This document discusses using clay minerals and organoclays as flocculants to pretreat brine wastewater (BWW) from the pickle industry. BWW is difficult to treat due to its low pH, high salt content, and high levels of suspended and organic matter. The study tested different clay minerals and berberine-modified organoclays in a two-step sedimentation process to reduce turbidity, total suspended solids (TSS), volatile suspended solids (VSS), and chemical oxygen demand (COD) in BWW. Preliminary tests showed Volclay KWK bentonite (VO) and Pangel C150 sepiolite (C150) were the most effective at reducing

1. Applied Clay Science 67–68 (2012) 119–124
Contents lists available at SciVerse ScienceDirect
Applied Clay Science
journal homepage: www.elsevier.com/locate/clay
Research paper
Brine wastewater pretreatment using clay minerals and organoclays as flocculants
Tom N. König a,b, Sivan Shulami a, Giora Rytwo a,b,⁎
a Tel Hai College, Dept. of Environmental Sciences, Upper Galilee 12210, Israel
b Environmental Physical Chemistry Laboratory, MIGAL, Galilee Technological Center, Kiryat Shmona, Israel
a r t i c l e i n f o a b s t r a c t
Article history:
Received 21 May 2011
Received in revised form 12 May 2012
Accepted 23 May 2012
Available online 12 July 2012
Keywords:
Pickle brine waste water
Flocculation
Organoclay
Smectite
Berberine
Sepiolite
Use of conventional pretreatment for pickle industry brine wastewater (BWW) is not efficient due to its low
pH, high salt content and high concentrations of suspended and organic matter. The goal of this work was to
inspect different clay minerals and berberine-based organoclays as possible flocculants to reduce BWWturbidity,
total and volatile suspended solids (TSS and VSS, respectively) and chemical oxygen demand (COD). Preliminary
flocculation tests showed Volclay KWK (VO) and Pangel C150 (C150) to be the best candidates for a two-step
sedimentation test, with the highest TSS, VSS, COD and turbidity reductions. Adsorption isotherms showed
that VO and C150 adsorb different amounts of berberine, and therefore a common reference line for organoclay
preparation was based on their point of zero charge. Two-step sedimentation tests showed that combining
VO-berberine and VO (organoclay and raw clay, respectively) better reduces the inspected parameters than
two steps with VO, whereas the opposite held true for C150-berberine and C150. Out of all treatments, two
steps using C150 showed the best TSS, COD and turbidity reduction. C150 appears to be an excellent candidate
for a future multistage flocculation and sedimentation processes for BWWtreatment.
© 2012 Elsevier B.V. All rights reserved.
1. Introduction
The pickle industry generates large volumes of brine wastewater
(BWW), mostly from the manufacturing line but also during routine
maintenance, such as equipment cleaning. BWW from this industry
is usually characterized by low pH (3.5–6), high salt content (mainly
NaCl; 2500–14,000 mg/L) and high concentrations of dissolved and
suspended solids, composed mostly of organic matter (Little et al.,
1976). This BWW is considered hazardous to the environment, and if
not treated properly, might cause groundwater and freshwater pollu-tion
and soil sodification (Sparks, 1995).
Conventional wastewater-treatment processes such as activated
sludge are not effective forBWW, because biological activity is inhibited
by the high salt concentrations. Therefore, different approaches were
examined, such as biological treatment using halobacteria (Kargi and
Dinçer, 1996; Kargi and Uygur, 1996; Lefebvre et al., 2005), chemical
flocculation (Song et al., 2004), and various membrane-filtration
processes such as membrane distillation (Gryta et al., 2006), reverse
osmosis (RO) and electrodialysis (Metcalf and Eddy, Inc., 2003).
Coagulation and flocculation are common practices for fine-particle sedi-mentation.
Reacting tannery BWWwith aluminum sulfate (“alum”) and
ferric chloride was shown to significantly reduce the concentration of
volatile suspended solids (VSS) and chemical oxygen demand (COD),
but efficiency of the process was pH-dependent (Song et al., 2004).
Alum's high pHdependency might constitute a drawbackwhen treating
pickleBWWdue to variations in the acidity of the effluentswhich might
cause decreased efficiency, and consequently increased treatment costs.
Even though the suitability of terms as VSS and TSS is arguable, since the
techniques measure as the matter of fact dispersed solids, both terms
are so widely used in water and wastewater literature (APHA, 2005;
Metcalf and Eddy, Inc., 2003), that we will employ them along the
manuscript as defined by the references above.
