Advances in Environmental Research 7 (2003) 389–403

High-pH–magnesium coagulation–flocculation in wastewater

treatment
L. Semerjian, G.M. Ayoub*
Faculty of Engineering and Architecture, American University of Beirut, P.O. Box 11-0236, Beirut, Lebanon

Accepted 9 January 2001

Abstract

Chemically enhanced wastewater treatment is attracting substantial interest, especially for wastewaters that are not
amenable to treatment by conventional biological treatment strategies. Among the currently employed chemical unit
processes in wastewater treatment, coagulation–flocculation has received considerable attention for yielding high
pollutant removal efficiency. Over the past years, several authors have investigated the role of magnesium ions as a
potential coagulant for the chemical clarification of wastewater. This paper presents a comprehensive review of high-
pH–magnesium coagulation–flocculation processes in wastewater treatment, describes their applicability and reveals
the contribution of such treatment strategies to the chemical clarification of various wastewaters. More importantly,
the paper discusses the advantages, disadvantages and process efficiency of high-pH–magnesium coagulation–
flocculation in relation to various sources of magnesium ions. The characteristics of sludges produced from lime-
based chemical wastewater treatment processes are also discussed. Finally, factors impacting the economics of the
process are considered to estimate the costs incurred.
䊚 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Wastewater; Chemical treatment; Coagulation–flocculation; Industrial wastewater; Seawater; Bittern; Magnesium;
Metals; Lime; Caustic

1. Introduction control and rising construction and energy costs, sub-

Chemical treatment of wastewater pollutants was
investigated and developed long ago; however, its full
implementation was delayed in favor of biological
treatment methods due to the elevated costs of chemicals
at that time (Culp, 1967; Culp et al., 1978). Neverthe-
less, biological treatment may not always be suitable,
especially for specific situations, such as intermittent
waste flows, wastes containing substances toxic to
biological growth and wastewaters containing non-bio-
degradable impurities.
In recent years, with the technological advancements
in polymer chemistry, increased interest in nutrient
*Corresponding author. Fax: q961 1 74 44 62.
E-mail address: gayoub@aub.edu.lb (G.M. Ayoub).
1093-0191/03/$ - see front matter 䊚 2002 Elsevier Science Ltd. All rights reserved.
PII: S 1 0 9 3 - 0 1 9 1 Ž 0 2 . 0 0 0 0 9 - 6
stantial interest has developed in chemically enhanced
wastewater treatment methods. This has evolved mostly
in response to several operational and regulatory obsta-
cles facing both the wastewater dischargers and the
wastewater treatment plants (Eilbeck and Mattock,
1987). At present, several countries rely on chemical
processes to treat their raw wastewaters, either as the
only advanced primary or the secondary chemical treat-
ment method, or as a pre-treatment stage prior to
biological treatment (Morrissey and Harleman, 1990;
Ødegaard, 1992). Moreover, various existing conven-
tional primary wastewater plants are shifting towards
chemically enhanced treatment to improve the quality
of the treated effluent. Such an improvement would
reduce the size, complexity and cost of secondary
treatment to conform with environmental regulations
and guidelines (Harleman et al., 1991).
390 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403

