Journal of Hazardous Materials 243 (2012) 59–66

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Journal of Hazardous Materials

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Nephelometric and functional parameters response of coagulation for the

purification of industrial wastewater using Detarium microcarpum
J.U. Ani a,∗ , N.J.N. Nnaji a,∗ , O.D. Onukwuli b , C.O.B. Okoye a
a
Department of Pure and Industrial Chemistry, University of Nigeria, 410001 Nsukka, Nigeria
b
Department of Chemical Engineering, Nnamdi Azikiwe University, Awka, Nigeria

h i g h l i g h t s

 Detarium microcarpum (DM) as effective coag-flocculant.

 DM functions well at pH of 6, 8 and 10; and 30 ◦ C.
 New expressions that predict the time evolution in particle counting has been proposed.

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

Article history: Turbidimetry was used to study the coagulation performance of Detarium microcarpum (DM) in a fibre
Received 28 March 2012 cement effluent (FCE) at room temperature. Analysis of variance (ANOVA) and Duncan new multiple range
Received in revised form test (DNMRT) statistics were used to determine statistical difference of the coagulation performance of
26 September 2012
DM at various dosages and varying FCE pH. Increasing the coagulant dosage from 100 mg/L to 500 mg/L
Accepted 27 September 2012
had no significant difference on the coagulation performance of DM at the same pH, however, varying
Available online 22 October 2012
FCE pH between 4 and 12 using the same coagulant dosage, had significant difference on the coagulation
performance of DM.
Keywords:
Detarium microcarpum © 2012 Elsevier B.V. All rights reserved.
Coagulation
ANOVA
Duncan new multiple range test
Coagulation kinetics

1. Introduction
There has been increasing interest in the search for ways to pro-
tect the environment from pollution. Among the major sources of
environmental pollution, the menace of indiscriminate discharge of
industrial wastewater into the surrounding lands and rivers attract
attention. This is because both flora and fauna are adversely affected
to the extent that communities, which depend on such rivers for
their water supplies are in danger.
Researches on the chemicals for the treatment of water and
wastewaters have documented the use of synthetic inorganic
salts like aluminium sulphate and ferric chloride, and some syn-
thetic organic chemicals like polyacrylimides and polydadmac
[1,2]. Recently, interest has also been demonstrated in the use of
natural organic derivatives like Moringa oleifera [3], mucuna seed
∗ Corresponding authors.
E-mail addresses: anijulius@yahoo.com (J.U. Ani), joemeks4u@yahoo.com
(N.J.N. Nnaji).
[4], periwinkle shell [5], snail shell [6] and other biocoagulants [7]
for the treatment of wastewaters. In this work, the potentials of
DM for the removal of colloids from aqueous solution have been
studied.
Detarium microcarpum seed is a non-toxic bio-degradable plant
product which has the potential to function as a coagulant or
coagulant aid. Proximate analysis (in this work) has revealed its
reasonable percentage protein content which suggests that DM can
be used as a precursor to coagulant. The removal of turbidity from
a fibre cement effluent (FCE) using DM has been carried out to eval-
uate the kinetics and efficiency of the coagulation processes by the
application of statistical tools like analysis of variance (ANOVA) and
Duncan new multiple range test (DNMRT) (see Table 1).
ANOVA is one of the commonly used statistical methods to com-
pare several groups [8]. It is appropriate for testing the significant
difference among k-population means simultaneously and with-
out altering the probability of making type one error [9]. When
differences between groups exist, a past hoc test can be done to
identify which group(s) that differ(s) from the others [8]. In this
paper, Duncan new multiple range test was used.

0304-3894/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.09.069
60 J.U. Ani et al. / Journal of Hazardous Materials 243 (2012) 59–66

Table 1 for 5 days for the remaining solvent to evaporate. The oil was then
Proximate analysis of Detaruim microcarpum (DM).
weighed and the percentage oil content determined.
Parameter Value
Woil
Percentage of oil yield = × 100 (5)
Yield (%) 70 Wsample
Weight loss (%) 30
Bulk density (g/mL) 0.837 where Woil is the weight of oil and Wsample is the weight of sample.
Ash content (%) 5.12
Oil content (%) 11.24
2.1.6. Percentage moisture content
Moisture content (%) 12.66
Protein (%) 37.10 2 g of the ground seeds were weighed into pre-weighed crucible.
The crucible and the content were weighed again. This was then put
in the oven at 150 ◦ C for 5 h after which it was removed, cooled and
This paper therefore demonstrates: the effects of coagulant weighed until a constant weight was obtained.
dosage and initial effluent pH variation on coagulation performance Wsample − Wdry
of D. microcarpum (DM); and identify the coagulant dosage or initial Moisture content (%) = × 100 (6)
Wsample
effluent pH which gave statistically different mean(s).
where Wsample is the weight of sample before drying, Wdry is weight
2. Experimental of sample after drying.

