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Coagulationflocculation mechanisms in
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potential measurements
Article in Journal of Hazardous Materials August 2014
Impact Factor: 4.53 DOI: 10.1016/j.jhazmat.2014.06.025

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Coagulationocculation mechanisms in wastewater treatment

plants through zeta potential measurements
E.A. Lpez-Maldonado a, , M.T. Oropeza-Guzman a,b , J.L. Jurado-Baizaval a ,
A. Ochoa-Tern b
a
Centro de Investigacin y Desarrollo Tecnolgico en Electroqumica, Unidad Tijuana, Carretera libre Tijuana-Tecate km 26.5,
esq. Blvd Nogales Parque Ind. El Florido CP 22444, Tijuana, B.C., Mexico
b
Centro de Graduados e Investigacin en Qumica del Instituto Tecnolgico de Tijuana, Blvd. Alberto Limn Padilla s/n, Mesa de Otay, C.P. 22500, Tijuana,
B.C., Mexico

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

A well planned polyelectrolyte dosing strategy plays a crucial role in successful coagulationocculation process.
pZpH plots are a powerful tool
to plan polyelectrolytes dosage and
to discover coagulationocculation
mechanisms.
Previously
prepared
polyelectrolytes
dispersions
improved
resulting water quality after a
coagulationocculation process.

a r t i c l e

i n f o

Article history:
Received 19 March 2014
Received in revised form 20 May 2014
Accepted 6 June 2014
Available online 21 June 2014
Keywords:
Coagulationocculation mechanism
Polyelectrolyte complexing capacity
Electroplating wastewater
ContaminantPE interaction

a b s t r a c t
Based on the polyelectrolyte-contaminant physical and chemical interactions at the molecular level, this
article analyzed and discussed the coagulationocculation and chemical precipitation processes in order
to improve their efciency. Bench experiments indicate that water pH, polyelectrolyte (PE) dosing strategy and cationic polyelectrolyte addition are key parameters for the stability of metalPE complexes.
The coagulationocculation mechanism is proposed based on zeta potential () measurement as the
criteria to dene the electrostatic interaction between pollutants and coagulantocculant agents. Polyelectrolyte and wastewater dispersions are exposed to an electrophoretic effect to determine . Finally,
zeta potential values are compared at pH 9, suggesting the optimum coagulant dose at 162 mg/L polydadmac and 67 mg/L of occulant, since a complete removal of TSS and turbidity is achieved. Based on
the concentration of heavy metals (0.931 mg/L Sn, 0.7 mg/L Fe and 0.63 mg/L Pb), treated water met the
Mexican maximum permissible limits. In addition, the treated water has 45 mg O2 /L chemical oxygen
demand (COD) and 45 mg C/L total organic carbon (TOC). The coagulationocculation mechanism is proposed taking into account both: zeta potential ()pH measurement and chemical afnity, as the criteria
to dene the electrostatic and chemical interaction between pollutants and polyelectrolytes.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Corresponding author. Tel.: +52 6646453278.
E-mail addresses: elopez@cideteq.mx, eduardo a lm@hotmail.com
(E.A. Lpez-Maldonado).
http://dx.doi.org/10.1016/j.jhazmat.2014.06.025
0304-3894/ 2014 Elsevier B.V. All rights reserved.

The electroplating wastewater, in the semiconductor industry,

contains dissolved and suspended heavy metals (such as Sn, Cr,
Ni, Pb, and Cu, among others), making necessary to nd a suitable

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

water treatment to remove them before disposal. Hazardous situation are challenged when dissolved and suspended heavy metals
are not completely removed before being discharged into the
sewage.
In recent years, several technologies have been developed
to regulate the hazard of wastewater containing heavy metals
and focusing in the decrease of wastewater volume and the
improvement in recovered water quality [1,2]. Within the
conventional physicochemical methods to treat electroplating
wastewater, it can be mentioned: chemical precipitation [36];
coagulationocculation [3,7]; otation [8,9]; electrocoagulation
[10,11]; zeolites, clays and resins ion exchange [1216] and membrane ltration (ultraltration, nanoltration and reverse osmosis)
[17,18]. In all these cases, wastewater content such as metals,
organic matter (OM) and total suspended solids content are
included.
Chemical precipitation has been applied to remove dissolved
heavy metals. This method is based on the chemical reaction
between the metallic cations and calcium hydroxide as precipitating agent resulting in the formation of insoluble compounds, and
the subsequent solid separation by sedimentation or ltration [19].
The general reaction for this process is:
Mn+ + nOH M(OH)n

