), or macromolecule and water pH.
Table 11 - Classification of some known coagulants used in destabilization/stabilization of colloidal systems

Origin of Inorganic or organic Destabilizing ionic or Characteristic reactions /
coagulants category molecular species interactions / usage doses
Natural (a) Organic natural coagulants
products -Alginic acid, manuronic - alginates are extracted from marine algae
- Na-Alginates
acid and guluronic acid (used doses of 5-150 mg/L)
Derivatives of - Starch - OH, =HC-O-CH=, - starch is extracted from cereals ( used
natural products -COO- doses of 1-150 mg/L together with
Fe2(SO4)3).
(a) Inorganic coagulants
Synthetic
Aluminium salts: - Al3+, or Al(H2O)63+, or 2AlCl3 + 6HCO3- ↔ 2Al(OH)3 + 6Cl- + 6CO2
products AlCl3, Al2(SO4)3, - monomeric, dimeric and Al2(SO4)3 + 6HCO3- ↔ 2Al(OH)3 + 3SO42- +
(Zaharia, 2006) lime + Al2(SO4)3; Al2(SO4)3 + polymeric hydroxo 6CO2
Na2CO3, NaAlO2, commercial aluminium complexes as Al2(SO4)3+ 3Ca(OH)2 ↔ 2Al(OH)3+ 3Ca2+ +
2+
product such as AlOH(H2O)5 , 3SO42-
4+
Aln(OH)p(Cl)2(SO4)r (e.g., WAC, Al2(OH)2(H2O)8 , Al2(SO4)3 + 6Na2CO3 + 6H2O ↔ 2Al(OH)3 +
Aqualene, Alcoclar), polyalu- Al13O4(OH)24(H2O)127+ +12Na++ 6HCO3- + 3SO42-
minium chloride (PAC) (used doses of 5-100 mg/L) NaAlO2 + Ca(HCO3)2 + H2O ↔ Al(OH)3 +
CaCO3 + Na+ + HCO3-
Iron salts: - Fe3+, or Fe(H2O)63+, or Fe2(SO4)3 + 6HCO3- ↔ 2Fe(OH)3+ 3SO42- +
+ +
- ferric salts: Fe2(SO4)3, FeCl3, - Fe(OH) , Fe(OH)2 6CO2
FeClSO4, - Monomeric, dimeric, and FeCl3 + 3H2O ↔ Fe(OH)3 + 3H+ + 3Cl-
lime+ Fe2(SO4)3, polymeric hydroxo iron 2FeClSO4 + 6HCO3- ↔ 2Fe(OH)3 + 2Cl- +
mixed product of Al3+/Fe3+ complexes as dimer 2SO42-+ 6CO2
as sulfate - AVR; polyferric Fe2(OH)24+, Fex(OH)y(3x-y)+ Fe2(SO4)3+ 3Ca(OH)2 ↔ 2Fe(OH)3+ 3SO42- +
(3x-3z-y)+
sulphate (PFS); , FexOx(OH)y 3Ca2+
(used doses of 1-120 FeSO + 2HCO - ↔ Fe(OH) + SO 2- + 2CO
- ferrous salts: FeSO4, 4 3 2 4 2
mg/L) FeSO4 + Ca(OH)2 ↔ Fe(OH)2 + Ca2+ + SO42-
lime + FeSO4
Lime CaO,Ca(OH)2,Ca(H2O)62+ CaO + H2O → Ca(OH)2
(used doses of 5-40 mg/L)
Acids (HA) H+, or (H3O)+ Anionic Colloid(-) + H3O+ → hydrated
(used doses of 5-50 mg/L) and relatively neutralized colloid + (H2O)
CuSO4. 5H2O Cu2+, Cu(H2O)62+ (used CuSO4 + 2HCO3- ↔ Cu(OH)2 + SO42- +
doses of 25-130 mg/L) 2CO2
(II ) Effects of surface charge and initial suspension stability on inorganic coagulant performance
(vanLoon and Duffy, 2005, 2010; Levine et al., 1991)
Colloidal CEC* range, Colloid CEC range, Colloid CEC range,
particle [cmol(+)/kg] [cmol(+)/kg] [cmol(+)/kg]
182
Kaolinite 3 – 15 (8) Chlorite 10-40 (25) Feldspar 1-2 (2)