2.1. Methods of analyses of DM 2.1.7. Determination of percentage protein

2.1.1. Preparation of DM coagulant
2 kg of (DM) seed was weighed out. The seeds were boiled for
45–60 min with distilled water and de-hulled. The seeds were sun
dried for 4 days, then ground with a milling machine and then
sieved with the US ASTM standard sieve.
2.1.2. Determinations of percentage yield weight loss
2 kg of DM seed was weighed out. The seeds were boiled for
45–60 min with distilled water and de-hulled. The seeds were sun
dried for four days and then milled. The seed flour was weighed to
obtain a new weight A using the following expression:
A
Percentage yield = × 100
2 Protein content (%) = % nitrogen × 6.25
2−A
Percentage weight loss = × 100
2
2 g of the powdered seed was transferred to a Kjeldahl diges-
tion flask and 8 g of the catalyst (96% anhydrous Na2 SO4 , 3.5%
CuSO4 ·5H2 O, 0.5% Selenium dioxide) were added. 20 mL of conc.
H2 SO4 were added in an inclined position and shaken occasionally
for 2 h. The liquid formed was cooled and washed into the distill-
ing flask with distilled water. 50 mL of boric acid (2%) solution and
screened methyl red indicator were added to the receiving flask.
The distillation apparatus was collected with the delivery tube
deeping below the boric acid solution. The diluted digest was made
alkaline by the addition of 50% NaOH solution. About 50 mL of the
distillate were collected and titrated with 0.1 M H2 SO4 . A blank was
also titrated under the same condition.
Percentage nitrogen (% nitrogen) = volume of 0.1 M H2 SO4 × 0.28 (7)
(1)
(8)
(2) 2.2. Methods of analyses of FCE