Clay minerals are inorganic colloids with large specific surface
area and a net negative charge which can be electrically compensated
for by inorganic or organic cations from the environment (Johnston,
1996). In dispersion, these counter ions are organized in two layers:
some of the neutralizing cations are relatively tightly bound to the clay
mineral surface (the Stern layer), whereas the rest of the counterions
formthe diffuse layer near the claymineral. The thickness of the electrical
double layer strongly depends on the ion concentration in the solution. A
relatively wide electrical double layermight prevent particle aggregation
and settling due to electrical rejection between the particles. The
electrical double layer narrows at higher concentrations of inorganic
or organic cations, resulting in faster aggregation and settling processes
(Lagaly, 2006). Therefore, high concentrations of cations (such as Na+)
in BWW will yield a relatively thin double layer, making clay minerals
possible candidates as flocculants.
Organoclays studied for the pretreatment of paper industry waste
water (Bouffard, 1998), olive oil waste water (Mousavi et al., 2006)
Abbreviations: BWW, brine waste water; C150, Pangel C150 sepiolite; COD, chemical
oxygen demand; PZC, point of zero charge; VSS, volatile suspended solids; TSS, total
suspended solids; VO, food-grade Volclay KWK bentonite.
⁎ Corresponding author at: Tel Hai College, Faculty of Sciences and Technology, Dept.
of Environmental Sciences, Upper Galilee 12210, Israel. Fax: +972 4 6944980.
E-mail addresses: giorarytwo@gmail.com, rytwo@telhai.ac.il (G. Rytwo).
0169-1317/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2012.05.009

2. 120 T.N. König et al. / Applied Clay Science 67–68 (2012) 119–124
and winery effluent (Rytwo et al., 2011a,b), might also be candidates
as flocculants, not only due to their ability to aggregate and settle
quickly (Lagaly, 2006), but also due to the adsorption of large
amounts of organic compounds (Rytwo and Gonen, 2006; Rytwo et
al., 2007).
Multistage coagulation and sedimentation processes for the treat-ment
of industrial effluents were implied by Garrote et al. (1995),
who used ferric chloride (FeCl3) and calcium hydroxide (CaOH) to re-move
COD from tannery wastewater, and by Rytwo et al. (2011b),
who used organosepiolites based on crystal violet and raw sepiolites
for the pretreatment of winery effluents. Clay minerals modified with
berberine (5,6-dihydro-9,10-dimehtoxybenzo[g]-1,3 benzodioxolo
[5,6-a] quinolizinium) were also suggested as possible flocculants for
the pretreatment of winery and BWW effluents (Rytwo et al., 2011a).
The goal of this study was to examine the use of different clayminerals
and berberine-based organoclays as flocculants in a two-step sedimen-tation
test for BWW treatment, and their efficacy as a pretreatment in
reducing concentrations of suspended solids and organic content of
the studied BWW.
2. Materials and methods
2.1. Materials
Raw BWW was sampled at Beit-Hashita pickle factory (Kibbutz
Beit-Hashita, Israel), transported to the laboratory in 10-L containers,
and kept at roomtemperature until experimentation. SWy-2Wyoming
Na-montmorillonite (SWy-2) was purchased from the Source Clay
Repository of The Clay Minerals Society (Columbia, MO). Food-grade
Volclay KWK bentonite (VO) (American Colloid Company, Arlington
Heights, IL) was generously supplied by Micha Vaadia (Galil Mountains
Winery, Israel). Egyptian bentonite (EB) (EBDC Bentonite Co., Alexandria,
Egypt) was obtained from Naheel Ibrahim (Ibrahim Construction Co.).
Two types of Yunclillos sepiolite, S9 and C150, (S9, C150) were provided
by Tolsa (Madrid, Spain). Berberine chloride was purchased from Sigma-
Aldrich (Rehovot, Israel). All materials were used without treatment or
purification except for VO, which was pulverized with a mortar and
pestle prior to use to eliminate large aggregates.
2.2. Clay and organoclay preparation
Clay mineral dispersions (10 g/L) were prepared by dispersing the
clays in distilled waterwith continuousmagnetic stirring. The organoclay
dispersions were prepared by adding the required weighed amount of
berberine to a pre-prepared 1% (m/v) dispersion during continuous
stirring and further agitation overnight to ensure complete adsorption.
Complete adsorption was confirmed by measuring the amount of
berberine remaining in the supernatant.