(1)

where Mn+ and OH represents the dissolved metal ions and the
precipitating agent, respectively, and M(OH)n is the insoluble metal
hydroxide. Chemical precipitation is, in many cases, unable to comply the permissible limits due to the fact that metallic hydroxides
in wastewater do not precipitate at the same pH [19], and depends
on metal concentration.
The colloidal nature of wastewater and surface charge of the
metallic hydroxide could make more difcult the solidliquid separation, as well as the presence of organic complexing agents that
reduce the removal effectiveness [6]. Even if the pH condition and
solubility product are known, it is uncertain to calculate the solubility of heavy metals in electroplating wastewater [2022]. It is
well known that large amount of impurities, such as organic matter, make the metal solubility greater than that expected, mainly
due to the chemical interactions between the metallic cations and
organic matter [23].
Zeta potential () is an interfacial parameter related to the low
solubility condition of dissolved metals when the isoelectric point
is reached. There are inclusive precipitating agents that assist the
formation of metal hydroxides by the zeta potential reduction of
residual water [24]. In all cases, the formation of metal hydroxides
depends on the change of surface charge as a function of pH [2528].
Other chemical precipitation treatments have been tested in the
last century, particularly those using sulde (Na2 S); however, high
cost and struggle in the disposal of toxic sludges discourage its use
[29]. Also, sodium phosphate was used to precipitate a metal phosphate, but the concentration of residual phosphorus in the treated
water exceeds the maximum allowable limit [19,30,31].
New technologies are oriented to mixed pollutants removal (i.e.
particles, organic matter and metals simultaneously). In particular, the combined coagulationocculation process is addressed
to eliminate suspended particles and insoluble substances. Even
though, removal of toxic heavy metals from electroplating wastewater by coagulationocculation remains being a challenge due
to the mixed of chemicals such as organic matter, suspended particles and metallic cations. Until now, there are no physicochemical
method to nd the optimal dose for each contaminant removal by
coagulationocculation, unless Jar test. However, exploring the
chelating ability of coagulant and occulant polyelectrolytes (PEs)
is an alternative to optimize the removal of various the types of
pollutants [32].

This paper explores the chelating ability of commercial coagulant and occulant polyelectrolytes (PEs) used in real wastewater
treatments. Selected conditions for coagulationocculation are
presented, as well as removal mechanisms suggested for suspended
solids, organic matter and metallic cations for four different strategies of PE dosing.
To explain the mechanisms and interfacial phenomena
occurring during coagulationocculation process under various
physicochemical conditions, four different sets of experiments
were planned and developed. The mechanism elucidation of
PEpollutants interactions can be used to set up the optimal process
conditions for wastewater treatment.
The rst of four sets of experiments was the characterization of
electroplating raw wastewater to compare against the permissible
limits of applicable Mexican environmental regulation (NOM-002SEMARNAT-1996); the second was to construct the  = f(pH) graphs
to establish different PE dosing strategies; and third, identify the
coagulationocculation regions for the removal of metals, suspended solids and organic matter.
The experimental strategy, to study the conditions of
coagulationocculation process was to examine the proles of
 = f(pH) of commercial PEs used in semiconductor assembly waste
water treatment plants. Once the isoelectric point of the coagulant and occulant was determined, as well as that of the sampled
wastewater, PE dosing was studied at different pH values. In parallel the effect of using an interpolyelectrolyte complex occulation
in the selected window was tested. Finally, the effect efciency
of coagulant dose in the occulation selected window by the
dual occulation process was established. Based on the nature of
the interfacial phenomena that occur between pollutants and PEs
in the coagulation-occulation process and the electrochemical
nature of the measurements of zeta potential, the experimental
methodology used allowed us to determine the mechanisms of
coagulationocculation.
2. Materials and methods
2.1. Reagents
Semiconductor industry commercial polyelectrolytes Polydadmac (OPTIFLOC C-1008) and Flocculant (Trident 27,506) were used
[32]. Commercial testing water quality reagents for Hach methods were used. All other reagents used in this work were reagent
grade.
2.2. Methods
2.2.1. Wastewater sampling in the assembling semiconductor
industry
The wastewater sampling protocol in the assembling semiconductor industry was followed as recommended by Mexican
sampling standard (NMX-AA-003-1980). A detailed chemical composition is uncertain due to the large amount of chemical mixtures
employed in the electroplating baths [33]. Sampling planning was
made in accordance to regulation parameters, selected electroplating process knowledge and water treatment control parameters.
Included parameters are: metals (Sn, Pb and Fe), total suspended
solids (TSS), turbidity, electrical conductivity (EC), zeta potential
(), particle size, color, pH, chemical oxygen demand (COD), total
organic carbon (TOC), biochemical oxygen demand (BOD5 ) and
total nitrogen (TN).
2.2.2. Preparation of wastewater dispersions
The wastewater dispersions were prepared by diluting 5 mL
of raw wastewater with deionized water in a 50 mL volumetric ask. Since the electroplating process was in continuous