2.1.3. Bulk density determination For elemental analyses, the samples were digested using HNO3 ,
83.7 g of the sample was used to fill up a container of 100 mL vol- then the metals (chromium, iron, manganese and magnesium)
ume and the bulk density was then calculated using the following were determined using atomic absorption spectrophotometric
expression: method (AAS) using Bulk Scientific 210 VGP model.
Turbidimetric measurements were done at the Enugu State
W
Bulk density = (3) Water Co-operation, Enugu, Nigeria. However, the following mea-
V surements were done at Project Development Institute (PRODA),
where W is weight of the seed and V is volume of the container. Enugu, Nigeria: conductivity, alkalinity, dissolved solid, suspended
solid, dissolved oxygen, and chemical oxygen demand; and pre-
2.1.4. Determination of percentage ash content sented in Table 2. The methods adapted however are reported
2.0 g of the seed flour was weighed into a pre-weighed cru- elsewhere [9].
cible and burnt over a Bunsen burner flame until there was no Table 2
more smoke. The sample was then placed in the muffle furnace Results of FCE analyses.
at 600 ◦ C until it turned grey-white. This was cooled in a dessicator
Parameter Fibre cement effluent
and weighed to a constant weight.
pH >11
Wash Conductivity (␮s/cm) 4 × 105
Ash content (%) = × 100 (4)
Wsample Temperature (◦ C) 30
Alkalinity (mg/L) 1350
where Wash is weight of ash and Wsample is weight of sample. Dissolved solid (mg/L) 1578
Suspended solid (mg/L) 450
Nitrate (mg/L) 20.20
2.1.5. Determination of percentage oil content Calcium (mg/L) 9418.8
20 g of powdered DMC seed were weighed into a filter paper Magnesium (mg/L) 4226.85
and the wrapped filter paper was placed inside the inner part of Dissolved oxygen (mg/L) 4.40
the Soxhlet extractor. The apparatus was then fitted to a round Chemical oxygen demand (mg/L) 58.70
Iron (mg/L) 36.30
bottom flask, which contained 200 mL of hexane solvent. It was the Chloride (mg/L) 106.38
attached to a reflux condenser. The set-up was clamped and heated Manganese (mg/L) 0.016
on a water bath such that extraction is considered completed by the Chromium (mg/L) 4.33
extracting solution becoming clear. The solvent was distilled off in Sulphate (mg/L) 951.2
Turbidity (mg/L) 686.40
the distillation set. The oil was then poured into a bottle and left
 J.U. Ani et al. / Journal of Hazardous Materials 243 (2012) 59–66
2.2.1. Determination of calcium (Ca2+ )
50 mL of distilled water was put into 250 mL Erlenmeyer flask,
25 mL of 20% KOH, 10 drops of calcium solution (0.5 g CaCO3 was
dissolved in 2 M HCl and made up to 1 L with 2 M ammonium
acetate), and few grains of 1% calcein indicator were added and
shaken. 50 mL of FCE was put in the flask and shaken too. 2 mL of
KCN was added to mask metals like Zn, Cu, and Co, also 2 mL of
hydroxyl amine hydrochloride was added to mask Fe and Al. The
obtained solution was titrated against standard EDTA with gen-
tle shaking to a fluorescent yellow end point. The concentration of
calcium was calculated using the following expression:
40, 080 × M × B
Ca (mg/L) = (9)
VFCE
where M is the molarity of EDTA and VFCE is the volume of FCE in
mL.
2.2.2. Determination of nitrate (NO3 − )
5 mL of FCE was put in a Kjeldahl flask and 10 mL of the digestion
solution added. The digestion solution was prepared by dissolving
134 g of K2 SO4 in 650 mL hot distilled water, cooled and 200 mL
conc. sulphuric acid added, stirred and made up to 1 L using distilled
water. At first the solution was heated gently and when clear solu-
tion was obtained, was boiled for 40 min, cooled and neutralized
with 35 mL of 1 M NaOH to give solution A. The resultant solu-
tion (solution A) was transferred to a 100 mL flask and made up
to mark using distilled water, 25 mL taken and put into a 50 mL
volumetric flask and the reagents added to develop the indophenol
blue colour. The absorbance of the resulted solution was taken in a
UV/vis spectrophotometer at 635 nm.
Total Kjeldahl nitrogen (mg/L) = CNH3 –N × DF (10)
where CNH3 –N is the concentration value read from the curve in
mg/L and DF is the dilution factor.
Development of indophenol blue colour was as follows: 10 mL
of phenol–nitroprusside–buffer reagent was added to solution A
gently and the hypochlorite reagent added up to 50 mL mark. This
resultant solution was stoppered and allowed to stand for 45 min.
Thereafter the absorbance was taken at 635 nm.
The phenol–nitroprusside–buffer reagent was prepared by dis-
solving 60 g of phenol in buffer solution and 0.2 g of sodium
nitroprusside was added and made up to 1 L with the buffer solu-
tion. To ensure that the pH was at 9.1, the phenol was first dissolved
in the solution before the nitroprusside was added.
The buffer solution was prepared by dissolving 30 g of trisodium
phosphate, 30 g of trisodium citrate, and EDTA (disodium ethylene-
diamine tetraethanoic acid) in water and make up to 1 L using
distilled water.
2.2.3. Determination of chloride (Cl− )
100 mL of FCE was taken and decolourised by shaking with 3 mL
Al(OH)3 suspension afterwards 1 mL H2 O2 was added to oxidize
present sulphite. 0.5 mL of mixed indicator solution was added
together with 0.2 M HNO3 in drops until solution became yellow
and further six drops of the acid added. The solution was immedi-
ately titrated against 0.005 M Hg(NO3 )2 ·H2 O with constant shaking
to give a persistent blue-purple colour.
(A − B) × M × 70, 900
Chloride (mg/L) = (11)
Vsample
where A is the volume of Hg(NO3 )2 ·H2 O in mL for titrating sample,
B is the volume of Hg(NO3 )2 ·H2 O in mL for titrating blank and M is
the molarity of Hg(NO3 )2 ·H2 O.
61
2.2.4. Determination of sulphate (SO4 2− )
100 mL FCE was filtered and hydrochloric acid solution (1:1, v/v
ratio) added in drops until it became acid to litmus and three drops
were added in excess and evaporated to 50 mL. The resultant solu-
tion was boiled and boiling BaCl2 was added until all the sulphate
precipitated. The solution therefrom was put in a water bath to
settle and filtered using filtering equipment connected to a vacuum
pump (Edwards, ES50, Britain) through sintered-glass crucible. The
precipitates were washed using hot water until free from chloride
(AgNO3 test). Afterwards, the precipitates and crucible were dried
in an oven at 105 ◦ C to a constant weight and the weight of the
precipitates calculated by subtracting the weight of the crucible.
WBASO4 × 411.5
Sulphate (mg/L) = (12)
Vsample
where WBASO4 is the weight of BaSO4 formed in mg and Vsample is
the volume of FCE in mL.
2.3. Coag-flocculation test
100–500 ppm (w/v) of DM dosages in 400 mL FCE were put in
400 mL standard flasks such that the standard flasks were filled up
to mark with FCE. After preparation of various DM concentrations,
the coag-flocculation processes were carried out as outlined by the
following steps:
1. Stirring vigorously for 2 min using a magnetic stirrer;
2. afterwards, they were stirred slowly for 20 min, transferred into
a glass cylinder and allowed to settle for 30 min;
3. during the settling period, 20 mL of the supernatant (that is the
upper layer of the settling effluent) respectively pipetted into
100 mL plastic bottles with after 5 min, 10 min, 15 min, 20 min,
25 min and 30 min; and
4. The turbidity of each supernatant collected at specified time was
measured and recorded.
The optimum DM dosage was determined and used for coag-
flocculation experiments while varying the pH of the effluent, and
as such, the optimum pH was obtained. The following steps were
involved:
1. The initial pH of FCE was measured using a pH metre;
2. 5.0 M HCl and 5.0 M NaOH were used to adjust the pH of each
400 mL volume of FCE to 12, 10, 8, 6, and 4; and
3. Steps 1–4 above were repeated.
2.4. Analysis of variance (ANOVA)
The ANOVA technique becomes appropriate in a situation where
there are K groups (where K > 2), to make for efficiency. Also, ANOVA
maintains the type one error rate at the pre-established alpha level
[10].
ANOVA test compares two variance estimations: variance
within group (the unsystematic variation or error in the data) and
variance between groups (effects due to the experiment) [11].
In this paper, independent variable (coagulant dosage and pH
variation) and dependent variable (coagulation performance) were
compared using ANOVA.
2.5. Duncan new multiple range test (DNMRT)
Duncan new multiple range test uses a studentised range statis-
tic within a multiple stage test, referred to as a multiple range
test. It differs from the Duncan multiple range test, in that, DNMRT
combines in one step the stages of multiple comparisons test [12].
62 J.U. Ani et al. / Journal of Hazardous Materials 243 (2012) 59–66