2.3. Tests
The concentration of “total suspended solids” (TSS) as defined in the
literature (APHA, 2005)was determined by filtering 5 mL of the sample
through a 47-mm glass fiber membrane (Sartorious Stedim Biotech
GmbH, Goettingen, Germany) with pore diameter of 0.45 μm, and
drying at 105 °C for 1 h. VSS concentrations were determined by
kilning the TSS filters in 550 °C. Both TSS and VSS concentrations were
calculated from the mass balance. Turbidity was measured using a
LaMotte 2020i turbidimeter. Chloride concentrations were measured
using a Merck Chloride kit (Aquamerck No. 1.11106.0001). Chemical
oxygen demand (COD) testswere performed using Merck COD solution
A (no. 1.14538.0065) and solution B (no. 1.14538.0065). CODtestswere
conducted by adding themanufacturer-recommended volumes of the re-agents
to 10 mL pre-prepared glass test tubes with white plastic screw
caps (Hach), and the required volume of sample (diluted 1:10). The test
tubes were then placed in a preheated reactor (Merck Thermoreaktor
TR300) at 148 °C for 2 h, and COD contents were measured using a
LaMotte SMART2 colorimeter. pH was measured using a Cyberscan 500
pH meter with a 6-mm plastic electrode.
2.4. Preliminary flocculation tests
Preliminary flocculation tests were conducted to choose the clays
which were most effective at reducing BWW turbidity, TSS, VSS, and
COD. The clay mineral dispersion was added to BWW to achieve a
final volume of 250 mL and a final clay concentration of 0.1% (m/v).
The dispersions were stirred thoroughly for 1 min and left to settle
for 1 h. The upper effluents were gently removed for the TSS, VSS and
turbidity tests. pH and chloride concentrations were also measured at
the beginning and end of the process. This procedure was conducted
in triplicate for all clay types tested. COD was measured once for each
clay type. The chosen clay minerals were then used in a two-step sedi-mentation
test.
2.5. Two-step sedimentation test
After choosing the clay minerals exhibiting the best reduction in
TSS and VSS, a two-step sedimentation test (Fig. 1) was conducted.
The first step was performed with organoclay dispersions which
were prepared as described in subsection 2.2. The organoclay dispersion
was mixed with BWW to achieve a final volume of 250 mL with an
organoclay concentration of 0.1%. The dispersion was stirred thoroughly
for 1 min and left to settle for 1 h. The effluent was gently removed for
the TSS, VSS, COD and turbidity tests. The second cycle was performed
by mixing the remaining effluent with a new clay dispersion giving a
final concentration of 0.1%. The dispersion was stirred for 1 min, and
left to settle for 1 h. Finally, the effluent was gently removed and again
TSS, VSS, COD and turbidity tests were performed. This entire procedure
was conducted in triplicate for each type of organoclay, and a control test
was performed using raw claymineral dispersions in both cycles. pHwas
measured at the beginning and end of each cycle.
2.6. Additional measurements
Adsorption isotherms of berberine on the chosen clay minerals
were determined in plastic tubes with screw caps by adding 2 mL of
1% clay dispersion and increasing volumes of 2 mM berberine solution.
Distilled water was added to reach a final volume of 20mL. The tubes
were shaken with an orbital shaker for 3 days. Then, a 10-mL aliquot
was centrifuged in a Juan C-3000 at 4000 RPM (app. 2860 g). The con-centration
of berberine remaining in each tube was determined by the
BWW with
organoclay
After 1
hour
BWW
Settled organoclay
Second step – adding
BWW raw clay dispersion
with clay
BWW
Raw BWW
After 1 hour
Clear Brine
Settled clay
Stirring 1
minute
Stirring
1 minute
First step – adding
organoclay dispersion
Fig. 1. Schematic description of the two-step sedimentation test.

3. T.N. König et al. / Applied Clay Science 67–68 (2012) 119–124 121
HP 8452A spectrophotometer at 422 nm (Rytwo et al., 2008). A 10-mL
aliquot of the dispersion was used for point of zero charge (PZC) mea-surements,
using a particle charge detector (Mütek PCD 03) connected
to an automatic titration unit (Mütek PCD titrator T3) with a charge-compensating
polyelectrolyte, as described by Rytwo et al. (2005).
The cationic polyelectrolyte poly-DADMAC (poly-diallyl-dimethyl-am-monium
chloride) and the anionic polyelectrolyte PES-Na (polyethene
sodium sulfonate) were used for titration of the negative and positive
surface charge of the samples, respectively.
Attenuated Total Reflection-Fourier Transform Infrared (ATR-FTIR)
spectra of air-dried samples of sepiolite and the organo-cations
adsorbed to it were measured in a Nicolet Avatar 320 FTIR, using a
MIRacle ATR device with a diamond crystal plate (Pike Technologies,
Madison, WI). Spectra were recorded at 4 cm– 1 nominal resolution
with mathematical corrections yielding a 1.0 cm– 1 actual resolution
and 100 measurements were averaged. OMNIC 8.1 (Thermo Fisher
Scientific Inc.) program analytical procedures were used to convert
the spectra from ATR to absorbance.