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

operation according a timetable protocol, the sampled water content was considered as process representative.
2.2.3. Nonstoichiometric polyelectrolyte complexes (NIPECs)
preparation
Anionic NIPECs synthetic solutions were prepared in ratios from
0.1 to 2 mg of cationic PE/mg anionic PE. Each solution was stirred
thoroughly stirred before  measurement.
2.2.4. Colloid titration
A synthetic solution of 10 mg polydadmac/L was prepared by
diluting the corresponding volume of 1.28 mM polydadmac solution to 10 mL with distilled water in a volumetric ask. The
prepared solution was poured into a 20 mL vial to measure the
initial . Then, sequential amounts of 1.24 mM poly(vinyl sulfate)
potassium salt (PVSK) titrant solution were added. The solution was
stirred after each addition and  measurement recorded. Titrant
additions were made to reach the isoelectric point corresponding
to turbidity appearance in the solution [34].
2.2.5. Chemical precipitation
Three waste water dispersions (see Section 2.2.2) were poured
into vials and the pH of each was adjusted to 5, 7 and 9 respectively
by adding NaOH 1 M. The vials were shaken for 2 min and allowed
to settle during 2 min. Finally the supernatant was separated to
measure , TSS, particle size and metals concentration.
2.2.6. Micro-Jar tests
The procedure was as described in Section 2.2.5 but this time PE
dosage tests (micro-Jar tests) were performed in 20 mL vials. Progressive additions of microliters of 0.1093 g/L occulant solution
were made. After each addition, the vials were shaken for 2 min
and allowed to settle for 2 min. Finally the supernatant was withdrawn to realize turbidity, , TSS, metals concentration, BOD5 , COD
and TOC measurements.
The coagulationocculation experiments are generally divided
into two parts: single occulation, optimum condition for operation
using only one PE and dual PE occulation.
2.2.7. Analytical techniques
Immediately after the samples treatment, they were analyzed
for biochemical oxygen demand in 5 days, BOD5 , chemical oxygen demand, COD, and metals quantitation by atomic absorption
spectroscopy, all of them following the test methods established
by Mexican Standards (NMX-AA-028-SCFI-2001, NMX-AA-030/2SCFI-2011 and NMX-AA-051-SCFI-2001) similar to ISO standards
and other published methods. Zeta potential and size particle measurements were performed following manufacturer instructions
(Zetasizer Nano-ZS, model ZEN3500). All other measurements were
performed in accordance to Hach methods using a Hach DR 890
colorimeter, a Hach Digital Reactor DRB200 (digestor) and HQ40d
Multiparameter (Luminescent dissolved oxygen LD0101-01 Probe
and Conductivity Meter CDC401-01 Probe).
2.2.8. Scanning electron microscopic (SEM) images and
energy-dispersive X-ray spectroscopy (EDS) microanalysis
The samples were analyzed by SEM and X-ray microanalysis.
The analysis was performed on a SEM coupled to EDS (JEOL, JSM6390 LV) microscope to observe the composition. SEM provides
images of rough material with a resolution down to fractions of a
micrometer, whereas energy-dispersive X-ray spectroscopy offers
in situ elemental analysis.
2.2.9. Speciation
Metal species were approached by predominance area diagrams
software named MEDUSA (making equilibrium diagrams using