The least significant range (LSR) was found from Duncan’s table It should be noted however that Eq. (24) can be applied
of new multiple range test at the confidence level, ˛, of 0.05. only when the particles do not experience other forms of non-
LSR were computed as shown below [8]: error mean square from hydrodynamic interactions like Lennard–Jones and soft–sphere
(MS) = 179.06, n = 9 and the standard error of each average: interaction potentials [14]. A work [13] has shown that the Smolu-
 chowski constant, k11 , has the following expression
MS
(S) = = 4.4604 (13) 4kB T
n k11 = (25)
30
There are five groups, hence, the total number of ranges are four.
From the Duncan (new) table, the four ranges were calculated as Furthermore, Zanten and Elimelech [15] revealed that the
shown below: Smoluchowski and the second-order rate constants are related
thus:
r2 = r0.05(2,40) = 2.86;
r3 = r0.05(3,40) = 3.01; K = ˛p k11 (26)
r4 = r0.05(4,40) = 3.10;
Therefore, comparing Eqs. (24) and (26) gives:
r5 = r0.05(5,40) = 3.17.
k11 = 8rD (27)
LSR can be calculated from Eq. (14):
where r is the particle radius, D is the Brownian diffusion coeffi-
Rp = rp × S (14)
cient, ˛p is the collision frequency, T is temperature in Kelvin, 0 is
Applying Eq. (14), LSR results obtained are: viscosity of effluent and kB is Boltzmann constant.
R2 = 12.751, R3 = 13.426, R4 = 13.827 and R5 = 14.139. The diffusion coefficient has been shown to have the following
expression [13]:
3. Theoretical and consideration of coagulation kinetics
kB T
D= (28)
6r0
The kinetics of Brownian coagulation of monodisperse particles
at early stage can be expressed as [5]: Including Eq. (28) into Eq. (27) makes the second order rate constant
dN become:
= −KN ˛ (15)
dt 4kB ˛p T
K= (29)
If ˛ = 1, Eq. (15) becomes: 30
dN The relationship between the second order rate constant and
= −KN (16)
dt friction factor (ˇBR ) is given as [13]:
Rearranging Eq. (16) and integrating within limits gives:
  ˇBR = 2K (30)
N t
dN
= −K dt (17) From Eqs. (25) and (27), the expression for effluent viscosity
N0
N 0
becomes:
Solving Eq. (17) gives:
kB T
0 = (31)
ln N = ln N0 − Kt (18) 6rD
For ˛ = 2, Eq. (15) becomes: An expression for the friction factor has been shown [1] for
dN charged particles undergoing diffusion to be
= −KN 2 (19)
dt kB T
ˇBR = (32)
Also, rearranging Eq. (19) and integrating within limits gives: D
N t Comparing Eqs. (28) and (32) gives:
dN
= −K dt (20)
N2 ˇBR = 6r0 (33)
N0 0
 1 N From Eq. (33), the effluent viscosity becomes:
∴ − = −Kt (21) ˇBR
N N0 0 = (34)
6r
and
Replacing the particle radius (r) with the radius of coag-
1 1
= + Kt (22) flocculant in Eq. (34) gives
N N0
is the final solution to Eq. (19). ˇBR
Nn = (35)
For Brownian coagulation monodisperse particles experienc- 6rNn
ing only hard sphere non-hydrodynamic interactions, the kinetics Note should be taken that charged spherical particles agglom-
involved at early stage can be expressed as [13] erate and form flocs which can sediment under gravity due to
dN destabilization caused by introduction of a coag-flocculant. Eq. (35)
− = 8rDN 2 (23)
dt arises from an approximation that considers the introduction of
Comparing Eqs. (19) and (23) gives an expression for the second a coag-flocculant in turbid water and neutralization of charges
order rate constant (K) on suspended particles results therefrom due to ‘cancellations’
of equal and opposite charges. It was assumed that the radius
K = 8r˛p D (24) of the coag-flocculant particle becomes (approximately) equal to
 J.U. Ani et al. / Journal of Hazardous Materials 243 (2012) 59–66 63

the radius of suspended particle. This approximation gives a dif- 100mg/L 200mg/L 300mg/L 400mg/L 500mg/L
ferent expression for the Smoluchowski constant (known here as
Smoluchowski–Nnaji constant) 90