3. Results and discussion
3.1. Preliminary coagulation tests
Results of the preliminary coagulation tests are shown in Table 1.
The high salinity of BWW causes a relatively thin electrical double
layer on the dispersed particles, allowing them to aggregate (Hanhui
et al., 2006). However, in the BWWused in this study, the spontaneous
sedimentation process was very slow, possibly due to the low mass or
density of the aggregates. Adding a higher density coagulant might
speed up sedimentation and indeed, addition of the clay minerals created
massive floccules that settled rapidly.
All tested clays considerably decreased TSS, VSS, and turbidity
levels, and a slight decrease in COD was also observed. Nevertheless,
the treatments with VO and SWy-2 were the most efficient, decreasing
the examined parameters to the lowest values (Table 1).SWy-2 and VO
are bentoniteswhichwere shown to possess similar features (Rytwo et
al., 2011a). This might explain the similarity of the flocculation test re-sults.
The presence of large ion concentrations in the highly saline
BWW(Table 1)might promote the formation and sedimentation of rel-atively
large aggregates. In a previous study, EB, which is a mixture of
80% expanding smectite and 20% of non expanding illite and kaolinite,
was tested (Rytwo et al., 2011a). The non-expanding fractions of EB
may have prevented the formation of aggregates as large as those
formed with VO and SWy-2, thus decreasing its efficiency in removing
suspended solids from the BWW.
C150 and S9 are non-expanding fibrous clay minerals with lower
specific surface area than exfoliated smectites (Ruiz-Hitzky, 2001).
Both sepiolites decreased the BWW turbidity and VSS to about the
same levels (Table 1). A combination of organo-sepiolite and sepiolite
was recently shown to be an effective pretreatment for winery waste-water,
presumably due to a bridging mechanism which creates the
floccules and promotes aggregation (Rytwo et al., 2011b). The large
concentration of inorganic salts in BWW should reduce electrostatic
repulsion and colloidal stability due to the reduced diffuse layer potential
as a consequence of increased Stern layer adsorption (Lagaly, 2006). In
other words, a thinner diffuse layer caused by high ionic strength may
also speed up flocculation when adding clay minerals to high-ionic-strength
systems such as BWW.
None of the treatments changed the pH of the BWW. However, an
unexpected 15 to 20% decrease of the chloride concentration was ob-served
after all treatments. A similar phenomenon was observed by
Zermane et al. (2005), who reported that adding commercial and
synthesized montmorillonites to synthetic sea water at low pH, de-creased
the solution conductivity. Clay mineral edge charge density
is highly influenced by pH. Usually, the edge charges are neutralized
at 6bpHb8 (Yariv and Michaelian, 2002). The studied BWW had
pH=5, and therefore the edge charge may be slightly positive, enabling
the binding of chloride ions as counterions. Another possibility is the
formation of chloride-based complexes, such as CaCl+, which are
bound as cation exchange. Additional research is needed to explain
this phenomenon.
Additional experiments were performed using VO and C150. Even
though SWy-2 and VO showed similar performance in all preliminary
tests, one of the aspects to be considered when choosing a clay for
such treatments is its price. SWy-2 is relatively expensive, whereas
VO is a food-grade bentonite used in the fining step of suspended solids
removal fromwine, juice, cider, and vinegar (American Colloid Company,
2001). Therefore, we decided to test VO in the two-step sedimentation
test. For comparison with a mineral with different characteristics, C150
was chosen from the fibrous minerals tested, since it reduced the
inspected parameters slightly better than S9 (Table 1), and was found
to be the fastest flocculating and settling clay of all five clay types tested
(results not shown).
3.2. Organoclay preparation
Berberine adsorption on VO and C150 was investigated to prepare
organoclays for using in the two-step sedimentation test. Berberine
adsorption isotherms are shown in Fig. 2. Both clays displayed an H
type isotherm, indicating their high affinity to the berberine (Sparks,
1995). Amounts of berberine up to 0.65 (VO) and 0.05 (C150) mmol/g
were completely adsorbed, and saturation was observed at approxi-mately
0.95 (VO) and 0.1 (C150) mmol/g. It was reported before that
VO completely adsorbed berberine up to 0.8 mmol/g (Rytwo et al.,
2011a). C150 has characteristics similar to other Yunclillos sepiolites
such as S9, although it is applied for different uses (Tolsa Group,
2008a,b). Therefore, under the assumption of similar CEC, the adsorbed
berberine amount of 0.1 mmol/g corresponds to about 70% of the CEC
(0.15mmolc/g, Ruiz-Hitzky, 2001).