The rationale for the increasing popularity of chemical than is produced by conventional primary treatment
treatment plants pertains to the following associated (Harleman and Morrissey, 1990). However, with
advantages (Poon and Brueckner, 1975; Stuckenberg, reduced chemical costs and feasible sludge disposal,
¨
1975; Forstner and Van Leirde, 1981; Eilbeck and chemically enhanced treatment could prove to be one
Mattock, 1987; Harleman et al., 1991; Ødegaard, 1987, of the most appropriate technologies in wastewater
1992): treatment, particularly when coastal waters are the final
destination of treated effluents (Ayoub, 1994).
● They proceed rapidly, are more predictable, more
As previously stated, coagulation–flocculation has
subject to control by simple techniques, and are most
always attracted considerable attention for yielding high
frequently amenable to automatic control.
removal efficiency in wastewater treatment. Over the
● They are relatively tolerant to toxic compounds and
past years, a wide array of laboratory- and pilot-scale
temperature changes, and can be operated on an on–
experiments were conducted to investigate the effect of
off basis without the need for an acclimatization
both calcium and magnesium precipitation on the chem-
period.
ical clarification of wastewater. This paper presents a
● In contrast to biological systems, they can accom-
comprehensive review of the coagulation of alkalized
modate variable input loads and flows, such as
wastewaters by high-pH–magnesium coagulation–floc-
seasonal flows, as well as intermittent and complex
culation processes and describes the chemical aspects
discharges, as in the case of industrial wastewaters.
of applied treatment strategies. It also reveals and
● When needed, chemical plants are flexible and can
compares the contribution of such treatment strategies
be readily modified without necessity for a change
to the chemical clarification of various wastewaters.
in the basic structure.
● Chemical treatment systems generally have lower
2. Background information on chemical treatment of
space requirements and substantially lower installa-
wastewater
tion costs. However, it is noteworthy to mention that
operation costs can be high, especially with large-
Generally, wastewater colloidal suspensions consist
scale plants.
of negatively charged particles. When particles are
● Chemically enhanced wastewater treatment can han-
similarly charged, the resulting repulsive forces tend to
dle higher hydraulic loads compared to conventional
stabilize the suspension and prevent particle agglomer-
treatment methods.
ation. The process of coagulation is complex and may
● When used as a pre-treatment stage, subsequent
involve several mechanisms to achieve destabilization,
biological systems become more efficient in dealing
which allows particle agglomeration and enhances sub-
with lowered biochemical oxygen demand influents.
sequent particle removal. Coagulation is typically
Moreover, following advanced primary treatment,
accomplished through chemical addition and mixing.
subsequent secondary biological systems occupy a
The process is used to enhance the degree of removal
considerably smaller land area and handle higher
of total suspended solids (TSS), biochemical oxygen
hydraulic loadings compared to conventional biolog-
demand (BOD), chemical oxygen demand (COD), and
ical systems.
bacterial population in primary settling facilities, as well
● Almost complete removal of phosphorus and limited
as to improve the performance of secondary treatment
quantities of nitrogen may be achieved at sites where
processes (Tchobanoglous and Burton, 1991).
eutrophication is a problem.
Flocculation is the physical process of bringing the
● Significant particle removal, and consequently effec-
destabilized particles in contact to form larger flocs that
tive removal of micro-pollutants, heavy metals, bac-
can be more easily removed from suspension. Floccu-
teria and viruses, may be achieved.
lation is almost always used in conjunction with and
● Usually, chemical processes can be designed to pro-
preceded by coagulation. The process is generally
vide useful by-products.
accomplished by slow mixing of the destabilized sus-
On the other hand, a number of disadvantages may pension to provide an opportunity for the particles to
accompany chemical treatment processes. For instance, come into contact with one another and bridge together.
relatively larger quantities of inorganic sludge are pro- Therefore, flocculation enhances subsequent sedimen-
duced, in addition to the higher salinity in the effluent tation or the performance of filtration systems by
discharged on account of the additive nature of the increasing particle size, resulting in increased settling
process (Eilbeck and Mattock, 1987; Tchobanoglous and filter-capture rates.
and Burton, 1991; Van Nieuwenhuiyzen et al., 1999). The most commonly used coagulants–flocculants in
Conventional chemical treatment processes produce wastewater treatment are: the trivalent salts of iron
between 1.5- and 2.0-fold more sludge than is produced wFeCl3, Fe2(SO4)3x and aluminum wAl(SO4)3 x; ferrous
by conventional primary treatment, whereas biological sulfate (FeSO4); and calcium hydroxide wCa(OH)2x.
treatment produces approximately 1.9-fold more sludge These are often used with various coagulant aids, such
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403
as synthetic polyelectrolytes (anionic, cationic, or non-
ionic polymers), fly ash and clay. The choice of a
specific coagulation reagent is firstly governed by its
effectiveness, and secondly by its cost, relative to
alternative reagents (Eilbeck and Mattock, 1987; Mc-
Ghee, 1991; Tchobanoglous and Burton, 1991; Casey,
1997). Recently, magnesium ions from various sources
have gained in popularity as coagulants for the chemical
clarification of various alkalized municipal and indus-
trial wastewaters. The following sections demonstrate
the role of various sources of magnesium ions in
wastewater treatment.
3. Experiences in the utilization of magnesium in
wastewater treatment
3.1. High-pHymagnesium processes
Traditionally, alkalizing agents, such as lime or caustic
soda, have been employed to raise the pH levels needed
to induce chemical clarification of wastewaters.
3.1.1. Lime alkalization
The use of lime in wastewater treatment was intro-
duced long ago. Lime, as a general term, includes
quicklime (CaO), hydrated lime wCa(OH)2 x, and dolo-
mitic lime as defined by the National Lime Association
(NLA, 1999). However, the two forms of lime mostly
used in wastewater treatment are CaO and Ca(OH)2.
Historically, lime has been used in treating wastewaters
for a multitude of reasons. It has the inherent advantage
of making no contribution to an increase in salinity, as
is the case when alum or iron salts are employed
(Dziubek and Kowal, 1984). Moreover, apart from its
positive economical impact in terms of chemical cost
and energy requirements, lime effectively acts as both a
precipitant for phosphates, many trace metals, and bac-
teria, and as a coagulant for the removal of suspended
and colloidal material in municipal wastewater. Achiev-
able percentage removals of BOD, COD, TSS and total
phosphorus are in the range 64–75%, 57–72%, 75–
91% and 71–93%, respectively (Black and Lewan-
dowski, 1969; Parker, 1972; Horstkotte, 1974;
Stuckenberg, 1975). In addition, algae removal of 80%
was attained when lime alone was added to wastewater
containing a sufficient amount of bicarbonate alkalinity,
hardness and phosphates (Ayoub et al., 1986; Ayoub,
1994). The mechanisms of chemical clarification are
explained by the following reactions (Culp et al., 1978;
Tchobanoglous and Burton, 1991):
CaŽOH.2qH2CO3°CaCO3xq2H2O (1)
CaŽOH.2qCaŽHCO3.2°2CaCO3xq2H2O (2)
3CaŽOH.2q2PO43y°Ca3ŽPO4.2xq6OHy (3)
391
4CaŽOH.2q3PO3y
4 qH2O
°Ca4HŽPO4.3xq9OHy (4)
The calcium carbonate formed according to Eq. (1)
and Eq. (2) precipitates out of solution at a pH range
of 9.1–9.5, and acts through the ‘sweep coagulation’
mechanism to entrap suspended and colloidal particles.
It also acts as a ‘weighting agent’ by increasing the
density of the settlable particles, thereby enhancing their
settlement (Leentvar and Rebhun, 1982). Precipitation
of phosphates wEq. (3) and Eq. (4)x occurs within the
pH range 10.5–11.0 (Dziubek and Kowal, 1984).
Another important aspect of lime precipitation is the
appreciable degree of disinfection occurring in the
process. It was reported that at pH 11.0–11.5 and a
contact time of 4 h, bacterial organisms are completely
inactivated (Riehl et al., 1952). Grabow et al. (1978)
noted that lime flocculation–sedimentation at pH 9.6
reduced the coliform organisms, enteric viruses and
coliphages by 62.35%, 99.98% and 57%, respectively.
At pH 11.2, these values increased to reach 99.98%,
100% and 99.95%, respectively. The decreased micro-
bial content attained in the effluent is due to the
combined effects of exposure to high pH and simulta-
neous flocculation of microorganisms by the coagulating
particles, as 60–100% of viruses in wastewater are
adsorbed to particles (Vrale,
¨ 1978; Ødegaard, 1989).
Lime requirements, for optimal clarification, vary
with the type of wastewater to be treated. Precipitation
of wastewater with lime has yielded variable results at
different treatment plants. This behavior is mostly attrib-
utable to the initial composition of wastewater, mainly
in terms of bicarbonate alkalinity and total hardness.
Moreover, lime dosages found in jar tests or in plant
operations were 10–50% higher than the theoretically
predicted doses, in view of the fact that lime dissolves
partially, and thus is not completely utilized (Merril and
Jordan, 1975).
3.1.2. Caustic soda alkalization
Caustic soda (sodium hydroxide, NaOH) can be used
as an alternative source of hydroxyl ions needed to raise
the pH to levels at which precipitation of calcium and
magnesium hydroxides are induced. The following
chemical reactions take place:
MgŽHCO3.2q2NaOH°MgŽOH.2xq2NaHCO3 (5)
CaŽHCO3.2q2NaOH°CaŽOH.2xq2NaHCO3 (6)
Removal of turbidity, suspended solids and organic
matter using only NaOH as the alkalizing agent was
reported to be comparable to that achieved when using
only lime (Merril and Jordan, 1975). However, from
the standpoint of economics and efficacy of phosphate
removal, the usage of lime is favored over NaOH.
Caustic soda was used as an alkalizing agent in
several studies. In a study by Ayoub et al. (1986), a
392 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403
solution of 5 N NaOH was used to test the effectiveness
of seawater for the removal of algae from oxidation
pond effluents. As a result, algae removal in excess of
80% was achieved at an initial pH of 10.5 and 5–10%
seawater. On the other hand, almost complete algae
removal ()95%) was attained at pH 11.0 and 10–15%
seawater. In another study, a lime dosage of 1000 mgyl
resulted in more than 80% algae removal. When caustic
soda was used instead of lime to raise the pH to the
same level, only 50% removal was achieved. Moreover,
the same study also revealed similar patterns of oil
removal from alkaline wastewaters (94–97%) when
using either lime or NaOH to raise the pH to similar
levels in the presence of 5–10% seawater (Ayoub,
1994).
3.1.3. Role of magnesium ions at high pH
As previously noted, flocculation at high pH achieves
efficient removal of particles, colloids and certain dis-
solved materials present in the wastewater. However,
alkaline flocculation was found to be most effective in
matrices containing relatively high concentrations of
magnesium ions (Minton and Carlson, 1976; Leentvar
and Rebhun, 1982; Elmaleh et al., 1996). When mag-
nesium is initially present in wastewater, an increase in
pH upon alkalization will result in the precipitation of
magnesium hydroxide:
Mg2qq2OHy°MgŽOH.2x (7)
Magnesium precipitation begins at approximately pH
9.5, becomes significant above pH 10.5, and is essen-
tially complete at pH 11.0–11.5. Good clarification is
usually not achieved until pH 11.0–11.5 is reached
(Merril and Jordan, 1975; Dziubek and Kowal, 1984).
The resulting magnesium hydroxide is a gelatinous
precipitate, which was found to serve as an efficient
coagulant and flocculant aid (Vrale,
¨ 1978). Therefore,
in order for the treatment process to operate efficiently,
either lime or NaOH should be used to increase the pH
of the original wastewater to pH 11.0–11.5 (Dziubek
and Kowal, 1989; Ayoub, 1994). At such a high pH,
two major reactions are effective in liquid–solid sepa-
ration: CaCO3 and Mg(OH)2 precipitation. Both the
CaCO3 precipitate (point-of-zero-charge at approximate-
ly pH 8–9, Parks, 1967) and the primary particles are
negatively charged. The formation of CaCO3 induces a
sweep coagulation process, whereby only the larger
particles are entrapped. On the other hand, the
Mg(OH)2 precipitate (point-of-zero-charge of magnesi-
um oxide is approximately at pH 12.4, Parks, 1967;
Stumm and Morgan, 1981) has a large adsorptive
surface area and a positive superficial charge, which
attracts the negatively charged colloidal particles,
including the CaCO3 flocs, thus inducing adsorption
and agglomeration. This explains the significant effi-
ciency achieved when Mg(OH)2 is precipitated. In fact,
the treatment efficiency steeply increases when the pH
value is at approximately the theoretical value for
Mg(OH)2 precipitation, pH 11.3 (Leentvar and Rebhun,
1982; Elmaleh et al., 1996).
The contribution of calcium and magnesium com-
pounds to the efficiency of water treatment was first
reported in the late 1920s (Dziubek and Kowal, 1986).
Since then, several researchers have investigated the
effects of high-pH magnesium and calcium precipitation
on coagulation using a variety of magnesium ion
sources, such as magnesium chloride, magnesium car-
bonate, magnesium hydroxide, processed dolomite, sea-
water, seawater liquid bittern and marine dried bittern.
In a study by Leentvar and Rebhun (1982), signifi-
cant reductions in suspended solid extinction (rate of
reduction of light absorbance) and total organic carbon
(TOC) were obtained by low-pH lime treatment (pH
9.5); however, even better efficiency was attained by
the high-pH lime treatment (pH 11.0–11.5), apparently
due to both CaCO3 and Mg(OH)2 precipitation. On
average, 45% of TOC and 85% of the extinction were
removed by CaCO3 formation; an additional 16% of
TOC and 7% of suspended solid extinction were
removed by Mg(OH)2 precipitation. The experiments
showed that, in practice, coagulation–flocculation with
lime give better removal when the initial magnesium
content in the wastewater is high. Also, as the magne-
sium concentration in the wastewater increases, the pH
value needed for precipitation of colloidal particles with
Mg(OH)2 is reduced (Vrale, ¨ 1978).
A high-pH lime–magnesium process was also used
by Dollof et al. (1972) for the treatment of municipal
wastewaters. The process yielded reductions of 31%,
91% and 97% for total nitrogen, suspended solids and
total phosphorus, respectively, and 80% for each of
TOC, COD and BOD.
Dubose (1973), in his raw municipal wastewater
treatment studies, concurrently used lime and recycled
magnesium ions. Compared to treatment with lime
alone, better removal efficiency was obtained for COD,
phosphates, TSS and color.
In a pilot-plant study, the high-pH lime–magnesium
process (pH 11.5) also proved efficient in the removal
of most pollutants from secondary effluents by the
mechanisms of coagulation–flocculation and sedimen-
tation (Idelovitch, 1978). The process led to a reduction
in suspended solids (including algae), colloidal and
soluble organic matter, bacteria, viruses and some inor-
ganic dissolved solids. In addition, phosphorus, partic-
ulate organic nitrogen, boron and fluoride concentrations
were reduced by 91%, 33%, 53% and 67% in the
summer (20–30 8C) and 75%, 30%, 35% and 55% in
winter (10–20 8C), respectively.
Finally, suspensions of lime were used by Dziubek
and Kowal (1984) as coagulant for the chemical treat-
ment of secondary wastewater effluent. Precipitation of
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403
Table 1
Most abundant solutes in seawater (Garrison, 1996)
Ion Seawater Dissolved ions
(wt.%) (wt.%)
Chloride (Cly) 1.9 55.04
Sodium (Naq) 1.1 30.61
Sulfate (SO2y
4 ) 0.3 7.68
Magnesium (Mg2q) 0.1 3.69
Calcium (Ca2q) 0.04 1.16
Potassium (Kq) 0.04 1.10
Bicarbonate (HCOy
3 ) 0.01 0.41
Bromide (Br-) 0.0065 0.19
magnesium was strongly correlated with the removal of
color, turbidity, COD and phosphates. Removal curves
showed a characteristic inflection at pH 10.5, above
which the degree of removal rapidly increased. The
highest degree of removal was obtained at a pH
approaching 11.5 with a lime dose of 200 g CaOym3.
To determine the actual contribution of Mg(OH)2, sup-
plements of magnesium ions in the form of Mg(OH)2
suspension were added to the secondary effluent. Com-
pared to coagulation with lime alone, the removal
efficiency increased by 42%, 24% and 13% for phos-
phates, TOC and COD, respectively. Moreover, in other
studies, Dziubek and Kowal (1983, 1989) used calcined
dolomite to act as the coagulant in a novel high-pH
surface water treatment technology. The optimum cal-
cined coagulant dose was found to be 300 gym3,
yielding a colorless and clear effluent, displaying high
removal of organic matter (60% COD and 65% TOC)
and heavy metals, as well as partial inactivation of
viruses and bacteria. The primary mechanism governing
the removal of organic matter is adsorption on both the
precipitating CaCO3 and the Mg(OH)2 flocs. The opti-
mum pH for the new technology approaches 10.5, and
thus is much lower than the value required for high
lime–magnesium treatment.
3.2. High-pHyseawater process
Coagulation–flocculation of alkalized wastewaters,
using seawater as an inexpensive source of magnesium
ions, was reported to be effective for the removal of a
wide range of impurities. Seawater is composed of
various cations and anions, as summarized in Table 1.
However, only magnesium cations, which result from
the presence of magnesium sulfate and magnesium
chloride, serve as effective coagulants at high pH levels
of 11.0–11.5.
In the course of coagulation with seawater,
Mg(OH)2 precipitation may occur by any of the follow-
ing chemical reactions, depending on the alkalizing
agent employed:
393
MgSO4qCaŽOH.2°MgŽOH.2xqCaSO4 (8)
MgCl2qCaŽOH.2°MgŽOH.2xqCaCl2 (9)
MgSO4q2NaOH°MgŽOH.2xqNa2SO4 (10)
MgCl2q2NaOH°MgŽOH.2xq2NaCl (11)
The minimum seawater concentration needed for
effective flocculation will be a function of the hydroxyl
ion concentration, the solubility of magnesium ions in
equilibrium with solid Mg(OH)2 and the minimum
amount of Mg(OH)2 that must be precipitated (Ayoub
et al., 1992).
Seawater flocculation at high pH levels was investi-
gated by Ayoub et al. (1986, 1992) for the removal of
algae from stabilization pond effluents, as well as
emulsified oil and suspended solids from wastewaters.
It was demonstrated that a reduction in algal concentra-
tions by 95% or more might be achieved at different
seawater concentrations and under alkaline conditions.
In addition, high oil removal (94–97%) was achieved
at seawater concentrations of 5% and greater, in the
presence of either lime or caustic soda. Various types
of highly alkaline industrial wastewaters were also
studied to assess the removal of selected pollutants. TSS
removal was in the range of 90–95%, whereas COD,
total Kjeldahl nitrogen (TKN) and total phosphorus
removal averaged approximately 80%, 65% and 95%,
respectively, at an optimal seawater dose of 10% and
without the need for a supplemental source of OHy
ions. These findings would allow great cost savings to
industries, especially in coastal regions.
Full-scale operation and laboratory studies have been
carried out to assess the chemical precipitation of
municipal wastewater with lime and seawater (Vrale, ¨
¨ 1984; Ødegaard, 1989). Both
1978; Ferguson and Vrale,
experiences revealed that seawater addition as low as
1–2% can considerably improve phosphorus removal
efficiency in the presence of lime as the precipitant
(pH)11). This phenomenon is attributable to the addi-
tion of magnesium contained in seawater to the waste-
water. Seawater addition results in both higher
phosphorus removal and a lower lime requirement, thus
improving the performance and economics of lime use.
Experimentation shows that the lime dosage needed to
reach a specific residual total phosphate or TSS is
reduced by 20–40% in the presence of seawater. The
process represents a feasible alternative for phosphorus
removal in coastal areas because of proximity to sea-
water (Vrale,
¨ 1978; Ferguson and Vrale, ¨ 1984). In fact,
Norway operates numerous lime–seawater plants for
wastewater treatment, especially in coastal tourist areas.
Operational data from such Norwegian plants reveal
average reductions of 67%, 70%, 92% and 93% for
COD, BOD, total phosphorus and suspended solids,
respectively, for seawater additions of 2–5% and lime
dosage of 158–300 mg Ca(OH)2 yl (Ødegaard, 1989).
394 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403