Coagulation Performance (%)

80
Nn 4kB T
k11 = (36) 70
3Nn
60
In addition, the modified expression of the collision frequency 50
(from Eq. (26)) becomes 40
30
k
˛Nn
p = Nn
(37) 20
k11
10
where rNn is the coag-flocculant radius (obtained from sieve mea- 0
surements) and Nn is the viscosity of effluent calculated on the 0 10 20 30 40
assumption that DM particles are of opposite charges but of the Time (min)
same size and dimension (spherical) with suspended particles.
Fig. 1. Variation of coag-flocculation efficiency with time for various DM dosage in
Functional parameters calculated using Eqs. (35)–(37) are pre-
FCE pH of 12.
sented in Tables 7 and 8.
For a coagulation period where the total number concentra-
Colloids have electric charges on their surfaces and by these,
tion is reduced by a factor of 2,  1/2 , cluster size distribution for
they can attract each other, when a coag-flocculant is present, and
aggregating colloids can be obtained from [5,13]
cluster. However, the colloid particles are surrounded by charged
m−1
Nm (t) (KN0 t/2) ions of surrounding medium capable of attracting other charged
= m+1
(38) particles of colloid to build up a system of particles. This sys-
N0 (1 + KN0 t/2)
tem of particles interact in such a way that a resultant charge
2 is sandwiched between the former colloid particle and the latter
for 1/2 = (39)
KN0 one; hence, results to formation of two distinguishable charges
Eq. (38) represents a generic expression for particle(s) of mth possessed by agglomerated/attracted colloid particles known oth-
order. Therefore, for monomers (m = 1) erwise as electric double layer [1].
The presence of ions in the effluent accounts for the high con-
N1 1 ductivity value obtained and presented in Table 2. This high value
= 2
(40)
N0 (1 + (KN0 t/2)) of conductivity affects the performance of DM as coag-flocculant.
Similarly, it has been explained [1] that high ionic strengths favour
∴ N1 = 4N0 (2 + KN0 t)−2 (41) flocculation of colloid particles. In fact, certain substances that
For dimmers (m = 2) possess charges have been shown to have coag-flocculation prop-
erties [7]. This is possible considering that at high ionic strength
N2 KN0 t/2 (conductivity) of the effluent, introducing a coag-flocculant, results
= 3
(43)
N1 (1 + (KN0 t/2)) in reducing the electrostatic repulsion between two colloid parti-
cles to favour coag-flocculation [1].
∴ N2 = 4N02 Kt(2 + KN0 t)−3 (44) It should be noted that the conversion of turbidity to mg/L unit
For trimmers (m = 3) is by the following expression [16]:

2 Turbidity (NTU) × Tf = Turbidity (mg/L) (49)

N3 (KN0 t/2)
= 4
(45)
N0 (1 + (KN0 t/2)) where Tf is 2.20, a conversion factor.

∴ N3 = 4N03 (Kt)2 (2 + KN0 t)−4 (46) 4.2. One-way factorial analyses

A general representation of Eqs. (41), (44) and (46) can be
In Fig. 1, the variations of coagulation–flocculation performance
expressed thus
with time for various DM dosages in FCE at pH 12 were shown.
Nm (t) = 4 N0m (Kt)m−1 (2 + KN0 t)−(m+1) (47) Observed variations of DM performance with time have no sig-
nificant difference for the different DM dosages as ANOVA results
At this point, however, it becomes pertinent to note that effi- presented in Table 3 reveal.
ciency of coag-flocculation (also coag-flocculant performance) was Coag-flocculation efficiency values for DM in various FCE pH
determined using the following expression conditions and for various DM dosage at the same pH were tested
N0 − Nt for significant difference on coagulation performance of DM.
E (%) = × 100 (48) Fig. 2 presents the variation of coag-flocculation efficiency with
N0
time for 100 mg/L DM dosage in FCE at different pH values. Fig. 3
4. Results and discussion presents the variation of coag-flocculation performance of DM at
different initial pH values. The variation presented in figure was
4.1. Coag-flocculation efficiency
Table 3
The presence of calcium in FCE is high, no wonder alkalin- ANOVA result for coagulant dosage effect on coagulation performance of DM.
ity value is high as Table 2 shows. From Table 2, the presence Source of variance SS df MS Fcal Fcrit Inference
of chromium, manganese and iron are low in FCE and they are
Between groups 1607.47 4 401.87 1.98 2.61 NS
(transition) metals capable of existing in variable oxidation states. Within groups 8136.44 40 203.41
Consequently, their measured low values account for the low value
Groups total 9743.91 44
of chemical oxidation demand (COD).
64 J.U. Ani et al. / Journal of Hazardous Materials 243 (2012) 59–66

pH4 pH6 pH8 pH10 pH12 - the analyzed means of coag-flocculation efficiency at
100
100–500 mg/L in FCE at pH of 12 were not enough to show
that statistical/significant difference exist between them; and
Coagulation Performance (%)