The amounts of berberine adsorbed on C150 were considerably
lower than those reported for other monovalent organic cations,
and even for neutral molecules. Maximal adsorbed amounts reported
were about 0.55, 0.64 and 0.30 mmol/g for methylene blue (MB)
(Aznar et al., 1992), crystal violet (Rytwo et al., 1998) and Triton-X
100 (Alvarez et al., 1987), respectively. Such large amounts were
explained by adsorption of those organic molecules to neutral silanol
(Si―O―H) sites in addition to the charged sites available on sepiolite
(isomorphic exchanges). The relatively lower amount of adsorbed
Table 1
Preliminary sedimentation test results.
Treatment Turbidity (NTU) TSS (mg/L) VSS (mg/L) COD
(mg/L)
pH Cl–
(mg/L)
Value Std. deviation Value Std. deviation Value Std. deviation
Raw BWW 167.2 1180 760 2840 5.03 8200
SWy-2 12.2 0.49 351.9 93.2 85.2 35.72 1867 5.07 7111
EB 61.7 8.12 433.3 40.1 92.6 16.97 1967 5.10 7111
VO 13.7 0.69 314.8 44.9 88.9 40.06 1878 5.09 6667
C150 39.8 7.80 418.5 28.0 96.3 6.42 1911 5.04 6889
S9 40.9 7.71 485.2 61.2 96.3 27.96 2189 5.07 7778

4. 122 T.N. König et al. / Applied Clay Science 67–68 (2012) 119–124
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
berberine found here raises the question of whether it adsorbs on
both types of sites. FTIR measurements showed that divalent organic
cations such as diquat and paraquat do not adsorb to neutral sites of
sepiolite (Rytwo et al., 2002), and a similar procedure was performed
in this study. The Si―O―H vibration cause a band at 3700 cm–1, and
a doublet due to O―H deformation was observed at approximately
800 cm–1 (Kodama, 1985; Nakanishi and Solomon, 1977). Shifts or
changes in these peaks may indicate interactions of the organic cations
with the silanol groups, and are interpreted as adsorption to the neutral
sites.
Fig. 3 shows FTIR spectra of both the doublet due to the O―H de-formation,
and the main Si―O―H vibration. Raw C150 sepiolite
exhibited two clear deformation bands at 786 and 766 cm–1. Adsorp-tion
of a monovalent organic cation that interacts with the silanol
such as MB at about 60% of the CEC (MB-C150) completely changed
this band into a single broad peak at 764 cm−1. Adsorption of the
same amount of berberine (Ber-C150) did not affect the O―H doublet.
Similar effects were observed for the main Si―O―H vibration whereas
the vibration band of raw sepiolite appeared at 3689 cm−1. Ber-C150
showed the same behavior, while MB adsorbed to C150 yielded a
bathochromic shift of about 10 cm−1. As in previous studies (Rytwo
et al., 2002), we concluded that in contrast to other monovalent
organo-cations such as MB, berberine does not adsorb on the neutral
sites of sepiolite, explaining the relatively low total adsorbed amounts
(Fig. 2). We speculate that this lack of interaction with the silanol
groups might be due to the relatively larger and more rigid structure
of berberine.
Particle charges were measured to test the influence of the
adsorbed berberine on this parameter. Fig. 4 shows the particle
charge as a function of the amount of berberine added. The PZC of
VO and C150 was reached at 100% CEC (0.8 mmol/g) and about 60%
CEC (0.09 mmol/g), respectively. In both clays, charge reversal was
observed above 100% CEC. The adsorption isotherm corresponded to
the charge variation of the clays. The PZC was reached when berberine
traces began to be detected in the supernatant. Similar results were ob-served
previously for crystal violet adsorption on sepiolite (Rytwo et al.,
2011b) and berberine adsorption on SWy-2 (Rytwo et al., 2008).
To provide a common reference line between the two very different
clays in the sedimentation experiments, the PZCwas taken as a suitable
base for comparison. Therefore, organoclays for the two-step sedimen-tation
testswere preparedwith the amount of berberine corresponding
to the PZC.