Halloysite 4-10 (8) Vermiculite 100-150 (125) Quartz 1-2 (2)
Montmorillonite 80-150 (100) Hydrous iron and ~4 Organic 150-500
aluminium oxides matter (200)
*
CEC – Cation Exchange Capacity of various materials found in colloidal size fraction.
(III) Effects of basicity, OH/Coagulant, ion charge in destabilization of colloidal particles from high turbidity
water with aluminium salts (Gillberg, 1994; Jiang et al., 1994; Tang et al., 1994)
Basicity, [%] Ion formula OH/Al * Average charge per Ion charge
aluminium atom
0 Al(H2O)63+ 0 +3.00 +3
33.3 AlOH(H2O)52+, 1 +2.00 +2
4+
33.3 Al2(OH)2(H2O)8 , 1 +2.00 +4
7+
82.1 Al13O4(OH)24(H2O)12 2.46 +0.53 +7
*
The OH/Al ratio of the coagulant and the other most efficiently precipitation agents for phosphates in the raw
waters are: (i) 1.9-2.1 (for 2.45 mg P/L) in Norweige (the best OH/Al=1.9), and (ii) 0-1.5 (for 9.03 mg P/L) in
Sweden (the best OH/Al=1.1), respectively.
(IV) Water treatment by coagulation (e.g., coagulants as ferric sulphate-FS, polyferric sulphate-PFS, aluminium
sulphate-AS (Jiang et al., 1994) and sedimentation leading to polluting compound removals of:
Coagulant Temperature, Algae Removal, [%] *
[°C] Total cell, Color UV Turbidity, COD,
[No./mL] (A436 nm) (A 254 nm) [NTU] [mg O2/L]
Ferric sulphate 4 Microcystis 53 81.2 69.2 50 12.5
(FS - FeSO4) 18 62 85.3 76.8 60.5 15.5
(8 mg/L Fe, 4 Asterionella 72 89.5 80.5 56 18
pH= 4.0) 18 77 91.1 84.8 68 24
Polyferric 4 Microcystis 75 91.3 82.2 68 22.4
sulphate (PFS) 18 81.6 92 83.2 69.5 24.5
(6 mg/L Fe, 4 Asterionella 78.5 89.6 80.6 70 27.5
pH= 4.0) 18 84 90.3 82.4 72.5 30.5
Aluminium (AS) 4 Microcystis 60 91.4 75.7 59 20
sulphate (pH5.0, 18 78 92.0 82.5 81 24
5 mg/L Al)
Raw water Fe=0.005 mg/L Microcystis 5.8 x104 4.86 / 5.82 38.8 /32.5 6.1 / 8.4 8.2 / 9.4
(pH=8.1) Mn=0.14 mg/L Asterionella 6.2 x 104 [m-1] [m-1] [NTU] [mg O2/L]
*
After water treatment by coagulation-sedimentation the concencentration of residual Fe(III) and Al(III) was no more
than 0.098 [mg Fe/L] (4°C) and 0.09 mg Fe/L (18°C] for PFS; 0.18 [mg Fe/L] (4°C) and 0.165 mg Fe/L (18°C] for PS,
and 0.074 [mg AL/L] (4°C) and 0.064 mg Al/L (18°C] for AS.
Table 12 - Classification of some known flocculants used in destabilization of colloidal systems

Origin of Non-ionic Anionic Cationic Amphoteric
flocculants
Natural - Gum guar; - tannins, - Chitin - Gelatine : albumen
products - Starch (Zaharia, 2012) - alginates (biopolymer from
(Divakaran and - carboxylic acid crustaceans-crab,
Pillai, 2001; biopolymers prawn shells,
Renault et al., 2009) arthropods, fungi)
- Starch derivatives; - Na-alginate; - Chitosan (polymer - Coss-linked gelatine:
Derivatives of - Dextrin; - Phosphated starch; of D-glucose) aminated tannin
natural products - Cellulose derivatives - Na-carboxy methyl - Cationic starches
cellulose (Na-CMC);
- Sulphated
polysaccharides;
- Modified lignin
sulphonates
183
Synthetic - Organics: - Organics: - Organics: - Polyacrylamide

