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High-pH-Magnesium Coagulation–Flocculation in Wastewater

Treatment

Article  in  Advances in Environmental Research · January 2003

DOI: 10.1016/S1093-0191(02)00009-6

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 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-

stantial interest has developed in chemically enhanced
Chemical treatment of wastewater pollutants was wastewater treatment methods. This has evolved mostly
investigated and developed long ago; however, its full in response to several operational and regulatory obsta-
implementation was delayed in favor of biological cles facing both the wastewater dischargers and the
treatment methods due to the elevated costs of chemicals wastewater treatment plants (Eilbeck and Mattock,
at that time (Culp, 1967; Culp et al., 1978). Neverthe- 1987). At present, several countries rely on chemical
less, biological treatment may not always be suitable, processes to treat their raw wastewaters, either as the
especially for specific situations, such as intermittent only advanced primary or the secondary chemical treat-
waste flows, wastes containing substances toxic to ment method, or as a pre-treatment stage prior to
biological growth and wastewaters containing non-bio- biological treatment (Morrissey and Harleman, 1990;
degradable impurities. Ødegaard, 1992). Moreover, various existing conven-
In recent years, with the technological advancements tional primary wastewater plants are shifting towards
in polymer chemistry, increased interest in nutrient chemically enhanced treatment to improve the quality
of the treated effluent. Such an improvement would
*Corresponding author. Fax: q961 1 74 44 62. reduce the size, complexity and cost of secondary
E-mail address: gayoub@aub.edu.lb (G.M. Ayoub). treatment to conform with environmental regulations
and guidelines (Harleman et al., 1991).
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
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) 389–403 391