3.3. Two-step sedimentation tests
The Adsorption isotherms (Fig. 2) showed that at 0.8 (VO) and
0.09 (C150) mmol/g added berberine, >99% of the berberine was
adsorbed. The traces of berberine remaining in solution yielded a
yellowish color. The assumption that exposure to large concentra-tions
of Na+might cause desorption of the organo-cation was evalu-ated
using a Gouy–Chapman–Stern adsorption model (Rytwo et al.,
1998; Rytwo, 2004; Margalit and Rytwo, 2011, unpublished results).
Calculation indicated that no desorption of berberine is expected, as
described also in previous studies for the influence of ionic strength
on the adsorption of organo-cations (Margulies et al., 1988). Therefore,
and as described in Fig. 1, the first step was conducted using the
organoclays, and raw clays were used in the second step for two rea-sons:
to further reduce the inspected parameters and to adsorb any
berberine left after first cycle.
TSS, VSS, COD and turbidity of the two-step sedimentation tests are
shown in Fig. 5. VO-berberine (Ber-VO) showed higher TSS, VSS,
COD and turbidity values after the first step than the control (raw VO).
However, the use of raw VO in the second step was effective, since no
berberine was visible after the second step, and the inspected parameters
were strongly reduced (354, 37, 1426 mg/L and 13 NTU for TSS, VSS, COD
and turbidity, respectively).
Differences between Ber-C150 and C150 in the first step were rela-tively
small: Ber-C150 showed slightly lower VSS and COD concentra-tions
than the control, while TSS and turbidity were slightly higher
(Fig. 5). Like VO, the use of raw C150 in the second step was successful
at adsorbing the residual berberine. However, the use of rawC150 in the
second step did not decrease the inspected parameters to values below
0.0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
Berberine equilibrium concentration [mmol/L]
Berberine adsorbed concentration
[mmol/g]
C150
VO
Fig. 2. Berberine adsorption isotherms on VO (squares) and C150 (rhombuses).
3690 3680
786
784
C150
Ber-C150
Wavenumbers (cm-1)
3679
3689
766
800 780 760
MB-C150
Fig. 3. FTIR spectra of Si―O―H stretching andO―H deformation vibrations of C150 sepio-lite,
MB adsorbed on C150 and berberine adsorbed on C150. The amounts of both organo-cations
added were 0.09mmol/g.
100
0
-100
-200
-300
-400
-500
5
-5
-15
-25
-35
0 20 40 60 80 100 120 140 160
Berberine added [%CEC]
VO particle charge
[mmolc/kg]
-45
C150 particle charge
[mmolc/kg]
VO
C150
Fig. 4. VO (squares, left axis) and C150 (rhombuses, right axis) charge as a function of
added berberine in relation to the CEC of the clay.

5. T.N. König et al. / Applied Clay Science 67–68 (2012) 119–124 123
a 1200
b
1000
800
600
400
200
c 180
d
160
140
120
100
80
60
40
20
the control values. In fact, two steps using raw C150 yielded the best
performance of all treatments and the largest reduction of TSS, COD
and turbidity (123, 1296mg/L and 8.2 NTU, respectively).
4. Conclusions
Brine effluents from the pickle industry contain high concentra-tions
of organic matter and suspended solids. This study presents a
pretreatment of BWW with clays and organoclays. Reacting BWW
with clay minerals in general was efficient . TSS, VSS and turbidity were
reduced by one order of magnitude, and COD was slightly reduced.
Two-step sedimentation tests were also examined for their ability to
further decrease the inspected parameters. However, the results were
inconclusive, with the two clays chosen for the process showing differ-ent
trends. Using Ber-VO in the first step and VO in the second step gave
slightly better results than using raw VO in both steps. On the other
hand, the combination of Ber-C150 and C150 was less effective than
using raw C150 in both steps. Rather unexpectedly, after two steps
C150 gave even better results than VO. These results, combined with
the very fast aggregation and settling observed with C150, make
the sepiolite an excellent candidate for a future multistage flocculation
and sedimentation processes for BWWtreatments.
It is important to note that this and previous experiments indicate
that wastewater pretreatment is a highly enigmatic process, involving
many known and unknown factors. As seen previously, reactingwinery
effluents with organo-sepiolites yielded better results than crude sepi-olites
(Rytwo et al., 2011b). On the other hand, in a previous study
(Rytwo et al., 2011a), EB reduced the turbidity values in brine to 15%
of the initial value, whereas VO increased the turbidity of the brine
effluents. In the present work, EB reduced the turbidity to 37% of its
initial value, whereas VO reduced it to 8%. Such completely different
behavior indicates that there are other factorswhich might affect a clay's
ability to clear different types ofwaste water, and sometimes even differ-ent
batches of the same waste water. In this specific case, BWWfor both
800
700
600
500
400
300
200
100
0
VO control Ber-VO C150 control Ber-C150
Treatment
3500
3000
2500
2000
1500
1000
500
studies was from the same factory and had similar salinity, but while in
this study it was from pickled cucumber preparation, wastewater for the
Rytwo et al. (2011b) study was collected froman olive-pickling process.