sophisticated algorithms) published by Ignasi Puigdomenech as

a free tool for chemical equilibrium studies, considering pH and
metals concentration commonly used in electroplating baths. Isoelectric points of metallic compounds were also used to determine
insoluble species [2628].
3. Results and discussions
3.1. Characterization of wastewater from electroplating process
in a semiconductor industry
As shown in Table 1 selected electroplating wastewater pH is
far away from regulation range, zeta potential is high in order to
stabilize suspended particles. Organic content measured by BOD5
and TOC is not of concern. Metals, TSS, turbidity and COD contents
are too high so these are the critical parameters for the wastewater treatment. All of them, as well as the zeta potential , are
directly related to the stability of the suspended solids. For raw
wastewater  = 45 mV (pH 0.8), indicating the presence of positively
charged particles suspended in water and probably related with
metallic cations adsorbed on suspended particles. As particle size
decrease, longer sedimentation times are expected. Physical properties as turbidity and TSS also indicate that raw wastewater is a
stable dispersion. Considering water properties, the separation of
heavy metals, and suspended solids using coagulationocculation
processes seems to require the addition of negatively PEs.
3.2. Determination of the isoelectric point for the electroplating
wastewater
In the rst stage (coagulation) suspended solids are destabilized
by changing the water pH and proting that  tends toward zero
when the isoelectric point is approached. A simple pH variation
could be enough to stabilize or destabilize dispersions. Moreover,
the performance of polymeric PEs is inuenced by the wastewater
pH. Thus the pH value may control both polyelectrolyte charge density and suspended particles surface charge. The isoelectric point of
the dispersion generated in the electroplating process is detected
in a  = f(pH) plot.
Using the colloidal titration method ( = 0, as detection point)
the charge density (CD) of the anionic and cationic PE (occulant
and coagulant) is determined as polydadmac 22 meq/g and occulant 5 meq/g. These values conrm the polydadmac high charge
density and its use as a coagulant, while the occulant does not
require high charge density to accomplish the solid agglomeration.
In Fig. 1 the  = f(pH) plot shows the charge density variation for
Table 1
Characterization of electroplating wastewater.
Parameter

Electroplating
wastewater

Maximum
permissible limita

Sn (mg/L)
Pb (mg/L)
Fe (mg/L)
TSS (mg/L)
Turbidity (FAU)
EC (mS/cm)
 (mV)
Particle size (nm)
Color
pH
COD (mg O2 /L)
TOC (mg C/L)
BOD5 (mg O2 /L)
TN (mg N/L)
Biodegradability (BOD5 /COD)

4854
1044
683
4510
2990
74
45
346
Milky
0.8
1432
125
30
50.6
0.02

NIb
1.0
NI
40
NI
NI
NI
NI
NI
5.510
NI
NI
30
NI
NI

a
b

Monthly average limit of NOM-002-SEMARNAT-1996.

Not included in the standard.

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

Fig. 1. Electrokinetic properties of the dispersion of wastewater from electroplating,

20.8 mg/L polydadmac and 21.9 mg/L occulant.

suspended particles in wastewater, as well as the proper pH to

achieve the isoelectric point. In the same plot it can be observed
that polydadmac does not reach an isoelectric point and occulant
reaches it at very low pH. These results imply that at pH higher than
5, occulant is expected to be very efcient, while polydadmac is
more effective at pH <10. For higher pH values polydadmac diminish its charge density certainly due to the ammonium hydrolysis
[35].
To corroborate the TSS observable phenomena in relation to
interfacial phenomena (through zeta potential) and nanoscale
particle diameters, different combinations were studied and are
discussed below. Further studies were conducted to analyze the PE
dosage inuence for organic matter content (COD and TOC).
3.3. Chemical precipitation
According to speciation thermodynamics of dissolved metals in
the electroplating waste water, predominance of insoluble metal
compounds in the form of micro and nanoparticles, as well as
the chemical surface changes that pollutants undergo at each pH
range are determined. In Fig. 2, the type of pollutant and the
chemical species that predominate in each pH range are shown.
In electroplating waste water at pH as low as 0.8 the metals are
in dissolved cationic form (Sn2+ , Pb2+ and Fe2+ ); metallic cations
complexed with organic material such as SnOM, FeOM, PbOM
and micro and nano suspended particles mainly of Sn. As the pH
of the wastewater increases, free metallic cations are converted
to their corresponding insoluble compounds such as SnO, Fe(OH)2
and Pb(OH)2 . While the content of metallic cations complexed with
organic material remains constant. When the pH of electroplating
waste water is adjusted to 5, Sn2+ is involved in a series of chemical precipitation and acid-base reactions, the insoluble compound
of Sn which predominates at pH 5 is SnO, according to literature
information, it has its isoelectric point at pH 4 [2628]. Particles
in suspension undergo acidbase reactions on its surface as the
pH increases. Physicalchemical surface character is a determining
factor in the adsorption of PEs on the surface of the metal particles. Sn particles in suspension at pH 5 acquire a slight negative
surface charge, leading to activate sites for adsorption of dissolved
metallic cations. Pb(OH)2 has its isoelectric point at pH 9.5 [2628],
due to this electrokinetic property and the adsorption of metals
on SnO particles, the waste water has a positive zeta potential of
11.7 mV.
When the wastewater pH is 7, insoluble SnO, Pb(OH)2 , Fe(OH)2
species predominate. However, the ionization of SnO surface group,
conferring it a negative charge which allows the adsorption of
metallic cations and the interaction with the metal hydroxides
of Fe and Pb. This promotes the aggregation phenomenon of the