polymers (e.g., -Polyacrylamide (AAm) - partially hydrolyzed - Polyethyleninimine (AAm)
polyelectrolytes) as commercial products: polyacrylamide (AAm) (PEI): Vinyl pyridine-
Superfloc 992, Polyfloc or copolymers of acryl- acrylamide copolymers
- the used polyelectro- 365P, Nalfloc N671, BTI, amide and acrylamide - Chitosan or polyglu-
lyte dosage of 0.1-10 or Teprofloc TE75, acid (AAm/AA), coseamine,
mg/L for organic, and Mahnafloc LT27 - Poly(styrene - DADMAC*,
5-100 (mainly 5-30)
-Polyethylene oxide sulfonic acid) (PSSA) - DMA/ECH**,
mg/L for inorganic - AAm/Q***
one.
(PEO),
-Polyvinyl alcohol (PVA) - inorganic: PAC-poly-
- Inorganic: sulphonic
aluminium-chloride;
acid polymers
PASS-polyaluminosi-
licate sulphate; ione-
nes; sulphonium
polymers
(II) Effects of surface charge and initial suspension stability on polymeric flocculant performance
(Hogg and Ray, 1988)
Colloidal particle pH Surface Initial disper- Min.dosage to reduce turbidity to < 50 NTU, [mg/L]
charge sion state Nonionic Anionic Cationic
Clay 3-4 - (+edge) Poor 3 2 5
7-8 - Moderate 20 nf 20
11 - Good 45 nf 30
Al2O3 4-5 + Good 50 120 nf
9 0 Poor 5 5 *
11 - Good ** nf 25
(III) Water treatment by using flocculants (MW varying from 10-3 to 10-6 - 10-7 [g/mol]) (Bolto, 1994; Barkacs et
al., 2000; ), having different unitary processes/operations such as:
Process Polymer type CD MW Example
(charge density) (molecular weight)
Dissolved air anionic L-M H AAm/AA
Flotation cationic L H AAm/Q
Foam flotation cationic L H AAm/Q
Enhanced primary treatment stage with:
Alum/Fe3+ anionic L H AAm/AA
Lime cationic L H AAm/Q
Sludge thickening anionic M H AAm/AA
cationic M H AAm/Q
Red mud ex bauxite anionic H H AAm/AA
*
DADMAC - poly(diallyl dimethylammonium chloride) (medium-high MW); ** DMA/ECH - polymer from dimethylamine and
epichlorohydrin (medium-high MW); *** AAm/Q - copolymer of acrylamide and quaternized dimethylaminoethylacrylate (R=H; high MW, or
low to high CD).
(IV) Water treatment by flocculation (e.g., flocculants as PDADMAC (100%), PEI (95%, or 6%), Chitosan (98%,
or 17%) (Bolto et al., 2001) and sedimentation leading to natural organic matter, color or clay removals of:
Optimal doses, Color removal, UV absorbersd
pH Polyelectrolyte Origin [mg/L] [%] removal, [%]
No clay Clayc No clay Clay No clay Clay
4.5 PDADMACa (100%) Synthetic 3.0 2.0 50 80 42 44
7.0 PDADMAC (100%) Synthetic 3.1 4.0 86 100 55 54
b
4.5 PEI (95%) Synthetic 0.5 0.4 60 60 43 43
7.0 PEI (6%) Synthetic 3.9 1.0 8 80 15 35
4.5 Chitosan (98%) Natural deriv. 1.5 2.0 100 60 40 43
7.0 Chitosan (17%) Natural deriv. 2.2 5.0 60 67 38 35
a
PDADMAC – polydiallyldimethylammonium chloride of high MW (CD 100%); b PEI – polyethyleneimine with low CD
at neutral pH and low MW; c Clay added (20 mg/L) as types of palygorskite, illite, bentonite, etc; d UV absorbers means
UV absorbing species.
184
Natural organic matter (NOM) together with fine turbidity particles is removing
from natural water resources for drinking purposes by primary coagulation-flocculation
with polyelectrolytes (especially cationic ones) followed by settling and filtration. The
target is to covert soluble organics into an insoluble form. The use of polymers as primary
coagulants avoids the production of extra solids like metal hydroxides formed by hydrolysis
when alum or metal salts are used as the coagulant, but the NOM reduction is only partial
and fine divided solids where present in water after filtration. The combination of metal salt
coagulants with long-chain polyeletrolytes of high charge density (CD) is more useful than
only metal coagulants which produce voluminous sludges than that resulted in shorter filter
runs. Mixes of coagulant and polymer are a convenient way to have suitably reactive
particles present, waters being more easier to treat.
The interactions involve polyvalent metals at the clay surface and adsorption of
humic acids or generally NOM (i.e. > M – OH + RCOO- → > M – OOCR + HO-, where
NOM is considered as ligand in exchange between carboxylate groups of organics and
hydroxyl groups bound to a metal on the surface of the solid) (Bolto et al., 2001), together
with H-bonding, hydrophobic interaction between polymer molecules adsorbed onto
adjacent particles, other ionic exchanges mainly because of water salinity, ionic strenght
and amount of divalent cations in water.
4. EXPERIMENTAL PART: A CASE STUDY OF

BAHLUI RIVER IN IASI CITY AREA (SPRING, 2007)
This work continues author research studies in which are presented some results performed
in laboratory scale set-up experiments applied on samples of Bahlui River (Romania) based
mainly on coagulation-flocculation tests followed by sedimentation, and analysis of the
most important influencing factors (pH, temperature, coagulant/flocculant dose, stirring
regime at almost neutral pH, operating time, or sedimentation) for separation of fine
turbidity particles from fresh water and its performance (in spring season, 2007).
4.1 Bahlui River – location and important characteristics
The Bahlui River is originated in Botosani County, at the Western part of Suceava Plateau,
and Northern part of Dealu Mare hill, 500 m far from Tudora site. The Bahlui River mouth
is in Jijia River, not far away from Chipiresti. The most important transitory cities are
Hârlău and Iasi (Zaharia and Suteu, 2013).
The total length of Bahlui River is 104 km, having an annual average flow of 2.8
m3/s. The total hydrographic basin surface is of ca 1,915 km2, being situated in a water
deficitary area, with a lot of industrial and agricultural units alongside that influence the
river quality and health status, mainly by ecological implications (Benchea et al., 2011;
Robu et al., 2008; Zaharia and Teslaru, 2012; Zaharia and Suteu, 2011 a,b).
The Bahlui River has a length of 14 km in Iasi city, and passes through it
separating the industrial site area by the important residential city areas. The principal
pollutants of Bahlui River are the organics in nature (biodegradable and non-biodegradable
compounds), nitrogen- and phosphorus-containing compounds, heavy metals, micro-
organisms or biotas. The Bahlui River was monitoring in spring time season (2007) in
seven control sections for rapid weekly control of some quality indicators (i.e. more than 10
185
physical-chemical indicators; e.g., pH, turbidity, suspended solids; oxygen regime:

dissolved O2, COD, BOD5; mineralization or salinity level; specific toxics: some heavy
metals, extractible substances in solvents, petroleum products, phenols), and in three rapid
daily control sections where Bahlui water corresponds or is obvious necessary to be of the
Ist quality category (i.e. Letcani, Tudor Vladimirescu, and Holboca).
Data from annual statistic report indicated globally the IInd and IIIrd water quality
categories of Bahlui River in Iasi city (from physical-chemical, microbiological and
biological quality indicators), with small exceptions.
4.2 Analysis methods of water quality
Some physical-chemical quality indicators were analysed based on Romanian standard

methods (RS) internationally approved (ISO or EN), together with its chemical reagents
(kits), stock reference solutions and operating parameters for the gravimetric, titrimetric and
spectrophotometer-based method used (Zaharia and Teslaru, 2012; Zaharia and Suteu,
2013; Zaharia and Radu, 2013; Zaharia, 2014 a,b,c), such as:
- General indicators as pH (HACH OneLine laboratory pH-meter, with specific
electrode, SR ISO 10523-97); colour (SR ISO 7887/1997, absorbance at 436, 525
and 620 nm, or Hazen colour unit); turbidity (SR EN ISO 7027: 2001, or test with
Drell DR 2000 spectrophotometer, Hach Co.), suspended solids (STAS 6963-81),
total hardness (titrimetric method with EDTA); oxygen regime indicators as dissolved
oxygen (SR EN 25814/1999), chemical oxigen demand (COD) (SR EN 1484/2001, or
SR ISO 6060/1996), biochemical oxygen demand (BOD5) (SR EN 1899/2002); salinity
indicators as fixed residue (STAS 6963-81);
- Specific indicators as some contents of anions and cations such as nitrites (STAS
3048/1-96), nitrates (STAS 8900/1,2-96), ammonium ions (STAS 6328-85), phosphates
(SR EN 1189/2000), sulphates (STAS 8601-70);
- Toxic indicators as phenol and phenolic derivates (SR ISO 6439/2001 or SR ISO 8165-
1/2000), extractible substances in organic solvents (SR 7587/1996), and heavy metals
(STAS 7884-91, STAS 8637-79; SR ISO 11083:1998).
All the chemical reagents were of analytical purity (p.a.) necessary for advanced
instrumental laboratory analysis. The pH adjustment was done with HCl 0.1M or NaOH
0.1M. There were used for water quality analysis some digital analysers (Hach One
Laboratory pH-meter; Drell DR/2000 spectrophotometer, Hach Co., with specific reagent
kits; SP Plus 830 spectrophotometer, Metertech Inc.), but also conventional methods
(gravimetric or titrimetric) for: chemical oxygen demand (COD), biochemical oxygen
demand (BOD5), total hardness, chlorides, sulphates, extractible substances, fixed residues,
and/or spectrophotometer-based methods for: nitrate, nitrite, phosphate, ammonium ion,
and phenol index (Surpateanu and Zaharia, 1999, 2002, 2006; Zaharia, 2014c).
Water sampling is performed in recipients (of plastic and glass, capacity of 2 L)
from the second daily control section of Iasi city (Tudor Vladimirescu) in spring season
(March-April). Some analysis were immediately done but for others the collected samples
were individually conserved and storaged (by refrigeration/cooling) for more than seven
days for later on contradictory data validation. The method sensibility is depending of type,
reference material and apparatus utilised, all analysis accuracy and precission being good
enough for evaluation of water quality (0.01-0.0001 M, deviation error of max. ± 10%).
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4.3 Working methodology
Surface water samples (300 mL) from Bahlui River were treated at laboratory scale set-up
scale by coagulation-flocculation processes using Jar tests mainly for removal of fine
turbidity solids, suspended solids and dissolved organics in as much as possible high
proportion; the solid separation is followed by sedimentation and/or filtration. All the
coagulation-flocculation tests were performed in the same operating mode (i.e. 2 min-
rapidly stirring at 300 rpm, and 20 min-slowly stirring at 50 rpm, followed by min. 30 min-
settling) for comparative performance study of different coagulants/flocculants (mainly
dose and type).
pH adjustment was not performed, and the studied coagulants and polymeric
flocculants in coagulation/flocculation-sedimentation tests were as follows:
- aluminium hydroxychlorosulphate – AHCS (CAS No. 17 927-65-0; EC No. 233-
1350; solubility in water of 600 g/L at 20°C, pH= 3.5 for 50 g/L-aqueous AHCS
solution; LD50 (on rats)= 5000 mg/lg) ,
- ferric sulphate (stock solution of 34 mmol/L, Fe2(SO4)3.18H2O, purchased from SC
Nordic Invest SRL Cluj Napoca), and
- bentonite (fine powder solid of indigen origin, Iasi city area);
- anionic Ponilit GT-2 polylectrolyte (Zaharia, 2000, 2006, 2013; Zaharia et al., 2006 a,
b, 2007), the sodium salt of a copolymer based on maleic acid and vinyl acetate
prepared at the “Petru Poni” Institute of Macromolecular Chemistry, Iasi (Patent,
1981), stock concentration of active compounds of ≅ 33-36% (w/w), density of 1.18-
1.21 g/cm3, pH range (6.5-8), water soluble, viscosity (20⁰C) of 1500-3000 cP, with
high macromolecular weight of 2x105 - 3x106 [g/mol]. The working polyelectrolyte
concentration was of 0.5 % (w/v).
Supernatant samples (25 mL) were analysed for determination of the important
studied quality indicators, especially turbidity, content of suspended solids, colour, COD,
and total iron content. The coagulation-flocculation performance for Bahlui River treatment
is appreciated by the treatment degrees or removals of turbididy, suspended solids, and
colour.
5. RESULTS AND DISCUSSION
The quality analysis of Bahlui River from annual report (spring season, 2007) is indicated
the IInd and/or IIIrd quality category, for majority of dissolved substances (Fig. 11) as
follows (Zaharia, 2008b; Zaharia and Teslaru, 2012; Zaharia and Suteu, 2013):
- in control section – Letcani-Iasi: COD of 5.34-10.23 mg O2/L (IIIrd category),
ammonium ions of 0.59-1.04 mg/L (IInd category), phenol of 0.002-0.033 mg/L (IIIrd
category), and total iron ions of 0.02-0.45 mg/L (IInd category),
- in control section - Tudor Vladimirescu-Iasi: COD of 10.71-16.17 mg O2/L (D-
degraded category), ammonium ions of 3.20-4.91 mg/L (IIIrd category), phenol of 0.003-
0.10 mg/L (IIIrd-D-degraded category), and total iron ions of 0.20-0.75 mg/L (IIIrd
category),
- in control section - Holboca-Iasi, downstream of Dancu wastewater treatment
plant: COD of 8.86-12.13 mg O2/L (IIIrd category), ammonium ions of 3.92-4.39 mg/L (IInd
category), phenols of 0.001-0.022 mg/L (IIIrd - D-degraded category), and total iron ions of
187
0.9-1.20 mg/L (IInd category).