90
- the analyzed means of coagulation efficiency at pH 4–12 were
80
not enough to show that statistical/significant difference exist
70
between them.
60
50
To account for the statistical non-difference at various DM
40
dosages, we posit that conductivity is proportional with/to coag-
30
flocculation. At the same initial FCE pH, conductivity is constant,
20
therefore DM coag-flocculation performance values were not sig-
10
nificantly different even when DM dosages were increased. This is
0
in perfect agreement with another work [13].
0 5 10 15 20 25 30 35
To consolidate our explanations, that initial FCE pH has signif-
Time (min)
icant difference on the DM performance, we subjected the mean
Fig. 2. Variation of coag-flocculation efficiency with time for 100 mg/L DM in dif-
values of coagulation efficiency of DM in FCE at various pH values
ferent initial FCE pH values. to another statistical analysis (Duncan new multiple range test –
DNMRT). The means of pH variations for pH 4, pH 6, pH 8, pH 10,
pH 12 are respectively X̄5 , X̄3 , X̄2 , X̄1 and X̄4 . Each group then was
compared as follows [8]:
Coag-Flocculation Performance
Actual difference X̄1 − X̄5 = 18.219 > R5 = 14.139.
100 Actual difference X̄1 − X̄4 = 17.552 > R4 = 13.827.
90 Actual difference X̄1 − X̄3 = 5.886 < R3 = 13.426.
80 Actual difference X̄1 − X̄2 = 0.552 < R2 = 12.757.
Coag-Flocculation
Performance (%)

70 Actual difference X̄2 − X̄5 = 17.667 < R5 = 14.139.

60
50
40
30
20
10
0 This statistic reveals that X̄ mean values of coag-flocculation effi-
0 5
pH
Fig. 3. Variation of DM coagulation efficiency with FCE at initial pH condi-
tions/values.
tested for significant difference to ensure that the variation was not
by chance. The Duncan new multiple range test (DNMRT) revealed
significant difference of coag-flocculation efficiency at different ini-
tial FCE pH conditions. In fact DNMRT further shows that at pH 4
and pH 12, DM efficiency was not significant and also at pH 6, pH
8 and pH 10, DM efficiency was not significant. There are therefore
two sets of conditions whereby the DM efficiency was not signifi-
cantly different: pH values 6, 8 and 10; and pH values 4 and 12, as
shown in Table 5.
It can be concluded from the analysis of variance (ANOVA)
results presented in Tables 3 and 4, that at ˛ = 0.05, the null
hypotheses were rejected because; Fcat < Fcrit , where Fcal = 1.98 (DM
dosage variation) and accepted because Fcal > Fcrit where Fcal = 4.00
(pH variation).
The tabulated ANOVA results of Tables 3 and 4 depict/infer the
following respectively:
Actual difference X̄2 − X̄4 = 17.000 > R4 = 13.827.
Actual difference X̄2 − X̄3 = 5.334 < R3 = 13.426.
Actual difference X̄3 − X̄5 = 12.333 < R5 = 14.139.
Actual difference X̄3 − X̄4 = 11.666 < R4 = 13.827.
Actual difference X̄4 − X̄5 = 0.667 < R5 = 14.139.
10 15 ciency at pH 4 and 12 are similar (not statistically different) but
differ from another set of similar/non statistically different mean
coagulation efficiency values at pH 6, 8 and 10. As such, Table 5 was
prepared to illustrate these results.
Results from DNMRT reveal that at different initial effluent pH
values, mean coag-flocculation performance values of DM vary
such that values at pH 4 and pH 12 have lower performance and are
not significantly different as Table 5 shows. In addition, mean coag-
flocculation efficiency values obtained for DM in FCE at initial pH
values of 6, 8 and 10 are higher and are not significantly different
as Table 5 shows.
4.3. Coagulation kinetics
The values of some coagulation kinetic parameters are pre-
sented in Tables 7 and 8. Coagulation order, ˛, obtained are 1 and 2
which is in agreement with a work reported elsewhere [5]. Coeffi-
cient of regression values, R2 are within 0.43 ≤ R2 ≤ 0.83 which are
moderate and high [17]. Obtained coefficients of regression val-
ues reveal the effectiveness of Eqs. (18) and (22) in describing the
coag-flocculation processes.
Derived Eq. (47) was used to predict the time evolution of aggre-
gating particles – monomers, dimmers and trimmers (for m = 1,
2, and 3 respectively). The trends of the aggregating particles, as

Table 4
ANOVA result for pH variation effect on coagulation performance of DM. Table 5
Mean coagulation efficiency of DM at various pH values.
Source of variance SS df MS Fcal Fcrit Inference
pH Coagulation efficiency
Between groups 2868.22 4 717.06 4.00 2.61 S
Within groups 7162.22 40 179.06 10 8 6 12 4

Groups total 10030.44 44 93.333 92.778 87.444 75.778 75.111

 J.U. Ani et al. / Journal of Hazardous Materials 243 (2012) 59–66 65

Table 7
Coagulant kinetic parameters of DM in FCE at varying dosage, pH of 12.2 and 30 ◦ C.