The addition of seawater has also proven to be advan- Table 2

tageous at treatment plants that use coagulation with Average chemical composition of marine bittern as a function
ferric chloride (FeCl3 ). In fact, it is claimed that the of density (Arshad Ali Beg et al., 1986a,b)
addition of 1–2% seawater has reduced FeCl3 dosages
Density (20 8C) Compound (% wyw)
by 20–30% (Berge and Sæther, 1985).
(gyml)
The beneficial effects of seawater addition in terms NaCl KCl MgCl2 MgSO4
of particle destabilization, aggregation and improved
1.020 3.05 0.19 0.51 0.26
settling are explained by the increased formation of
1.027 3.05 0.19 0.43 0.30
insoluble Mg(OH)2 and the abundance of electrolytes, 1.030 3.30 0.19 0.61 0.31
leading to a compaction of the colloidal double layer, 1.037 4.06 0.19 0.52 0.42
thus resulting in improved coagulation (Ødegaard, 1.069 7.37 0.38 1.27 0.74
1989). Additional benefits of the lime–seawater process 1.095 9.66 0.32 0.30 1.01
include the lower E. coli content achieved, as well as 1.139 14.23 0.57 1.79 1.23
the lower total operational costs. It was found that 1.169 11.69 1.33 4.96 1.09
coagulation with the lime–seawater process would be 1.202 14.99 1.52 6.09 2.48
28% cheaper in operation than FeCl3 coagulation 1.222 16.62 1.86 5.36 5.69
(Ødegaard, 1989). 1.241 14.93 1.37 6.26 4.09
1.251 8.37 2.42 10.46 6.52
In another study, seawater was used as an anolyte,
1.260 8.31 2.41 11.04 6.85
while wastewater served as the catholyte. As a current 1.270 6.49 2.86 13.55 7.18
was applied to the electrolytic cell, the hydrogen ions 1.281 7.37 2.56 11.86 7.30
present in the seawater were reduced to hydrogen gas. 1.295 4.94 3.46 14.73 7.78
This resulted in the formation of excess OHy ions, and 1.302 2.79 3.87 18.03 5.90
consequently to an increase in pH. Under these alkaline 1.315 2.55 4.16 19.28 6.38
conditions, magnesium ions in the seawater precipitate 1.321 0.91 1.42 25.50 4.54
as Mg(OH)2 flocs, which are made to float to the
surface by virtue of the rising hydrogen bubbles. The
Mg(OH)2 flocs formed contribute to the removal of (1983) found liquid bitterns to be effective and econom-
phosphates (98%), ammonia-nitrogen (90%), total ical coagulants for color removal in pulp and textile
nitrogen (80%), BOD (85% after 60 min of operation) industries. A color reduction of 85% was achieved in
and TSS (87% after 60 min of operation) (Poon and both alkaline and acid bleach-pulp industrial effluents
Brueckner, 1975). with the addition of 2% liquid bittern when maintained
Finally, a study carried out by Shin and Lee (1997) at the optimum pH level using lime. In addition, color
revealed 62% removal of ammonia and 95% removal removal of approximately 80% was obtained with 2%
of phosphorus from alkalized wastewater in the presence liquid bittern added to a textile waste stream containing
of seawater. acid and direct azo dyes. The vital reaction in achieving
color clarification is the development of chemical inter-
3.3. High-pHyseawater liquid bittern process actions between magnesium and color-causing com-
pounds, leading to the formation and settling of
Seawater liquid bittern is defined as the residual insoluble aggregates. The high ionic strength of liquid
concentrated liquor remaining after the complete depo- bittern induces the destabilization of colloids. This can
sition of calcium salts (CaSO4 and CaCO3 ) and crystal- be explained on the basis of the Gouy–Chapman theory
lizing out most of the sodium chloride (NaCl) upon the of the electric double layer, where the thickness of the
solar evaporation of seawater (Lozano, 1993; Abdallah, double layer decreases with the increasing ionic strength
1996). This concentrate is known to contain valuable in a way that is consistent with the rise in efficiency of
chemicals. However, this rich ore is seldom appropriate- colloid removal corresponding to the rise in the ionic
ly exploited, and is often allowed to be discharged back strength (Sundstorm and Klei, 1980; Ødegaard, 1989;
into the sea, thus significantly augmenting magnesium Casey, 1997).
salts at the discharge area. The chemical composition In another study, in which liquid bittern was used as
of liquid bittern is a function of its density. Table 2 the coagulant, nutrient removal of 72% and 99% for
presents the average chemical composition of marine ammonia and phosphorus, respectively, was reported.
liquid bittern obtained from a solar salt factory. Percentage removals dropped to 62% and 95% when
The enriched magnesium content (1.32–2.85 molykg seawater served as the coagulant (Shin and Lee, 1997).
at 1.252–1.319 gyml), as well as the high ionic strength Several other laboratory studies were conducted to
(4.05=10y2 salinity0.8), encouraged several investiga- determine the efficacy of seawater bittern as a coagulant
tors to utilize marine bitterns as coagulants for the for the chemical purification of alkalized municipal and
treatment of various wastewaters. Wang and Chen industrial wastewaters. In the case of municipal waste-
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403 395