Fig. 2. Contaminant type and the chemical species that predominate in each pH
value.

coagulated particles by neutralization of charge, which is observed

as an increase of particle size (784 nm) and a  value of
0.7 mV.
At pH 9, Thermodynamics predicts that the chemical equilibria give advantage to the formation of SnO, Pb(OH)2 and Fe(OH)2
insoluble products. The  value of 18.6 mV suggests that the surface groups of metal hydroxides and oxides particles are completely
ionized and confer stability to the suspended particles.
The removal of suspended metals is determined by the particle
size and surface charge of formed metal species. The content of
dissolved metals is determined by the relative amount of metallic
cations complexed with organic ligands.
The removal efciency of metals from waste water treatment
only by chemical precipitation at different pH values is shown in
Table 2. Also the  values of the supernatant. It is observed that
metal removal efciency increased as pH does. The resulting EDS
and SEM analysis of obtained solids from this neutralization is presented in Fig. 3. The EDS spectrum shows that the chemical content
of solids follows the order: O > Sn > P > Pb > Fe > Si > Al. This order
conforms to contents presented in Table 1, except for phosphorus,
element not included as critical parameter but appearing as a major
component. The zeta potential varies from 0.7 to more negative values with increasing pH from 7 (isoelectric point) to 10, suggesting
that the solids can be stabilized, however, the removal of metals
Table 2
Efciency of metal removal by chemical precipitation.
Metal

Sn
Pb
Fe
 (mV)

% Metal removal efciency

pH 5

pH 7

pH 8

pH 9

pH 10

45
35
25
11.7

50
40
30
0.7

57
45
36
7.5

60
50
50
18.6

59
49
48
23.2

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

Fig. 3. SEM micrograph and EDS spectrum of the solid obtained from electroplating process wastewater.

increases, reaching the maximum removal efciency of 60% Sn, 50%

Pb and 50% Fe at pH 9. The metals removal remains practically constant at pH 10 despite that, accordingly to  value; the suspended
particles are expected to be more stable in suspension.
At the isoelectric point, pH 7, corresponding to the neutralization of wastewater the separation of the solids is not the most
efcient due to factors such as particle size, metal complex stability
and gravity sedimentation time.
3.4. Process coagulationocculation (single occulation A)
The anionic PE has its isoelectric point at pH 23; therefore in
the coagulation step at pH 5 the PE has some ionized functional

groups (partially ionized) that confer negative charge density. Thus

PE chains acquire a slightly extended conguration (see Fig. 4). In
the low PE dose region, before the electroplating wastewater isoelectric point, the ionized surface groups of the macromolecules are
able to interact with both positives surface groups of metal particles
and with dissolved metals.
When the electroplating waste water isoelectric point is reached
at pH 5 by subsequent PE dosing, all suspended metals are separated
and exceeding PE can complex the remaining dissolved metals. In
the region of PE overdose stable aggregates (particlePEmetal)
are formed. The elimination of Sn shows a very similar behavior of SST removal, suggesting that most of SST correspond to
SnO.

Fig. 4. PEcontaminant interaction and coagulationocculation mechanism at pH 5.

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

Fig. 5. TSS and occulation of residual metals at pH 5 using single occulant.