Thus, while raw clay treatments were highly susceptible to the exact
composition of the waste water, berberine-based organoclays provided
a relatively efficient pretreatment in both previous and present studies.
Acknowledgments
Part of this study was performed using instruments purchased with
the aid of the J.C.A. Berberine desorption evaluations were performed
with the support of the Israeli Ministry of Agriculture program no.
862-0231-10.
References
Alvarez, A., Santaren, J., Perez-Castells, R., Casal, B., Ruiz-Hitzky, E., Levitz, P., Fripiat, J.J.,
1987. Surfactant adsorption and rheological behavior of surface modified sepiolite.
In: Schultz, L.G., van Olphen, H., Mumpton, F.A. (Eds.), Proceedings of the Interna-tional
Clay Conference, Denver, 1985. The Clay Minerals Society, Bloomington, IN,
pp. 370–374.
American Colloid Company, 2001. Volclay KWK Food Grade Technical Data. American
Colloid Company, Arlington Heights, IL.
APHAAWWAWEF, 2005. Standard Methods for the Examination of Water and Wastewater,
21st ed. American Public Health Association, Washington DC, USA.
Aznar, A.J., Casal, B., Ruiz-Hitzky, E., Lopez-Arbeloa, I., Lopez-Arbeloa, F., Santaren, J.,
Alvarez, A., 1992. Adsorption of methylene blue on sepiolite gels: spectroscopic
and rheological studies. Clay Minerals 27, 101–108.
Bouffard, S.C., 1998. Application of Natural and Tailored Minerals to the Treatment of
Thermomechanical PaperMillWhite Water. MSc Thesis, University of British Columbia,
BC.
Garrote, J.I., Bao, M., Castro, P., Bao, M.J., 1995. Treatment of tannery effluents by a two
step coagulation/flocculation process. Water Research 29, 2605–2608.
Gryta, M., Tomaszewska, M., Karakulski, K., 2006. Wastewater treatment by membrane
distillation. Desalination 198, 67–73.
Hanhui, Z., Xiaoqi, Z., Xuehui, Z., 2006. Coagu-flocculationmechanismof flocculant and its
physical model. 2004 ECI Conference on Separations Technology VI: New Perspective
on Very Large-Scale Operations. The Berkeley Electronic Press, Berkeley, CA.
VSS [mg/L]
1st. step
2nd. step
0
VO control Ber-VO C150 control Ber-C150
Treatment
VO control Ber-VO C150 control Ber-C150
Treatment
VO control Ber-VO C150 control Ber-C150
Treatment
TSS [mg/L]
1st. step
2nd. step
0
turbidity [NTU]
1st. step
2nd.step
0
COD [mg/L]
1st. step
2nd. step
Fig. 5. TSS, VSS, turbidity and COD (a, b, c and d, respectively) concentrations after two 1-h sedimentation steps. Bold lines represent raw BWW parameters. Ber-VO and Ber-C150
series denote the use of the organoclays and raw clay minerals in the 1st and 2nd step, respectively, whereas VO control and C150 control series denote the use of the raw minerals
for both steps.

6. 124 T.N. König et al. / Applied Clay Science 67–68 (2012) 119–124
Johnston, C.T., 1996. Sorption of organic compounds on clay minerals: a surface functional
group approach. In: Sawhney, B. (Ed.), CMSWorkshop Lectures. Organic Pollutants in
the Environment, vol. 8. The Clay Mineral Society, Boulder, CO, pp. 1–44.
Kargi, F., Dinçer, A.R., 1996. Enhancement of biological treatment performance of saline
wastewater by halophilic bacteria. Bioprocess and Biosystems Engineering 15,
51–58.
Kargi, F., Uygur, A., 1996. Biological treatment of saline wastewater in an aerated percolator
unit utilizing halophilic bacteria. Environmental Technology 17, 325–330.
Kodama, H., 1985. Infrared Spectra of Minerals: Reference Guide to Identification and
Characterization of Minerals for the Study of Soils. Research Branch, Agriculture
Canada, Ottawa, p. 156.
Lagaly, G., 2006. Colloid clay science. In: Bergaya, F., Theng, B.K.G., Lagaly, G. (Eds.),
Handbook of Clay Sceince. Elsevier Ltd., Amsterdam, pp. 309–377.