water, turbidity and suspended solids removal was found Table 4

to exceed 95% and COD reduction was in excess of Physico-chemical characteristics of the liquid bittern produced
75%, while dissolved organic carbon (DOC) removal (Semerjian, 2000)
averaged approximately 30%. The mode of alkalization,
Parameter Value
whether by the addition of slaked lime or caustic soda,
measured
had a very limited effect on the efficiency of treatment.
However, the addition of lime resulted in a lower pH 6.78
percentage increase in TDS and EC, in contrast to the Density (20 8C) (gyml) 1.2705
addition of NaOH. This is attributed to the precipitation TDS (mgyl) 396 000
of both Mg(OH)2 and CaCO3 in the former, while the Electrical conductivity (25 8C) 794 000
(mmhosycm)
latter induces the formation of soluble sodium carbonate
Mg2q (mgyl) 53 473
(Na2CO3), which remains dissolved as Naq and CO32y Ca2q (mgyl) 0
in the effluent and contributes to an increase in TDS Cly (mgyl) 279 913
(Merhebi, 1996; Ayoub et al., 1999, 2000). For munic- Naq (mgyl) 70 883
ipal wastewater, the lime–LB treatment process resulted Kq 14 000
in better phosphorus, COD and TSS removal efficiency SO2y
4 (mgyl) 46 278
when compared to the corresponding efficiency obtained
Conversion factors for concentration units in mgyl to meqy
in conventional preliminary, primary and secondary l are Mg2qs0.0823; Naqs0.0435; Clys0.0282; and
wastewater treatment schemes, as reported in Table 3. SO2y
4 s0.0208.
In the case of industrial wastewater effluents, opti-
mum magnesium requirements and pollutant removal
percentages varied, depending on the type of industry. higher ionic strength than seawater, a characteristic
At matrix-specific optimum conditions, the respective shown to enhance colloidal destabilization (Wang and
TSSyturbidity and COD reductions were in excess of Chen, 1983).
95% for the ceramic tile manufacturing industry; 95% In another study, the effectiveness of seawater LB to
and 80.4% for the paper and cardboard industry; 95% remove heavy metals from alkalized MWW was evalu-
and 61.4% for the dairy products industry; 95% and ) ated. The average physico-chemical composition of the
95% for the marble tiles industry; )98% and 43% for seawater LB harvested is summarized in Table 4.
the leather tanning industry; and finally, approximately Selected metals were added, either individually or
90% and 83% for the ready-mix concrete industry concurrently, to 1 l of MWW alkalized by caustic soda
(Merhebi, 1996; Ayoub et al. 2000). or slaked lime. The optimum Mg2q concentration was
In all the experiments performed, liquid bittern dem- established to be approximately 107 mgyl, regardless of
onstrated an added advantage over seawater and dried the alkalization mode employed. The experimental pro-
bittern by contributing to the least increase in total gram covered eight metals, including arsenic, cadmium,
dissolved solids (TDS) in the treated effluent. This is chromium, copper, lead, mercury, nickel and zinc. Each
attributable to crystallizing out most of the NaCl during metal exhibited a characteristic removal efficiency in
the solar evaporation process. In fact, sodium and relation to its hydroxide solubility properties, as well as
chloride ions comprise the highest percentage by weight its affinity towards the precipitating suspended solids.
of dissolved ions in the seawater (Table 1). Thus, their Lime-treated MWW samples showed higher metal
removal will significantly reduce needless TDS increase removal efficiency compared to caustic soda treatment.
in the treated effluent. Additional advantages of liquid Upon the addition of LB to the alkalized MWW
bittern are its reduced bulk when compared to seawater samples, turbidity and metal removal was significantly
as a source of magnesium ions, as well as its 10-fold enhanced, especially for MWW alkalized with caustic

Table 3
Pollutant removal efficiency in various municipal wastewater treatment schemes (Shin and Lee, 1997; Ayoub et al., 1999; Qasim,
1999)

Type of treatment Removal efficiency (%)

P COD TSS
Preliminary Small 0–5 5–10
Primary sedimentation 10–20 30–40 50–65
Conventional activated-sludge system 10–25 80–85 80–90
High-rate trickling filter 8–12 60–80 60–85
Lime–LB 99 )75 )95
396 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403

Table 5 Table 6
Percentage of total metal concentration bound to suspended Comparison of removal efficiency for various individually add-
solids in raw wastewater (Ødegaard, 1989) ed metals from MWW by alkalization and alkalization–LB
processes (Semerjian, 2000)
Metal Zn Cu Ni Cr Pb Cd
Metal Metal removal (%)a
Bound (%) 51 48 13 71 71 82
NaOH NaOHqLB Ca(OH)2 Ca(OH)2qLB