The average values of some heavy metal concentrations, dissolved oxygen and
total phosphorus (total P) content are illustrated in Fig. 12 (Benchea et al., 2011; Robu et
al., 2008; Zaharia and Suteu, 2013). It seems that these values are in the admissible limits,
exceeding sometimes a little bit the limits as consequence of periodic climate change
(seasonal change), thermal stratification of in-deep water layers, and soil errosions.
The relative high content of suspended solids, turbidity and coloured water bodies
in this period of year (spring season) was always a serious concern for environmental
protection regulators. Some in situ induced water treatments can be considered for
improving the water and sediment quality in some control sections, especially for Tudor
Vladimirescu-Iasi control section of Bahlui River (for suspended solids, dissolved organics
and also heavy metals). Therefore, some laboratory scale set-up coagulation-
flocculation/sedimentation tests were performed for some collected water samples.
Fig. 11 - Average values [mg/L] of some quality indicators (COD, BOD, ammonia, nitrate, nitrite,
phenols) of Bahlui River in Tudor Vladimirescu-Iasi control section area (spring season, 2007)
Fig. 12 - Average values [mg/L] of some quality indicators (pH, dissolved oxygen, total P,
some heavy metals) of Bahlui River in Tudor Vladimirescu-Iasi control section (spring 2007)
188
Some coagulation-floculation – sedimentation laboratory scale set-up tests (Jar

test: 2 min-rapidly stirring at 300 rpm, and 20 min-slowly stirring at 50 rpm, followed by
30 min-settling) were organized for study the efficiency of two types of coagulants (AHCS,
ferric sulfate), a coagulation aid (bentonite), an anionic polyelectrolyte (Ponilit GT-2), and
some combinations of these, together with at least once annually mechanical sediment
minimization and cleaning (sediment evacuation with special devices and vaccum tools).
All tests were performed on the same collected samples of Bahlui River with the main
characteristics presented in table 13, in order to obtain high removals using iron-based
coagulants, coagulation aids and/or convenient polyelectrolyte.
Table 13. Some physical-chemical quality indicators of Bahlui River (Tudor Vladimirescu control
section-Iasi, spring 2007)
Indicator Measured value Indicator Measured value
Colour, absorbance 456 nm (HU) 1.797 (1604.5) CODCr, [mg O2/L] 20.12
Turbidity, [FTU] 554 BOD5, [mg O2/L] 5.11
Suspended solids (SS), [mg/L] 656 Extractible substances, [mg/L] 15.60
pH 7.80 Phenol and its derivates, [mg/L] 0.96
Chlorides, [mg/L] 70.7 Sulfates, [mg/L] 117.8
Total hardness, [°G] 7.86 Fixed residues, [mg/L] 895
The results of coagulation-sedimentation experiments (Jar tests) are summarized in