Fig. 5 shows the variation of residual metals and TSS content

in the single occulation A at pH 5. TSS removal requires higher
doses, up to 100%, compared with the single occulation at pH 7.
At a occulant dose of 33.5 mg/L the maximum removal of TSS is
reached, while at pH 7 15.6 mg/L of occulant are required.
This fact shows the pH effect on the charge density of the occulant (see Fig. 1) that decreases at lower pH corresponding to
negative  values. The residual concentration of Pb and Fe decreases
slowly compared to the Sn diminution. The optimal occulant dose
of 33.5 mg/L for TSS removal implies a residual metal content of
66 mg/L of Sn, 105 mg/L of Pb and 120 mg/L of Fe.
At a higher dose than the optimal dose for TSS removal, 40 mg/L,
the maximum metal removal is reached (Sn 65 mg/L, Pb 89 mg/L
and Fe 74 mg/L) without re-stabilization and particles dispersion.
This establishes the optimum dose for both the TSS and metals

removal. However, the residual metal concentration in the supernatant is higher (50% Sn, 60% Pb and 51% Fe) compared with single
occulation supernatant at pH 7.
At a higher dose than the optimal dose of 40 mg/L, the TSS
removal decreases and the dissolved metal content increases, thus
this is the particles re-dispersion region. It is noteworthy that
the re-stabilization is less pronounced compared to the overdose
region of single occulation at pH 7.
This is because at pH 7 the charge density is increased and
any increase in concentration greater than the optimum dose
results in stabilization of suspended particles. Furthermore, the
occulation window for removing TSS shifted at higher concentrations (33.540 mg/L) compared with single occulation at pH 7.
It is noteworthy that in the occulation window of 33.540 mg/L
of occulant residual Sn concentration remains virtually constant (6765 mg/L), while the concentration of Pb (15089 mg/L)
and Fe (12074 mg/L) has a higher diminution. The minimum
residual metal concentration in the optimal occulant dose of
40 mg/L is related to the afnity of the occulant to each metallic
cation.

3.5. Process coagulationocculation (single occulation B)

As discussed above the isoelectric point of the waste water is pH
7. However, the settling time of the solids by gravity is about 1 h
without addition of PE and the supernatant exceeds the maximum
permissible metals content and suspended solids. This demonstrates the need to adding PE to favor the settling rate of suspended
solids.
The residual concentration of Pb and Fe decreases slowly
compared to the Sn diminution. At the optimal occulant dose
(15.6 mg/L) for the TSS removal (0 mg/L) indicates that the optimal dose complies the maximum permissible limit of TSS content,
while metals content is 30 mg/L of Sn, 90 mg/L of Pb and 65 mg/L of
Fe (see Fig. 7).

Fig. 6. PEcontaminant interaction and coagulationocculation mechanism at pH 7.

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

Fe concentration from 65 to 38 mg/L and wastewater COD content

from 1558 to 122 mg O2 /L. However, TOC remains broadly constant
at 119 mg C/L (see Fig. 6).
3.6. Process coagulationocculation (single occulation C)
NIPECs were prepared at a ratio of 1.5 mg polydadmac/mg
occulant with the following characteristics: size 132 nm and
 = 25 mV (Fig. 7). The formed complexes are used as a new occulant destabilizing the dispersed solids of the electroplating process
wastewater (see Fig. 8).
At NIPECs dose of 35.6 mg/L maximum metals removal is
provided (34 mg Sn/L, 42 mg Pb/L and 30 mg Fe/L). At the optimal NIPECs dose interval (2435.6 mg/L) the removal of TSS and
residual metal content slightly decrease. At doses greater than
41 mg NIPECs/L TSS and residual metal concentration increases
(see Fig. 9).
Fig. 7. TSS and occulation of residual metals at pH 7 using single occulant.