soda. The addition of LB increased the initial metal Nickel 32.5 75.3 52.3 75.5
removal efficiency by 14.8–58.2% when MWW was Chromium 64.6 93.0 87.3 98.7
Copper 43.3 63.2 70.8 82.8
alkalized with caustic soda, and 1.6–23.2% when slaked
Lead 77.4 92.2 92.4 95.9
lime was the alkalizing agent. It is apparent that the Cadmium 72.8 97.5 82.4 99.1
contribution of LB is greater in the former process, Zinc 46.6 75.2 80.0 91.5
since the sole employment of caustic soda alkalization Arsenic 22.8 70.7 63.0 71.1
resulted in lower metal removal efficiency compared to Mercury 14.9 84.0 77.8 99.5
that attained in the lime alkalization process. For the a
Average of triplicate trial experiments.
lime–LB treatment process, high removal ()90%) was
achieved for cadmium, chromium, lead, mercury and
zinc, and reasonably good removal (71%, 82% and 75 until a batch of white crystals is obtained. The settled
%) for arsenic, copper and nickel, respectively. As crystals are washed and harvested to be used as DB.
stated earlier, efficiency enhancement can be attributed Chloride and sulfate are the major anions in DB. The
to the enriched magnesium content, as well as to the major cation of bittern solids is magnesium, weighing
high ionic strength of LB. In conclusion, metal removal approximately 10.1% of the total bittern solid weight.
patterns were directly correlated with suspended solid Thus, the magnesium concentration of this bittern is
removal patterns. This is explained by the fact that approximately 40-fold greater than that of seawater
metals are associated with suspended colloidal particles (Wang and Chen, 1983). The typical chemical constit-
to a great extent, but with varying affinity, as summa- uents of DB collected from salt production and process-
rized in Table 5. ing industries are presented in Table 9.
Table 6 compares the average removal efficiency for Seawater DB was also evaluated as a potential source
various individually added metals by alkalization and of magnesium for the coagulation of alkalized waste-
alkalization–LB processes. Table 7 compares the aver- waters. Several jar-test experiments were conducted
age removal efficiency for individually and concurrently using DB as the coagulant, in an attempt to compare its
added metals during the alkalization and the alkaliza- coagulating power relative to other sources of magne-
tion–LB treatment processes (Semerjian, 2000; Ayoub sium ions, such as seawater and LB. Known amounts
et al., 2001). of seawater, LB or DB were successively added to each
The data in Table 7 suggest that, regardless of the of six jars containing 2 l of alkalized municipal waste-
alkalization mode, the concurrent presence of metals water. Table 10 compares the efficiency of seawater,
does not induce a significant hindrance effect, except LB and DB in terms of percentage removal of turbidity,
for nickel. In fact, in the lime–LB treatment process, TSS and DOC, and the percentage increase in TDS.
the percentage removal of nickel increased by 18.5%
when the metal was concurrently present with other Table 7
metals. The same study has also revealed that higher Comparison of removal efficiency for individually vs. concur-
influent concentrations of a single metal showed higher rently added metals from MWW by the alkalization–LB pro-
removal efficiency (Semerjian, 2000; Ayoub et al., cess (Semerjian, 2000)
2001). On the other hand, when compared to the metal
removal efficiency obtained in pilot-scale activated- Metal Metal removal (%)a
sludge systems, the lime–LB process exhibited higher NaOH q LB Ca(OH)2 q LB
efficiency. The average removal efficiency of a range
of metals attained in various pilot activated-sludge Individual Concurrent Individual Concurrent
treatment plants are summarized and presented in Table Cadmium 97.5 91.9 99.1 99.3
8. Chromium 93.0 94.4 98.7 98.7
Copper 63.2 60.8 82.8 86.8
3.4. High pHyseawater dry bittern Lead 92.2 86.1 95.9 93.8
Nickel 75.3 74.1 75.5 94.0
Zinc 75.2 76.3 91.5 87.3
Seawater dry bittern (DB) may be prepared by the
a
evaporation of liquid bittern, followed by direct heating Average of replicate trial experiments.
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403 397

Table 8
Metal removal efficiency in activated-sludge pilot plants (Esmond, 1980; Petrasek and Kugelman, 1983; Lester, 1987; Chino et al.,
1991)

Parameter Influent Average Reference

concentration removal
(mgyl) efficiency
(%)
Cd 68 35 Patterson and Kodukula, 1984
21 39 Esmond and Petrasek, 1974
NR 49 Esmond, 1980
37 51 Davis and Jacknow, 1975
17 000 54 Petrasek and Kugelman, 1983
1 56 Chino et al., 1991
12 66 Stephenson et al., 1985
21 67 Rossin et al., 1982
Cr 171 5 Patterson and Kodukula, 1984
51 33 Petrasek and Kugelman, 1983
83 929 44 Barth et al., 1965
500 57 Esmond and Petrasek, 1974
76 59 Rossin et al., 1982
203 61 Davis and Jacknow, 1975
5 61 Chino et al., 1991
89 65 Stephenson et al., 1985
NR 65 Esmond, 1980
Cu 1373 33 Esmond and Petrasek, 1974
276 38 Patterson and Kodukula, 1984
172 43 Davis and Jacknow, 1975
NR 68 Esmond, 1980
570 72 Petrasek and Kugelman, 1983
36 000 75 Barth et al., 1965
79 545 78 McDermott et al., 1963
0.06 78 Chino et al., 1991
153 83 Rossin et al., 1982
135 83 Stephenson et al., 1985
Fe 831 57 Chino et al., 1991
2440 59 Petrasek and Kugelman, 1983
Pb 100 36 Patterson and Kodukula, 1984
NR 54 Esmond, 1980
216 56 Esmond and Petrasek, 1974
18 59 Chino et al., 1991
138 60 Davis and Jacknow, 1975
63 76 Rossin et al., 1982
580 81 Petrasek and Kugelman, 1983
57 93 Stephenson et al., 1985
Mn 89 25 Esmond and Petrasek, 1974
69 26 Chino et al., 1991
550 27 Petrasek and Kugelman, 1983
Hg -2000 0 Petrasek and Kugelman, 1983
NR Negligible Esmond, 1980
0.51 69 Esmond and Petrasek, 1974
Ni NR Negligible Esmond, 1980
715 0 Patterson and Kodukula, 1984
152 9 Davis and Jacknow, 1975
87 18 Stephenson et al., 1985
92 21 Esmond and Petrasek, 1974
130 22 Rossin et al., 1982
8333 28 Barth et al., 1965
1493 33 McDermott et al., 1965
270 33 Petrasek and Kugelman, 1983
6.7 36 Chino et al., 1991
Ag 9000 44 Petrasek and Kugelman, 1983
398 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403

Table 8 (Continued)
Parameter Influent Average Reference
concentration removal
(mgyl) efficiency
(%)
Zn 612 16 Patterson and Kodukula, 1984
598 54 Rossin et al., 1982
1226 57 Davis and Jacknow, 1975
NR 62 Esmond, 1980
1280 64 Petrasek and Kugelman, 1983
915 65 Esmond and Petrasek, 1974
554 65 Stephenson et al., 1985
224 70 Chino et al., 1991
102 273 89 McDermott et al., 1962
81 818 89 Barth et al., 1965

Table 10 reveals that the three sources of Mg2q ions geous over other chemically enhanced processes, such
generally produced satisfactory results. Turbidity and as polymer–ferric chloride or polymer–alum treatment.
TSS removal efficiency was highest (99.6% and 99.4%, From the standpoint of operation and process per-
respectively) when Mg2q ions were supplied by LB at formance, all of the experiments discussed earlier sug-
a concentration of 140–150 mgyl. Dried bittern was gest that magnesium ions, regardless of their source,
second in turbidity and TSS removal (98.0% and 96.5%, can be regarded as an effective coagulant for the
respectively) at a Mg2q concentration of 130 mgyl, purification of wastewater. However, process advantages
followed by seawater (95.4% and 88.6%) at a Mg2q and disadvantages may vary with varying sources of
dose of 165 mgyl. With respect to DOC, the most magnesium ions. Table 11 summarizes such character-
efficient removal was observed for seawater (55%), istics in relation to the various sources of magnesium
whereas approximately similar efficiency (35–36%) ions.
was recorded for liquid and dried bitterns. The addition
of optimum doses of Mg2q resulted in percentage
increases in TDS of approximately 405%, 53% and Table 10
102% for seawater, LB and DB, respectively. Thus, the Percentage removal of selected parameters from lime-alkalized
use of LB results in an appreciably lower increase in MWW using different sources of Mg2q ions (Ayoub et al.,
effluent TDS when compared to seawater and DB. An 1999)
approximate eight-fold increase in TDS is obtained
when seawater is used compared to LB, and four-fold Mg2q source Total Mg2q Removal (%) TDS
when compared to DB. This is attributed to the different concentration increase
(mgyl) Turbidity TSS DOC (%)
ionic compositions of the various sources of Mg2q ions.
Seawater 51.0 94.2 80.7 36 136
4. Discussion 87.6 95.7 76.8 50 234
126.2 91.1 76.3 54 232
4.1. Operation and process performance 166.8 95.4 88.6 55 405
209.6 94.2 76.3 56 527
255.0 93.4 72.8 51 657
As stated earlier, the lime–magnesium process has
been investigated by various researchers in the past two Liquid bittern 36.5 97.6 97.7 20 72
decades (Vrale,
¨ 1978; Ferguson and Vrale,¨ 1984; Ayoub 72.0 97.8 98.3 25 53
and Koopman, 1986; Ayoub et al., 1986, 1992; 107.6 98.9 97.9 29 44
143.2 99.6 99.4 35 53
Ødegaard, 1992). The process proved to be advanta-
178.9 99.5 97.5 36 104
214.5 99.5 97.5 30 142
Table 9
Chemical constituents of seawater dry bittern (Wang and Chen, Dried bittern 19.4 98.3 96.5 23 135
1983) 54.9 97.9 96.5 16 121
90.8 97.3 94.5 24 111
Chemical constituent Cly SO2y Naq Kq Mg2q H2O 126.5 98.0 96.5 36 102
4
162.2 97.9 95.1 43 95
Total solid weight (%) 33.5 2.3 0.5 0.6 10.1 53 197.9 97.3 94.7 39 84
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403
Table 11
Process advantages and disadvantages of various sources of Mg2q ions
Source of Mg2q Advantages
Seawater Readily available
No need for evaporation
No additional space requirements
for evaporation basins
Acceptable removal of algae,
emulsified oil, turbidity, TSS
and nutrients
Seawater Very high treatment efficiency
liquid bittern for TSS, turbidity, color,
COD, metals and nutrients
Higher magnesium content
and a 10-fold higher ionic strength
compared to seawater
Basically sterile solution
Easily produced from seawater
using solar energy
Appreciably low TDS increase (53%)
when compared to seawater
and seawater dry bittern
No algal growth problems
More amenable for transportation
to inland regions
Economically feasible
Seawater Moderate removal efficiency for
dry bittern TSS and turbidity
Less bulk volume for transportation
inland
Low TDS increase in effluent
when compared to seawater
(102% vs. 405%)
Certified Pure products
magnesium salts Moderate TDS increase
and hydroxides Very high removals of nutrients
It is noteworthy to mention that the pollutant removal
efficiency achievable is greatly affected by the initial
physico-chemical composition of the wastewater, mainly
in terms of the concentration of magnesium ions, sus-
pended solids, bicarbonate alkalinity, total hardness and
the presence of organic complexes or chelating agents.
The type and dosage of coagulant employed, the pres-
ence of flocculants or coagulant aids, the type and
structure of the particles, the pH and the temperature
may also alter process efficiency. Physical operational
variables, most notably mean velocity gradient and
mixing time, are also important determinants of the
performance of coagulation–flocculation processes. Oth-
er operational factors, such as overflow rate, settling
time and recirculation ratio, should also be taken into
account (Lee et al., 1994). Therefore, since most of the
399
Disadvantages
May induce the growth of algae and
marine organisms in inlet pipes
Significant increase in TDS
of effluent (405%)
May contain bacteria
Bulky if transported inland
Lower treatment removal efficiency
when compared to liquid bittern
Needs further evaporation of seawater
Use of additional land area for
evaporation process
More corrosive than seawater
Moderate TDS increase in effluent
when compared to liquid bittern
(102% vs. 53%)
Needs further processing of seawater
liquid bittern
Lower TSS and turbidity removal
efficiency when compared
to liquid bittern
Relatively expensive
Not readily available to many
communities
Requires proper storage areas
experiments discussed were conducted under controlled
laboratory conditions, the coagulant requirements and
process efficiency may vary under actual operational
conditions, such as large-scale wastewater treatment
plants. It is advisable that optimum conditions and
achievable performance in the treatment of wastewaters
produced under different environmental conditions be
separately evaluated.
4.2. Sludge characteristics of lime based treatment
processes
The increased volume of sludge generated in chemical
wastewater treatment has mostly hindered the adoption
of the process as a wastewater treatment strategy. How-
ever, lime-based chemical treatment processes have been
400 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403