table 14 (Zaharia and Suteu, 2013) using all tested coagulants individually or in mixture,
and the removal efficiency for turbidity, suspended solids (SS) and colour are illustrated in
Figs. 13-14 working with inorganic coagulants, Fig. 15 using anionic polyelectrolyte, and
comparatively working with all types of tested chemicals in Fig. 16.
Table 14. Results of Jar tests applied for Bahlui River samples (Tudor Vladimirescu-Iasi control
section, spring 2007) using the tested chemicals (AHCS, ferric sulphate, bentonite) (Zaharia and
Suteu, 2013)
Bentonite, Fe2(SO4)3, Quality Dose of AHCS, [mg/L]
[g/L] [mg/L] indicator 0 3 5 15 25 50 75
0 0 Colour (A456) 1.797 1.875 1.290 1.017 0.567 0.137 0.304
Turbidity, [FTU] 552 596 410 306 165 38 83
SS, [mg/L] 652 652 475 361 188 42 100
0 3.45 Colour (A456) 1.797 0.952 1.085 0.385 0.515 0.175 0.296
Turbidity, [FTU] 552 278 330 109 145 50 76
SS, [mg/L] 652 323 377 118 165 53 90
0 10.35 Colour (A456) 1.797 0.854 0.489 0.357 0.293 0.096 0.205
Turbidity, [FTU] 552 246 142 99 81 27 58
SS, [mg/L] 652 292 154 110 89 30 63
3.35 0 Colour (A456) 2.096 1.541 1.475 1.183 1.012 0.854 1.297
Turbidity, [FTU] 1020 492 464 372 311 289 333
SS, [mg/L] 1288 504 452 416 343 312 396
3.35 3.45 Colour (A456) 2.096 1.280 1.506 1.107 0.941 0.833 1.189
Turbidity, [FTU] 1020 415 492 331 276 212 244
SS, [mg/L] 1288 482 758 393 297 256 324
3.35 10.35 Colour (A456) 2.096 1.323 1.442 0.731 0.541 0.722 1.013
Turbidity, [FTU] 1020 449 460 214 172 198 224
SS, [mg/L] 1288 521 686 250 187 232 288
189
There were performed relative good removals higher than 70 % for AHCS
coagulant doses higher than 25 mg/L, but maximal doses of 75 mg/L are enough in these
Jar tests, because the removals were decreased for colour and turbidity at higher coagulant
doses. The best removals were performed with 50 mg/L AHCS (i.e. 88.59% for colour,
89.49% for turbidity, and 90.34% for suspended solids).
Fig. 13 - Removals by coagulation-sedimentation Fig. 14 - Removals by coagulation-sedimentation

with Fe3+ ions-based coagulant dose (3-75 mg/L) with different AHCS coagulant dose (3-75 mg/L)
and ferric sulphate (3.35 and 10.35 mg/L)
It is observed that the most high removals are performed with a mixture of coagulants,
AHCS + Fe2(SO4)3, but with individual AHCS coagulant, the removals of all three quality
indicators are closed enough.
Fig. 15 - Removals by coagulation-sedimentation with individual and mixed

coagulants/flocculants of: 1 - ferric sulphate; 2 - Ponilit GT-2 anionic polyelectrolyte+ferric sulphate,
and 3 - Ponilit GT-2 polylectrolyte+ferric sulphate+bentonite
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The use of organic polyelectrolyte (Ponilit GT-2) increases with only 12.1 – 38.6 %
the removals in all Jar tests, the highest removals (colour – 91.87%, turbidity – 80.59%, and
suspended solids – 87.99%) being performed with combination of relative small doses of
polylectrolyte (0.3 mg/L), trivalent iron salt (5 mg/L ferric sulphate) and coagulation aid –
bentonite (0.3 g/L). Without bentonite, the best removals (colour – 93.66%, turbidity –
95.11%, and suspended solids – 95.4%) where obtained with relative small concentration of
coagulant (15 mg/L) and flocculant (10 mg/L) being closed enough to the above mentioned
ones, and usable mainly in cost-restrictive times.
Fig. 16 - Removals by coagulation/flocculation-sedimentation with individual or mixed