At a higher occulant dose of 20.1 mg/L, higher metal removal

is obtained (30.4 mg/L Sn, 56 mg/L Pb and 38 mg/L Fe) indicating that increasing metal removal requires an overdose of
occulant. At higher occulant doses than 20.1 mg/L, TSS and
metals content increases, this corresponds to the re-dispersion
region.
The occulation dose range for TSS removal of 15.620.1 mg/L
but occulation dose for maximum metal removal is punctually
20.1 mg/L of occulant. Within the occulation range residual
Sn concentration remains virtually constant (31 mg/L) which
means that lower occulant concentration is required to achieve
maximum Sn removal and a greater Snocculant afnity compared to the other two metals. Within the occulant window
(15.620.1 mg/L), Pb concentration is decreased from 90 to 56 mg/L,

3.7. Process coagulationocculation (dual occulation D)

The maximum removal by chemical precipitation of metals is
achieved at pH 9 where the particles have a negative surface charge,
 = 18.6 mV. Therefore the cationic PE was added in the coagulation step to neutralize the surface charge of the dispersed particles
(see Fig. 10).
Fig. 11 shows the residual metal content and TSS dual occulation at pH 9 using polydadmac and occulant. At 162 mg/L
polydadmac dose, TSS and metals removal is strongly dependent
on the occulant dosage. At occulant dose of 26.36 mg/L a maximum TSS removal is provided (0 mg/L); however, the concentration
of metals (16 mg Sn/L, 45 mg Pb/L and 28 mg Fe/L) exceeds the
maximum permissible limits.
The optimal occulation window of TSS removal is wider
(2667 mg/L of occulant) compared to single NIPECs occulation
at pH 5 and 7. Within the occulation window of optimal TSS
removal, the tendency is of decreasing residual dissolved metals

Fig. 8. NIPECspollutant interaction and coagulationocculation mechanism at pH 7.

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

Fig. 9. TSS and residual metal concentration of occulation at pH 7 using single

NIPECs.

Fig. 11. TSS and residual metals dual occulation at pH 9 using polydadmac and
occulant.

concentration as occulant dose increases to 67 mg/L, as well as

in other single occulation cases, without particles re-stabilization
for its dispersion.
However, occulation dose of 67 mg/L provides maximum metal
removal (0.931 mg Sn/L, 0.627 mg Pb/L and 0.7 mg Fe/L). This occulation condition comply the maximum permissible limits of
Mexican regulation. Unlike single occulation, the residual Sn concentration decreases from 16 to 0.9 mg/L within the occulation
window. By adding a occulant excess (77 mg/L) TSS and the residual metals concentration increases. Fig. 10 shows that at this dose
the  value is 16.7 mV, indicating increased stability of the dispersed particles.

According to the waste water characteristics (TSS and metals),

in the simplest systems and dual occulation is observed that TSS
removal requires lower doses of occulant than those required
to increase metal removal. Furthermore, according to Lopez et al.
[32] this is due to the degree of afnity of the occulant with
the metals present in the waste water, lower doses of occulant
are required for the Sn removal compared to Pb and Fe. The proposed organic removal mechanism is shown in Fig. 12. Once the
optimal dose of occulant for the removal of TSS and metals is
reached, the cationic PE interacts with organic matter and simultaneously occulant compete for metallic cations complexed. So at
a occulant dose of 67 mg/L treated water has both COD and TOC
reduced.

Fig. 10. PEcontaminant interaction and coagulation-occulation mechanism at pH 9.

E.A. Lpez-Maldonado et al. / Journal of Hazardous Materials 279 (2014) 110

Fig. 12. PEcontaminant interaction and coagulationocculation mechanism at pH 9.

4. Conclusions

References

Based on literature thermodynamic information and experimental data obtained in this work, coagulationocculation
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knowledge facilitating the selection of optimal treatment conditions.
In the single occulation techniques at pH 5 and pH 7 complete
SST removals is achieved but heavy metals content remains high in
treated water.
Through the occulation process at pH 9, the optimum coagulant dose of 162 mg polydadmac/L and 67 mg occulant/L complete
TSS and turbidity removal is achieved. The remaining heavy metals
concentration in the treated water (0.931 mg Sn/L, 0.627 mg Pb/L
and 0.7 mg Fe/L) represents a removal greater than 99%. Treated
water has a COD of 45 mg O2 /L and TOC of 45 mg C/L. These results
meet the maximum permissible limits of Mexican regulations.
The occulant dose not only depends on the amount of suspended particles, but also on the amount of dissolved metals. The
dual occulation shows that the addition of 162 mg polydadmac/L
promotes coagulation and organic matter removal.

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Acknowledgements
Authors acknowledge the enterprise International Rectiers, S.
A., which through Manuel Gonzlez, Eng., gave a condent vote to a
research group situated in Tijuana, to develop a systematic and scientic work that helped for a better operation of their Waste Water
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