Table 12
Chemical costs of alternative coagulation–flocculation processes (Semerjian, 2000)

Coagulant type FeCl3a Alumb LimeqLB

Coagulant dose (mgyl) 253 183 900
Unit price ($ylb) 0.13c 0.13c 0.036d
Total cost ($ym3 wastewater) 0.073 0.052 0.072
Coagulant aid type Anionic Anionic None
Coagulant aid dose (mgyl) 0.5 2.8 0
Unit price ($ylb) 4.69d 4.69d 0
Total cost ($ym3 wastewater) 0.0051 0.029 0
Sludge dewatering polymer type Organic NR None
Dewatering polymer dose (mgyt dry solids) 2.86 2.86 0
Unit price ($ylb) 4.69d 4.69d 0
Total cost ($yt dry solids) 0.029 0.029 0
Total treatment chemical costs ($) 0.078q0.029 0.081q0.029 0.072
a
Mean data of 50 Norwegian wastewater treatment plants (Ødegaard, 1992).
b
Mean data of nine Norwegian wastewater treatment plants (Ødegaard, 1992).
c
2000 US$ converted from 1990 US$ (Morrissey and Harleman, 1990) using CPI-U conversion factors for the year 2000 (US
Department of Labor, 2001).
d
2000 US$ converted from 1989 US$ (US EPA, 1998) using CPI-U conversion factors for the year 2000 (US Department of
Labor, 2001).