coagulants/flocculants of: 1- 50 mg/L AHCS+ 3.35 mg/L Fe2(SO4)3, 2- 50 mg/L AHCS+3.35 mg/L
Fe2(SO4)3+3.35 g/L bentonite, 3- 50 mg/L AHCS, 4- 30 mg/L Fe2(SO4)3, 5- 15 mg/L Fe2(SO4)3+10
mg/L Ponilit GT-2, 6- 5 mg/L Fe2(SO4)3+0.30 mg/L Ponilit GT-2+0.3 mg/L bentonite
It seems that the highest removal for all three quality indicators (colour – 95.66%,
turbidity – 95.11%, and suspended solids – 95.4%) is performed with the combination of
inorganic coagulants together with the coagulation adjuvant (i.e. 50 mg/L AHCS + 3.35
mg/L Fe2(SO4)3 + 3.35 g/L bentonite) but the removal value is closed enough to the
removal performed with combination of only iron-based coagulants (colour – 92.38%,
turbidity – 93.12% and suspended solids – 93.56%).
The lowest removal had AHCS alone (colour - 51.67%, turbidity - 80.59%,
suspended solids – 81.99%) closely followed by that with ferric sulphate as coagulant. The
utilization of organic anionic flocculant (Ponilit GT-2 polyelectrolyte) in combination with
ferric sulphate and also bentonite was beneficial but not exceeded the removal results
performed with only inorganic coagulants used (colour – 91.67%, turbidity – 80.59% and
suspended solids – 87.99%).
For obtaining water treatment degrees higher than 70-75% for all quality indicators
can be used combination of twice (i.e. AHCS + Fe2(SO4)3, or Fe2(SO4)3 + Ponilit GT2) or
three (i.e. AHCS + Fe2(SO4)3 + bentonite, or Fe2(SO4)3 + Ponilit GT-2 + bentonite)
stabilizing/destabilizing chemicals.
191
The residual concentrations of total iron (Fe2+ + Fe3+) in the clear supernatant after
45 minutes of Jar tests at the normal pH of Bahlui River samples directly collected (no
addition of pH regulators) are indicated in table 15 (Zaharia and Suteu, 2013), together with
the volume of sludge/sediment produced during coagulation-sedimentation treatment.
The increasing of ferric ions dose decreases the residual iron concentration in the
supernatant, mainly because of coagulation-flocculation-sedimentation process. The higher
dose of ferric sulfate increased supersaturation of Fe(OH)3, and consequently increased
nucleation rate of Fe(OH)3, and removed the dissolved iron in solution by adsorption and/or
retaining by the precipitate. Increasing in the supersaturation of Fe(OH)3 nuclei favors their
union and hence effective coagulation/flocculation (Zaharia, 2000, 2013; Zaharia and
Suteu, 2013; Zaharia et al., 2006 a,b, 2007).
Table 15. Residual concentration of iron (Fe2++ Fe3+) (mg/L) and sludge/sediment volume vs. coagulant
dose (Zaharia, 2000, 2013; Zaharia and Suteu, 2013)
AHCS coagulant Fe2(SO4)3 dose, Bentonite dose, Residual (Fe2+ + Sludge/sediment

dose, [mg/L] [mg/L] [mg/L] Fe3+), [mg/L] volume, [mL/L]
0 0 0 2.44 4
3 0 0 2.13 7
5 0 0 1.72 7
15 0 0 1.34 9
25 0 0 0.68 9
50 0 0 0.64 9
75 0 0 0.52 9
3 3.35 0 2.28 14
50 3.35 0 1.94 12
75 3.35 0 1.84 11
3 10.35 0 2.36 3
50 10.35 0 2.06 14
75 10.35 0 1.83 12
3 3.35 3.33 1.83 27
50 3.35 3.33 1.72 24
75 3.35 3.33 1.23 23
3 10.35 3.33 0.96 22
50 10.35 3.33 0.73 38
75 10.35 3.33 0.54 37
Coagulation process using 50 mg/L AHCS efficiently reduced colour, turbidity

and total suspended solids by more than 90 %. Increasing the coagulant dose above 75
mg/L caused total suspended solids (TSS) to increase in a diminishing fashion. The pH
values of 7.10-7.30, required higher dose of metallic cations. This is the reason of addition
of ferric ions as coagulant, or higher increasing of coagulant dose. This fact might pose a
health hazard as a result of residual quantities of excess chemical additives (aluminium and
iron ionic species), which can also interfere with fish survival and growth in the receiving
surface water.
The data from table 15 indicate that the total iron (Fe2+ + Fe3+) ions are still in
admissible limits in the aquatic environment treated by coagulation-sedimentation
(legislative reference data; Zaharia, 2008a).
The sediment separated at the bottom of basin must be periodically evacuated
from Bahlui River, dried and treated in order to be efficiently valorized (e.g., as soil in
192
mixture with the reference soil from covering area or ingredient in preparation of composite
materials).
6. CONCLUSIONS
This chapter is written firstly to support the statement of theoretical knowlege in