Parameters 100 mg/L 200 mg/L 300 mg/L 400 mg/L 500 mg/L

˛ 2 2 2 2 2
R2 0.8388 0.6292 0.4328 0.8214 0.4802
K (m3 kg−1 s−1 ) 3E−06 9E−06 6E−05 2E−06 0.0003
−1
ˇBR (m3 kg s−1 ) 6E−06 18E−06 12E−05 4E−06 0.0006
 1/2 (s) 971.251 161.875 242.813 728.438 4.856
Nn
k11 (kg2 /s) 0.350 × 10−17 0.117 × 10−17 0.175 × 10−18 0.525 × 10−17 0.035 × 10−18
−3
˛Nn
p (m3 kg ) 8.571 × 1011 7.692 × 1012 3.429 × 1013 3.810 × 1011 8.571 × 1015
D (kg2 m−1 s−1 ) 6.969 × 10−16 2.323 × 10−16 3.485 × 10−16 1.045 × 10−15 6.969 × 10−18

Table 8
Coagulant kinetic parameters of DM in FCE at varying dosage, pH of 12.2 and 30 ◦ C.

Parameters pH 4 pH 6 pH 8 pH 10 pH 12

˛ 2 1 2 2 2
R2 0.7392 0.4271 0.4531 0.3512 0.8668
K (m3 kg−1 s−1 ) 3E−06 0.0005 4E−05 3E−06 2E−06
−1
ˇBR (m3 kg s−1 ) 6E−06 0.001 8E−05 6E−06 4E−06
 1/2 (s) 971.251 58.480 728.438 971.251 1456.876
Nn
k11 (kg2 /s) 0.350 × 10−17 0.210 × 10−19 0.263 × 10−18 0.350 × 10−17 0.525 × 10−17
−3
˛Nn
p (m3 kg ) 8.571 × 1011 2.381 × 1016 1.521 × 1012 8.571 × 1011 3.810 × 1011
D (kg2 m−1 s−1 ) 6.969 × 10−16 4.181 × 10−18 5.227 × 10−16 6.969 × 10−16 1.045 × 10−15

∑N Monomers Dimmers Trimmers ∑N Monomers Dimmers Trimmers

800
Particle Concentration (mg/L)

800
Particle Concentration (mg/L)

700
700
600
600
500
500
400
400
300
300
200
200
100
100
0
0 0 500 1000 1500 2000 2500
-100
0 500 1000 1500 2000 2500 Time (s)
Time (s)
Fig. 5. Time evolution of the cluster size distribution for 100 mg/L DM in FCE at pH
Fig. 4. Time evolution of the cluster size distribution for 100 mg/L DM in FCE at pH 6.
4.
DM dosage, collision frequency increases with ˛th order coagu-
lation in FCE containing various DM dosages. These are in contrast
a function of time, are shown in Figs. 4–8. The trend is similar with results obtained elsewhere [5,13]. However, it should be noted
for all the curves and represents particle distribution expected in that low energy barrier for coag-flocculation has been favoured
a typical coagulation process. The numbers of primary particles
(monomers), as shown in Figs. ∑N Monomers Dimmers Trimmers
 4–8, decrease more rapidly than the
Particle Concentration (mg/L)

total number of particles ( N). This is because dimmers and trim- 800
mers are formed because of the quick destabilization of monomers 700
which facilitated coagulation process. These bring to limelight the 600
suitability of Eq. (47) in particle size distribution and in agreement
500
with previous works on coagulation [5,13]. Fig. 5 however reveals
the presence of dimmers and trimmers to be very minimal. This 400
implies low flocculation. As Table 8 shows, coag-flocculation at pH 300
6 has the minimum 1/2 value suggesting very fast coagulation rate. 200
This is in agreement with highest coagulation rate constant value 100
of 0.0005 at pH 6 as shown in Table 8. Therefore at pH 6, only very
0
high hydrodynamic shear force can cause flocculation to be reduced
0 500 1000 1500 2000 2500
drastically.
Time (s)
Observing Table 8, reveals that collision frequency increases
with ˛th order of coagulation (K) in FCE at various pH conditions. Fig. 6. Time evolution of the cluster size distribution for 100 mg/L DM in FCE at pH
Also, a close observation of Table 7 shows that but for 300 mg/L 8.
66 J.U. Ani et al. / Journal of Hazardous Materials 243 (2012) 59–66

∑N Monomers Dimmers Trimmers 5. Conclusion

Particle Concentration (mg/L)