reported to produce sludges that are relatively compact
and possess certain advantageous qualities over other
chemical sludges. Improved sludge settling, compacti-
bility and dewatering characteristics; bacterial inactiva-
tion capability; recirculation and recycling potentiality;
and sludge stability comprise the major advantages of
lime-based sludges. Such advantages could partly offset
the burden of increased sludge volumes (Minton and
¨
Carlson, 1976; Ramirez and Malina, 1980; Forstner and
Van Leirde, 1981; Westphal and Christensen, 1983;
¨
Ferguson and Vrale, 1984; Teringo, 1987; Che et al.,
1988; Ødegaard, 1989; Suthaker et al., 1993; Guldner
et al., 1994; Poon and Boost, 1996; Boost and Poon,
1998; Ayoub and Merhebi, in press).
However, further research and experimentation are
highly recommended for more comprehensive and crit-
ical quantification and characterization of sludge in
chemical wastewater treatment systems.
4.3. Factors impacting the economics of the lime–LB
treatment process
The lime–LB chemical treatment process bears a
great resemblance to a conventional primary chemical
treatment strategy in terms of system configuration, and
thus capital costs. The components of the system include
a chemical feed system, a rapid mix tank, a flocculating
tank, a clarifier and sludge handling units, which are
typical for any chemical coagulationyprecipitation treat-
ment scheme. Additional land areas, and thus capital
costs, may be needed if seawater is to be evaporated
on-site for the production of concentrated liquid bittern.
Otherwise, the liquor can be transported from nearby
salt production works.
Regarding operation and maintenance costs, the lime–
LB process introduces appreciable savings in chemical
costs, especially since lime is readily available in most
countries and LB can be easily obtained in coastal
regions. Table 12 compares the cost of treatment chem-
icals associated with the lime–LB process to those used
in currently operating secondary chemical treatment
facilities.
Additional savings resulting from the lime–LB treat-
ment process include the costs associated with disinfec-
tion. The high pH of the process induces almost
complete disinfection, thus eliminating the need for a
separate disinfection process in the treatment system
(Ayoub et al., 1999, 2000). Bacterial inactivation is not
achieved in either the ferric chloride (pH 5.5–6.5) or
the alum (pH 5.0–6.0) coagulation–flocculation pro-
cesses. On the other hand, such high-pH effluents are
not suitable for direct discharge into inland waters.
Therefore, a recarbonation stage becomes necessary with
the lime–LB treatment process when the receiving water
bodies are inland waters. However, when discharging to
sea, the high effluent pH does not pose any adverse
effect, since it will be rapidly neutralized when dis-
charged through an efficient outfall diffuser (Ferguson
¨ 1984; Ødegaard, 1989).
and Vrale,
Another advantage of the lime–LB system, which
translates into long-term cost-effectiveness, is the poten-
tial of the system to be more heavily loaded hydrauli-
cally than primary precipitation plants operating with
alum, ferric chloride or lime alone as the coagulant.
The reason given for this potential is that flocs in the
lime–seawater process flocculate and settle very well;
however, this has not yet been scientifically demonstrat-
ed (Ødegaard, 1989).
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403
The main disadvantage presented by the lime–mag-
nesium process remains the large amounts of sludge
generated compared to the amounts produced in con-
ventional secondary chemical processes employing alum
or ferric chloride as coagulants. Fortunately, sludges
resulting from lime treatment possess superior thicken-
ing and dewatering characteristics and are suitable for
filter pressing at lower cost than sludges generated from
ferric chloride or alum (Forstner
¨ and Van Leirde, 1981).
In practice, the thickened sludge production is only 0.6–
1% of the wastewater flow (Ferguson and Vrale, ¨ 1984).
Another advantageous characteristic of the sludge pro-
duced is that it can be efficiently dewatered without the
addition of polymers or more lime, which are necessary
for the conditioning of sludges produced from ferric
chloride or alum coagulation processes. This character-
istic results in further savings in treatment chemicals.
Because of its high lime content and high pH, the sludge
produced is chemically ‘stabilized’, does not decompose
rapidly, and causes few odor problems (Ødegaard,
1989). Although sludge generation is higher for the
lime–magnesium process, the quality of the sludge
partly offsets equivalent escalations in sludge handling
and treatment costs. Moreover, the increased metal
content of the sludge may encourage metal recovery
and reuse. In addition, a fraction of the sludge produced
may be recirculated back into the system in a controlled
way, since it has a high pH and a great coagulating
capacity (Ødegaard, 1989). Sludge recirculation in actu-
al lime–seawater wastewater treatment plants optimized
the lime use, reduced effluent turbidity and phosphate
levels, and improved the process performance during
transient failures of seawater or lime dosing (Ferguson
¨ 1984). Finally, sludge recycling into econom-
and Vrale,
ically viable products, such as cement or other cemen-
titious material, may also help in minimizing the impact
of increased sludge production.
5. Summary, conclusions and recommendations
High-pH–magnesium coagulation was employed in a
wide array of experiments dealing with wastewater
treatment. The presence of an additional source of
magnesium in the experimental matrix has proved to
promote the coagulation–flocculation process, and thus
contributes to higher removal efficiency for most pol-
lutants. A comparison of the process efficiency for
various sources of magnesium ions reveals that seawater
liquid bittern has very high removal efficiency in terms
of TSS, turbidity, color, COD, nutrients and metals
when compared to seawater and seawater DB. As
mentioned earlier, the removal efficiency reported may
vary with wastewater characteristics, and thus it is
always advisable that the treatment of wastewaters
produced under different environmental conditions be
individually evaluated.
401
Economically, the lime–LB process appears to impose
moderately higher total operation and maintenance
costs, mostly due to sludge handling and processing.
However, the various advantages associated with the
lime–magnesium process, such as: (a) local availability
of treatment chemicals; (b) marine discharge of resulting
effluents; (c) simplicity, flexibility and reliability of the
system; (d) enhanced efficiency for TSS, total phos-
phates and metal removal; (e) savings incurred in
coagulant and disinfection chemicals costs; and finally,
(f) enhanced sludge characteristics, will offset the costs
resulting from handling and treatment of the increased
sludge volumes. However, in-depth economic assess-
ment is highly recommended as further research for a
more accurate and comprehensive evaluation of the
capital, operation and maintenance costs incurred by the
high-pH–magnesium treatment process.
Further research is also highly recommended to over-
come the burden of handling and treating increased
sludge volumes. Sludge reuse and recycling into eco-
nomically viable products may help in minimizing the
impact of increased sludge production.
References
Abdallah, R.I., 1996. Seawater: A Source of Magnesium for
Wastewater Treatment. Department of Civil and Environ-
mental Engineering, American University of Beirut, Leba-
non. ME thesis.
Arshad Ali Beg, M., Mahmood, N., Nayeemuddin, N., 1986.
Production of marine chemicals in Pakistan, Part I: sea salt
and deterioration of its quality. Pak. J. Sci. Ind. Res. 29,
301–306.
Arshad Ali Beg, M., Mahmood, N., Nayeemuddin, N.,
Ahmed Khan, W., Zafar, I., 1986. Production of marine
chemicals in Pakistan. Part II: studies on manufacture of
chemicals from seawater bittern. Pak. J. Sci. Ind. Res. 29,
389–396.
Ayoub, G.M., 1994. The lime–seawater process: a potential
for chemically enhanced wastewater treatment. Proceedings
of the 1st Regional Conference of the ASCE, Saudi Arabia
Section, Bahrain.
Ayoub, G.M., Koopman, B., 1986. Algal separation by the
lime–seawater process. J. Water Pollut. Control Fed. 58,
924–931.
Ayoub, G.M., and Merhebi, F. Characteristics and quantities
of sludge produced by coagulating wastewater with seawater
bittern, lime, and caustic. Adv. Environ. Res., in press.
Ayoub, G.M., Lee, S.I., Koopman, B., 1986. Seawater-induced
algal flocculation. Water Res. 20, 1265–1271.
Ayoub, G.M., Lee, S.I., Mazidji, C.N., Seo, I.S., Cho, H.M.,
Koopman, B., 1992. Seawater flocculation of emulsified oil
and alkaline wastewaters. Water Res. 26, 817–823.
Ayoub, G.M., Merhebi, F., Abdallah, R., Acra, A., El-Fadel,
M., 1999. Coagulation of alkalized municipal wastewater
using seawater bittern. Water Environ. Res. 71, 443–453.
Ayoub, G.M., Merhebi, F., Acra, A., El Fadel, M., Koopman,
B., 2000. Seawater bittern for the treatment of alkalized
industrial effluents. Water Res. 34, 640–656.
402 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403
Ayoub, G.M., Semerjian, L., Acra, A., El-Fadel, M., Koopman,
B., 2001. Heavy metal removal by coagulation with seawater
liquid bittern. J. Environ. Eng. Am. Soc. Civ. Eng. 127,
196–207.
Barth, E.F., Ettinger, M.B., Salotto, B.V., McDermott, G.N.,
1965. Summary report on the effects of heavy metals on
the biological treatment processes. J. Water Pollut. Control
Fed. 47, 86.
Berge, A.B., Sæther, R., 1985. Better and Cheaper Treatment
by the Addition of Seawater at VEAS. pp. 3 VA report, in
Norwegian.
Black, S.A., Lewandowski, W., 1969. Phosphorus Removal by
Lime Addition to a Conventional Activated-Sludge Plant.
Water Resources Commission, Toronto, Ontario. Research
publication No 36.
Boost, M.V., Poon, C.S., 1998. The effect of a modified
method of lime-stabilization sewage treatment on enteric
pathogens. Environ. Int. 24, 783–788.
Casey, T.J., 1997. Unit Treatment Processes in Water and
Wastewater Engineering. John Wiley & Sons, Chichester,
England.
Che, M.D., Logan, T.J., Traina, S.J., Bigham, J.M., 1988.
Properties of water treatment lime sludges and their effect-