stabilization/destabilization field of fine turbidity solids in natural waters and final effluents
discharged in its, as the different principles and mechanisms that govern the various particle
separation unit processes, and also by demonstations of water characteristics (e.g., a
Romanian watercourse case study of Iasi city) and different destabilization process
performances mainly by coagulation-flocculation-settling (Jar tests) using different
destabilizing inorganic and/or polymeric chemicals, in laboratory scale set-up practice.
An important part of contaminants in raw water is associated with particles, and
therefore the direct particle separation is the most effective way of lowering contaminants
levels in the water. In addition, coagulation-flocculation / precipitation / formed floc
separation is probably the most cost effective practical way to remove contaminants in raw
waters and discharging effluents in its.
Improved particle removal in physical-chemical and biological treatments may be
performed by improving coagulation-flocculation prior to settling (e.g., by implementing
the sludge recirculation in biological flocculation, and chemical coagulation-flocculation in
the total phosphorus post-precipitation).
In order to evaluate the particle separation efficiency of different treatment
processes, water samples should always be analyzed for total and soluble matter, but also of
turbidity and suspended solids content. From all the presented information, it is concluding
the strong opinion that the only safe methods of fine turbidity particles separation are firstly
by chemical precipitation, then the coagulation-flocculation and land (or other) filtration or
air flotation, and afterwards river or other watercourse oxidation.
Some practice results of various water and wastewater treatments by coagulation-
flocculation processes followed by settling, filtration or air flotation are illustrated in terms
of efficiency, cost, and load changes. Also, some general remarks on the optimisation of
coagulation/flocculation within respect to the floc separation process used are discussed
together with the factors influencing the separation of newly formed agglomerates like
particles type and content, organic loading and coagulation-flocculation conditions during
treatment on subsequent particle separation. Must be mentioned that the removal of organic
matter in many of these treatments is suprisingly high, and higher than what is normally
experienced in the pre-precipitation step of some continental water treatments.
In addition, a study of coagulation-flocculation-sedimentation using the ferric
sulphate, AHCS, synthetic PONILIT GT-2 anionic polyelectrolyte with/without bentonite
was applied at laboratory scale set-up for Bahlui River samples collected in spring season
of 2007, for removing of water turbidity and color. Therefore, the values of some physical-
chemical quality indicators were analyzed, and permitted the estimation of Bahlui River
quality of IInd and IIIrd category in the Tudor Vadimirescu-Iasi control section.
The most indicated values for coagulant dose are of 25-75 mg/L AHCS, 3.35-
10.35 mg/L ferric sufate, and 0-3.33 g/L bentonite, and permitted to get removals closed to
68.45-89.49 % for turbidity, 28.21-88.59 % for colour, and 27.15-90.34 % for suspended
solids. The combination of iron-based coagulants has as direct result the production of
193
sludge, but in a reduced volume with more than 30-40 % in comparison with that formed
with individual (solely) use of coagulant for water treatment.
The use of organic flocculants as the anionic polyelectrolyte (Ponilit GT-2) was
beneficial for use in combination with ferric salts, but did not surpassed the removals
performed with only inorganic iron-based coagulants in mixture.
These laboratory results are useful as direct, ease and simple remediation actions,
in case of serious and severe local pollution episodes of Bahlui River by fine turbidity
particles loading.
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Coagulation-ﬂocculation processes in water and wastewater treatment. (II)

Chapter · September 2014

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Coagulation-flocculation processes in water and wastewater

Keywords: coagulation, colloids, destabilization agents, flocculation, quality indicator, inorganic

complex processes and/or operations such as natural sedimentation, filtration, or

Indicator/expression mode of Classification of contaminants in water

These fine particles (both hydrophilic and hydrophobic colloids) possess

2. THEORETICAL PART ON THE IN / EX SITU COAGULATION AND

≡Si – OH2+ ↔ (K1)/-H+ Si – OH ↔ (K2)/-H+ Si – O- (1)

Cu (s) + 2H2S ↔ Cu(SH)22- (surface) + 2H+ (2)

The charges of colloidal particles are essential to the understanding of colloidal

The exact concentration of electrolyte (monovalent, divalent, or trivalent metal

Fig. 3. Representation of a double Fig. 4. Particles’ agglomeration behaviour for different

(i) interparticles bridging. The polyelectrolytes (i.e. polymer or macromolecular

(resulting stable colloids) (coagulation-flocculation process) (Zaharia, 2006; Zaharia

Bridging between polymers (polelectrolytes) and colloid particles

The separation of dense formed agglomerates or flocs from surface water is

Table 5 - Orthokinetic flocculation versus perikinetic flocculation

parameters or measures particles are not sufficient for separation,

Table 7 - Comparison between coagulation/flocculation-sedimentation, flotation and filtration

The efficiency of coagulation-floculation process in sedimentation of natural

Tabel 9 – Effect of coagulation-flocculation in primary sedimentation of a surface water (Zaharia, 2006)

3. COMMON ELECTROLYTES AND POLYELECTROLYTES ACTING AS

Table 11 - Classification of some known coagulants used in destabilization/stabilization of colloidal systems

Kaolinite 3 – 15 (8) Chlorite 10-40 (25) Feldspar 1-2 (2)

Table 12 - Classification of some known flocculants used in destabilization of colloidal systems

Synthetic - Organics: - Organics: - Organics: - Polyacrylamide

4. EXPERIMENTAL PART: A CASE STUDY OF

4.1 Bahlui River – location and important characteristics

physical-chemical indicators; e.g., pH, turbidity, suspended solids; oxygen regime:

4.2 Analysis methods of water quality

Some physical-chemical quality indicators were analysed based on Romanian standard

4.3 Working methodology

5. RESULTS AND DISCUSSION

0.9-1.20 mg/L (IInd category).

Some coagulation-floculation – sedimentation laboratory scale set-up tests (Jar

The results of coagulation-sedimentation experiments (Jar tests) are summarized in

Fig. 13 - Removals by coagulation-sedimentation Fig. 14 - Removals by coagulation-sedimentation

Fig. 15 - Removals by coagulation-sedimentation with individual and mixed

Fig. 16 - Removals by coagulation/flocculation-sedimentation with individual or mixed

AHCS coagulant Fe2(SO4)3 dose, Bentonite dose, Residual (Fe2+ + Sludge/sediment

Coagulation process using 50 mg/L AHCS efficiently reduced colour, turbidity

This chapter is written firstly to support the statement of theoretical knowlege in

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