Lefebvre, O., Vasudevan, N., Torrijos, M., Thanasekaran, K., Moletta, R., 2005. Halophilic
biological treatment of tannery soak liquor in a sequencing batch reactor. Water
Research 39, 1471–1480.
Little, L.W., Lamb III, J.C., Horney, L.F., 1976. Characterization and treatment of brine
wastewaters from the cucumber pickle industry. UNC Wastewater Research Center,
Department of Environmental Sciences and Engineering. UNC Wastewater Research
Center, Department of Environmental Sciences and Engineering, School of Public
Health University of North Carolina at Chapel Hill. ESE Publication No. 399.
Margulies, L., Rozen, H., Nir, S., 1988. Model for competitive adsorption of organic cations
on clays. Clays and Clay Minerals 36, 270–276.
Metcalf and Eddy, Inc., 2003. Wastewater Engineering: Treatment and Reuse, fourth
ed. McGraw-Hill, New York.
Mousavi, S.M., Alemzadeh, I., Vossoughi,M., 2006. Use ofmodified bentonite for phenolic ad-sorption
in treatment of olive oil mill wastewater. Iranian J. Sci. Technol. 30, 613–619.
Nakanishi, K., Solomon, P.H., 1977. Infrared Absorption Spectroscopy. Holden-Day,
Oakland, CA, p. 54.
Ruiz-Hitzky, E., 2001. Molecular access to intracrystalline tunnels of sepiolite. Journal
of Materials Chemistry 11, 86–91.
Rytwo, G. 2004 A worksheet adsorption/desorption model on clays, in Clay Surfaces:
Fundamentals and Applications, Wypych F. and Satyanarayana, K.G. (Eds.) in the
Series: “Interface Science and Technology book series”, Series Editor: A Hubbard,
Elsevier Academic Press, Amsterdam, The Netherlands, p. 153–183.
Rytwo, G., Gonen, Y., 2006. Very fast sorbent for organic dyes and pollutants. Colloid &
Polymer Science 284, 817–820.
Rytwo, G., Nir, S., Margulies, L., Casal, B., Merino, J., Ruiz-Hitzky, E., Serratosa, J.M., 1998.
Adsorption of monovalent organic cations on sepiolite: experimental results and
model calculations. Clays and Clay Minerals 46, 340–348.
Rytwo, G., Serban, C., Tropp, D., 2002. Adsorption and interactions of diquat, paraquat and
methyl green on sepiolite: experimental results and model calculations. Applied Clay
Science 20 (6), 273–282.
Rytwo, G., Gonen, Y., Afuta, S., Dultz, S., 2005. Interactions of pendimethalin with an
organo-montmorillonite complex. Applied Clay Science 28, 67–77.
Rytwo, G., Kohavi, Y., Botnick, I., Gonen, Y., 2007. Use of CV- and TPP-montmorillonite for
the removal of priority pollutants from water. Applied Clay Science 36, 182–190.
Rytwo, G., Gonen, Y., Afuta, S., 2008. Preparation of Berberine–montmorillonite–
metolachlor formulations from hydrophobic/hydrophilic mixtures. Applied Clay
Science 41, 47–60.
Rytwo, G., Rettig, A., Gonen, Y., 2011a. Organo-sepiolite particles for efficient pretreatment of
organic wastewater: application to winery effluents. Applied Clay Science 51, 390–394.
Rytwo, G., Varman, H., Bluvshtein, N., König, T.N., Mendelovits, A., Sandler, A., 2011b.
Adsorption of berberine on commercial minerals. Applied Clay Science 51, 43–50.
Song, Z., Williams, C.J., Edyvean, R.G.J., 2004. Treatment of tannery wastewater by
chemical coagulation. Desalination 164, 249–259.
Sparks, D.L., 1995. Environmental Soil Chemistry. Academic Press, Inc., London, UK.
Tolsa Group, 2008a. Pangel C150 Technical Data Sheet. Tolsa SA, Madrid 28022, Spain.
Tolsa Group, 2008b. Pangel S9 Technical Data Sheet. Tolsa SA, Madrid 28022, Spain.
Yariv, S., Michaelian, K.H., 2002. Structure and surface acidity of clay minerals. In: Yariv,
S., Cross, H. (Eds.), Organo-Clay Complexes and Interactions. Marcel Dekker, Inc.,
New York, pp. 1–38.
Zermane, F., Naceur, M.W., Cheknane, B., Messaoudene, N.A., 2005. Adsorption of
humic acids by a modified Algerian montmorillonite in synthesized seawater.
Desalination 179, 375–380.