iveness as agricultural limestone substitutes. J. Water Pollut.
Control Fed. 60, 674–680.
Chino, M., Moriyama, K., Saito, H., Mori, T., 1991. The
amount of heavy metals derived from domestic sources in
Japan. Water Air Soil Pollut. 57y58, 829–837.
Culp, G.L., 1967. Chemical treatment of raw sewage. Water
Wastewater Eng. 4, 61–63.
Culp, R.L., Wesner, G.M., Culp, G.L., 1978. Handbook of
Advanced Wastewater Treatment. 2nd ed.. Van Nostrand
Reinhold Company, New York.
Davis, J.A., Jacknow, J., 1975. Heavy metals in wastewater in
three urban areas. J. Water Pollut. Control Fed. 47, 2292.
Dollof, F.B., Thomas, P.O., John, B.S., 1972. Physical–chem-
ical treatment of municipal wastewater. J. Water Pollut.
Control Fed. 44, 361–371.
Dubose, A.T., 1973. The Effect of Magnesium Coagulation on
Municipal Wastes. Department of Environmental Engineer-
ing, University of Florida. PhD thesis.
Dziubek, A.M., Kowal, A.L., 1983. Water treatment by coag-
ulation–adsorption with dolomite. Proceedings of Chemistry
for Protection of the Environment, 9–25 September 1983,
Toulouse, France.
Dziubek, A.M., Kowal, A.L., 1984. Effect of magnesium
hydroxide on chemical treatment of secondary effluent under
alkaline conditions. Proceedings of Water Reuse Symposium
III, American Waterworks Association Research Foundation,
San Diego.
Dziubek, A.M., Kowal, A.L., 1986. Effect of pH and magne-
sium on color and turbidity removal from aqueous solutions.
Stud. Environ. Sci. 29, 325–334.
Dziubek, A.M., Kowal, A.L., 1989. High-pH coagulation-
adsorption: a new technology for water treatment and reuse.
Water Sci. Technol. 21, 511–517.
Eilbeck, W.J., Mattock, G., 1987. Chemical Processes in
Wastewater Treatment. Ellis Harwood Ltd, Chichester,
England.
Elmaleh, S., Yahi, H., Coma, J., 1996. Suspended solids
abatement by pH increase: upgrading of an oxidation pond
effluent. Water Res. 30, 2357–2362.
Esmond, S.E., 1980. The Removal of Metals and Viruses in
Advanced Wastewater Treatment Sequences. Municipal
Environmental Research Laboratory, Cincinnati, Ohio. US
EPA 600y2-80-149.
Esmond, S.E., Petrasek, A.C., 1974. Trace metal removal. Ind.
Water Eng. 11, 14.
¨ L., 1984. Chemical aspects of the lime–
Ferguson, J.F., Vrale,
seawater process. J. Water Pollut. Control Fed. 56, 355–363.
¨
Forstner, U., Van Leirde, J.H., 1981. Trace metals in water
¨
purification processes. In: Forstner, U., Wittmann, G.T.W.
(Eds.), Metal Pollution in the Aquatic Environment. Spring-
er-Verlag Publishers, Berlin.
Garrison, T., 1996. Oceanography: An Invitation to Marine
Science. Wadsworth Publishing Company, New York.
(http:yywww.pitt.eduy;bpeeryclassesychemistry.html.).
Grabow, W.O.K., Middendorff, I.G., Basson, N.C., 1978. Role
of lime treatment in the removal of bacteria, enteric viruses,
and coliphages in a wastewater reclamation plant. Appl.
Environ. Microbiol. 35, 663–669.
Guldner, C., Hegemann, W., Peschen, N., Solter, K., 1994.
Use of lime for the upgrading of existing wastewater
treatment systems. Water Sci. Technol. 29, 279–282.
Harleman, D.R., Morrissey, S., 1990. Chemically enhanced
treatment: an alternative to biological secondary treatment
for ocean outfalls. Proceedings of the National Conference
on Hydraulic Engineering, American Society of Civil Engi-
neers, San Diego, California.
Harleman, D.R., Morrissey, S., Murcott, S., 1991. The Case
for Chemically Enhanced Primary Treatment in a New
Boston Harbor Clean-up Plan. Ralph M Parsons Laboratory,
Massachusetts Institute of Technology, Cambridge,
Massachusetts.
Horstkotte, G.A., 1974. Full-scale testing of a water reclama-
tion plant. J. Water Pollut. Control Fed. 46, 181–186.
Idelovitch, E., 1978. Wastewater reuse by biological–chemical
treatment and groundwater recharge. J. Water Pollut. Control
Fed. 50, 2723–2740.
Lee, S.I., Seo, I.S., Koopman, B., 1994. Effect of mean velocity
gradients and mixing time on particle removal in seawater-
induced flocculation. Water Air Soil Pollut. 78, 179–188.
Leentvar, J., Rebhun, M., 1982. Effect of magnesium and
calcium precipitation on coagulation–flocculation with lime.
Water Res. 16, 655–662.
Lester, J. (Ed.), 1987. Heavy Metals in Wastewater and Sludge
Treatment Processes, vol. II, CRC Press Inc, Florida, pp.
17–20.
Lozano, J.A., 1993. Production of potassium sulfate–magne-
sium sulfate double salt and magnesium chloride-rich solu-
tion from seawater bitterns. Chem. Eng. J. 52, 89–92.
McDermott, G.N., Barth, E.F., Salotto, V., Ettinger, M.B.,
1962. Zinc in relation to activated sludge and anaerobic
digestion processes. In Proceedings of 17th Industrial Waste
Conference, Purdue University.
McDermott, G.N., Moore, W.A., Post, M.A., Ettinger, M.B.,
1963. Effects of copper on aerobic biological sewage treat-
ment. J. Pollut. Control Fed. 35, 227.
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403
McDermott, G.N., Post, M.A., Jackson, B.N., Ettinger, M.B.,
1965. Nickel in relation to activated sludge and anaerobic
digestion processes. J. Pollut. Control Fed. 37, 163.
McGhee, T.J., 1991. Water Supply and Sewerage. McGraw
Hill Inc, New York.
Merhebi, F.M., 1996. Chemical Clarification of Municipal and
Industrial Wastewaters with Seawater Bittern. Department
of Civil and Environmental Engineering, American Univer-
sity of Beirut, Lebanon. ME thesis.
Merril, D.T., Jorden, R.M., 1975. Lime-induced reactions in
municipal waters. J. Water Pollut. Control Fed. 47,
2783–2808.
Minton, G.R., Carlson, D.A., 1976. Effects of lime addition
on treatment plant operation. J. Water Pollut. Control Fed.
48, 1697–1727.
Morrissey, S., Harleman, D.R., 1990. Chemically Enhanced
Wastewater Treatment. Ralph M Parsons Laboratory, Mas-
sachusetts Institute of Technology, Cambridge, Massachu-
setts. Report No 331.
National Lime Association, 1999. Lime: The Essential Chem-
ical. (http:yywww. lime.orgyaboutlime.html.).
Ødegaard, H., 1987. Particle separation in wastewater treat-
ment.Documentation on the 7th EWPCA Symposium,
Munich, Germany. pp. 351–400.
Ødegaard, H., 1989. Appropriate technology for wastewater
treatment in coastal tourist areas. Water Sci. Technol. 21,
1–17.
Ødegaard, H., 1992. Norwegian experiences with chemical
treatment of raw wastewater. Water Sci. Technol. 25,
255–264.
Parker, D.S., 1972. Process development for nitrogen removal
of the CCCSD water reclamation plant. Advanced Waste
Treatment Design Seminar, University of California, River-
side.
Parks, G.A., 1967. Equilibrium concepts in natural water
systems. Advances in Chemistry Series, vol. 67. American
Chemistry Society, Washington, DC.
Patterson, J.W., Kodukula, P.S., 1984. Metals distribution in
activated sludge systems. J. Water. Pollut. Control Fed. 56,
432–441.
Petrasek, A.C., Kugelman, I.J., 1983. Metal removal and
partitioning in conventional wastewater treatment plants. J.
Water Pollut. Control Fed. 55, 1183–1189.
Poon, C.S., Boost, M., 1996. The stabilization of sewage
sludge by pulverized fuel ash and related materials. Environ.
Int. 22, 705–710.
Poon, C.P., Brueckner, T.G., 1975. Physico-chemical treatment
of wastewater–seawater mixture by electrolysis. J. Water
Pollut. Control Fed. 47, 66–78.
Qasim, S.A., 1999. Wastewater Treatment Plants: Planning,
Design and Operation. Technomic Publishing Co Inc, Lan-
caster, PA.
Ramirez, A., Malina, J.F., 1980. Chemicals disinfect sludge.
Water Sewage Works 127, 52–53.
Riehl, M.L., Weiser, H.H., Rheins, R.T., 1952. Effect of lime-
treated water upon survival of bacteria. J. Am. Water Works
Assoc. 44, 466–471.
403
Rossin, A.C., Lester, J.N., Perry, R., 1982. The influence of
process parameters on the removal of heavy metals in
activated sludge. Water Air Soil Pollut. 17, 185.
Semerjian, L., 2000. Heavy Metal Removal from Alkalized
Wastewaters using Seawater Liquid Bittern. Department of
Civil and Environmental Engineering, American University
of Beirut, Lebanon. MS thesis.
Shin, H.S., Lee, S.M., 1997. Removal of nutrients in waste-
water using magnesium salts. Environ. Technol. 19,
283–290.
Stephenson, T., Perry, R., Lester, J.N., 1985. The influence of
transient phenomena on the biodegradation of nitrilotriacetic
acid in the activated sludge process. Water Air Soil Pollut.
25, 431.
Stuckenberg, J.R., 1975. Physico-chemical treatment using a
coagulation–adsorption process. J. Water Pollut. Control
Fed. 47, 338–353.
Stumm, W., Morgan, J.J., 1981. Aquatic Chemistry. 2nd ed..
Wiley InterScience, New York.
Sundstorm, D.W., Klei, H.E., 1980. Wastewater Treatment.
Prentice Hall, Englewood Cliffs, NJ.
Suthaker, S., Smith, D.W., Stanley, S.J., 1993. Characteristics,
quantity and thickening of sludge from partial lime softening
plant. Environ. Technol. 14, 1001–1014.
Tchobanoglous, G., Burton, F., 1991. Wastewater Engineering:
Treatment, Disposal and Reuse. Metcalf and Eddy Inc, New
York.
Teringo, J., 1987. Magnesium hydroxide reduces sludgey
improves filtering. Pollut. Eng. 19, 78–83.
Van Nieuwenhuiyzen, A.F., Van der Graaf, J.H., de Koning,
J., 1999. Physical–Chemical Pretreatment: Identification and
Evaluation of Wastewater Treatment Scenarios. Department
of Sanitary Engineering, Delft University of Technology,
Delft, Netherlands. (http:yywww.ct.tudelft.nl.).
¨
Vrale, L., 1978. Chemical precipitation of wastewater with
lime and seawater. Prog. Water Technol. 10, 645–656.
Wang, S., Chen, K.Y., 1983. Bitterns as coagulants for the
treatment of color effluents.Proceeding of an International
Conference on Chemistry for the Protection of the Environ-
ment, Toulouse, France, 19–25 September 1983. pp.
193–203.
Westphal, P.A., Christensen, G.L., 1983. Lime stabilization:
effectiveness of two process modifications. J. Water Pollut.
Control Fed. 55, 1381–1386.
US Department of Labor, 2001. Consumer Price Index—All
Urban Consumers (CPI-U). Bureau of Labor Statistics,
Washington, DC. (http:yystats.bls.govy cpihome.htm.).
US Environmental Protection Agency, 1998. Detailed Costing
Document for the Centralized Waste Treatment Industry.
Office of Water, Washington, DC. (EPA 821-R-98-016,
http:yywww.epa.govyostwatery guideycwt).
L. Semerjian is a research associate at the Environ-
mental Engineering Research Center, Faculty of Engi-
neering and Architecture, American University of
Beirut, Lebanon.
G.M. Ayoub is a professor of environmental engi-
neering at the Faculty of Engineering and Architecture,
American University of Beirut, Lebanon.