800 The following highlight the major conclusions of this present

700 study:
600
500 - DM is a very effective coag-flocculant for treatment of FCE at room
400 temperature (303 K);
300 - varying dosage had no significant difference on the coag-
200 flocculation performance of DM at the same effluent (FCE) pH
100 condition;
0 - however, varying the pH conditions of FCE had significant differ-
0 500 1000 1500 2000 2500 ence on the coag-flocculation performance of DM. Subsequently,
Time (s) it is the surface chemistry of DM (presence of proteins) that favour
its coag-flocculation performance in different FCE pH conditions.
Fig. 7. Time evolution of the cluster size distribution for 100 mg/L DM in FCE at pH
10. From experimental optimum conditions, DM becomes an effec-
tive coag-flocculant for the purification of industrial wastewaters
∑N Monomers Dimmers Trimmers within pH range of 6–10 using as little as possible without exceed-
ing 100 mg dosage in treating 1 L of effluent at 30 ◦ C.
800
Particle Concentration (mg/L)

700
600
500
400
300
200
100
0
0 500 1000
Time (s)
Fig. 8. Time evolution of the cluster size distribution for 100 mg/L DM in FCE at pH
12.
since the ˛th order of coagulation (K) has relationship with it
[5,13]. Consequently, low ˛th order of coagulation resulted to
low energy barrier favouring fast coagulation. No wonder DM, as
presented in Figs. 1 and 2, displayed efficient and effective coagu-
lation/flocculation.
Furthermore, collision frequency values have small variations
suggesting high kinetic energy that overcame the zeta potential,
favouring fast coagulation. Values of 1/2 are high, corresponding to
low collision frequency values, suggesting existence of electrostatic
repulsion interactions between colloid particles for particles of like
charges and also attraction for particles of unlike charges, hence,
there is strong indication of existence of van der Waals attraction
forces between colloid particles and coag-flocculant. The resultant
attraction effect due to van der Waals forces allowed the adsorption
of colloid particles on surface active sites of DM particles which led
to formation of flocs.
 [17] N.M. Dowine, R.W. Heath, Basic Statistical Methods, 4th ed., Harper and Row,
Where total number of particles is represented with N.
References
[1] P.W. Atkins, Physical Chemistry, 4th ed., Oxford University Press, Oxford, 1990.
[2] S.K. Ghosal, S.K. Sanyal, S. Datta, Introduction to Chemical Engineering, Tata
McGraw-Hill Publishing Company Limited, New Delhi, 1993.
[3] J.U. Ani, M.C. Menkiti, O.D. Onukwuli, Coagulation–flocculation performance of
snail shell biomass for waste water purification, N.Y. Sci. J. 4 (2) (2011) 81–90.
[4] M.C. Menkiti, O.D. Onukwuli, Coag-flocculation of Moringa oleifera coagulant
(MOC) in brewery effluent: nephelometric approach, J. Am. Sci. 6 (12) (2010)
88–806.
[5] M.C. Menkiti, P.C. Nnaji, O.D. Onukwuli, Coag-flocculation kinetics and func-
tional parameters response of periwinkle shell coagulant (PSC) to pH variation
1500 2000 2500 in organic rich coal effluent medium, Nat. Sci. 7 (6) (2009) 1–18.
[6] M.C. Menkiti, P.C. Nnaji, C.I. Nwoye, O.D. Onukwuli, Coag-flocculation kinetics
and functional parameters response of mucuna seed coagulant to pH variation
in organic rich coal effluent medium, J. Miner. Mater. Charact. Eng. 2 (8) (2010)
89–103.
[7] K.A. Yongabi, Biocoagulants for water and wastewater purification: a review,
IReChE 2 (3) (2010) 444–458.
[8] E.P. Adhistya, R.A.R. Dayang, P.D.D. Dhanapal, Forecasting method selection
using ANOVA and Duncan multiple range tests on time series data, IEEE (2010)
941–945.
[9] C.M.A Ademoroti, Standard Methods for Water and Effluent Analysis, Foludex
Press Ltd., Ibadan, 1996.
[10] B.G. Nworgu, Educational Research – Basic Issues and Methodology, University
Trust Publishers, Nsukka, 2006.
[11] D.E. Hinkle, W. Wlersma, S.G. Jurs, Applied Statistics for the Behavioural Sci-
ences, Houghton, Mifflin, Boston, 1998.
[12] I.U. Obi, Statistical Methods of Detecting Differences Between Treatment Means
and Research Methodology Issues in Laboratory and Field Experiments, AP
Express Publishers Limited, Nsukka, 2002.
[13] M.C. Menkiti, O.D. Onukwuli, Coag-flocculation studies of Afzelia belia coagulant
(ABC) in coal effluent using single and simulated multiangle nephelometry, J.
Miner. Mater. Charact. Eng. 10 (3) (2011) 279–298.
[14] J.S. Abel, G.C. Stangle, C.H. Schilling, I.A. Aksay, Sedimentation in flocculating
colloidal suspensions, J. Mater. Res. 9 (2) (1994) 451–461.
[15] J.H.V. Zanten, M. Elimelech, Determination of absolute coagulation rate
constants by multiangle light scattering, J. Colloid Interface Sci. 154 (1) (1992)
1–7.
[16] G. Tchobanoglous, F.L. Burton, H.D. Stensel, Wastewater Engineering: Treat-
ment and reuse, Tata McGraw-Hill, New Delhi, 2003.
New York, 1974.