as synthetic polyelectrolytes (anionic, cationic, or non- 4CaŽOH.2q3PO3y

4 qH2O
ionic polymers), fly ash and clay. The choice of a °Ca4HŽPO4.3xq9OHy (4)
specific coagulation reagent is firstly governed by its
effectiveness, and secondly by its cost, relative to The calcium carbonate formed according to Eq. (1)
alternative reagents (Eilbeck and Mattock, 1987; Mc- and Eq. (2) precipitates out of solution at a pH range
Ghee, 1991; Tchobanoglous and Burton, 1991; Casey, of 9.1–9.5, and acts through the ‘sweep coagulation’
1997). Recently, magnesium ions from various sources mechanism to entrap suspended and colloidal particles.
have gained in popularity as coagulants for the chemical It also acts as a ‘weighting agent’ by increasing the
clarification of various alkalized municipal and indus- density of the settlable particles, thereby enhancing their
trial wastewaters. The following sections demonstrate settlement (Leentvar and Rebhun, 1982). Precipitation
the role of various sources of magnesium ions in of phosphates wEq. (3) and Eq. (4)x occurs within the
wastewater treatment. 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
3. Experiences in the utilization of magnesium in process. It was reported that at pH 11.0–11.5 and a
wastewater treatment contact time of 4 h, bacterial organisms are completely
inactivated (Riehl et al., 1952). Grabow et al. (1978)
3.1. High-pHymagnesium processes noted that lime flocculation–sedimentation at pH 9.6
reduced the coliform organisms, enteric viruses and
Traditionally, alkalizing agents, such as lime or caustic coliphages by 62.35%, 99.98% and 57%, respectively.
soda, have been employed to raise the pH levels needed At pH 11.2, these values increased to reach 99.98%,
to induce chemical clarification of wastewaters. 100% and 99.95%, respectively. The decreased micro-
bial content attained in the effluent is due to the
3.1.1. Lime alkalization combined effects of exposure to high pH and simulta-
The use of lime in wastewater treatment was intro- neous flocculation of microorganisms by the coagulating
duced long ago. Lime, as a general term, includes particles, as 60–100% of viruses in wastewater are
quicklime (CaO), hydrated lime wCa(OH)2 x, and dolo- adsorbed to particles (Vrale,
¨ 1978; Ødegaard, 1989).
mitic lime as defined by the National Lime Association Lime requirements, for optimal clarification, vary
(NLA, 1999). However, the two forms of lime mostly with the type of wastewater to be treated. Precipitation
used in wastewater treatment are CaO and Ca(OH)2. of wastewater with lime has yielded variable results at
Historically, lime has been used in treating wastewaters different treatment plants. This behavior is mostly attrib-
for a multitude of reasons. It has the inherent advantage utable to the initial composition of wastewater, mainly
of making no contribution to an increase in salinity, as in terms of bicarbonate alkalinity and total hardness.
is the case when alum or iron salts are employed Moreover, lime dosages found in jar tests or in plant
(Dziubek and Kowal, 1984). Moreover, apart from its operations were 10–50% higher than the theoretically
positive economical impact in terms of chemical cost predicted doses, in view of the fact that lime dissolves
and energy requirements, lime effectively acts as both a partially, and thus is not completely utilized (Merril and
precipitant for phosphates, many trace metals, and bac- Jordan, 1975).
teria, and as a coagulant for the removal of suspended
3.1.2. Caustic soda alkalization
and colloidal material in municipal wastewater. Achiev-
Caustic soda (sodium hydroxide, NaOH) can be used
able percentage removals of BOD, COD, TSS and total
as an alternative source of hydroxyl ions needed to raise
phosphorus are in the range 64–75%, 57–72%, 75–
the pH to levels at which precipitation of calcium and
91% and 71–93%, respectively (Black and Lewan-
magnesium hydroxides are induced. The following
dowski, 1969; Parker, 1972; Horstkotte, 1974;
chemical reactions take place:
Stuckenberg, 1975). In addition, algae removal of 80%
was attained when lime alone was added to wastewater MgŽHCO3.2q2NaOH°MgŽOH.2xq2NaHCO3 (5)
containing a sufficient amount of bicarbonate alkalinity,
CaŽHCO3.2q2NaOH°CaŽOH.2xq2NaHCO3 (6)
hardness and phosphates (Ayoub et al., 1986; Ayoub,
1994). The mechanisms of chemical clarification are Removal of turbidity, suspended solids and organic
explained by the following reactions (Culp et al., 1978; matter using only NaOH as the alkalizing agent was
Tchobanoglous and Burton, 1991): reported to be comparable to that achieved when using
only lime (Merril and Jordan, 1975). However, from
CaŽOH.2qH2CO3°CaCO3xq2H2O (1) the standpoint of economics and efficacy of phosphate
CaŽOH.2qCaŽHCO3.2°2CaCO3xq2H2O (2) removal, the usage of lime is favored over NaOH.
Caustic soda was used as an alkalizing agent in
3CaŽOH.2q2PO43y°Ca3ŽPO4.2xq6OHy (3) 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 the treatment efficiency steeply increases when the pH
of seawater for the removal of algae from oxidation value is at approximately the theoretical value for
pond effluents. As a result, algae removal in excess of Mg(OH)2 precipitation, pH 11.3 (Leentvar and Rebhun,
80% was achieved at an initial pH of 10.5 and 5–10% 1982; Elmaleh et al., 1996).
seawater. On the other hand, almost complete algae The contribution of calcium and magnesium com-
removal ()95%) was attained at pH 11.0 and 10–15% pounds to the efficiency of water treatment was first
seawater. In another study, a lime dosage of 1000 mgyl reported in the late 1920s (Dziubek and Kowal, 1986).
resulted in more than 80% algae removal. When caustic Since then, several researchers have investigated the
soda was used instead of lime to raise the pH to the effects of high-pH magnesium and calcium precipitation
same level, only 50% removal was achieved. Moreover, on coagulation using a variety of magnesium ion
the same study also revealed similar patterns of oil sources, such as magnesium chloride, magnesium car-
removal from alkaline wastewaters (94–97%) when bonate, magnesium hydroxide, processed dolomite, sea-
using either lime or NaOH to raise the pH to similar water, seawater liquid bittern and marine dried bittern.
levels in the presence of 5–10% seawater (Ayoub, In a study by Leentvar and Rebhun (1982), signifi-
1994). cant reductions in suspended solid extinction (rate of
reduction of light absorbance) and total organic carbon
3.1.3. Role of magnesium ions at high pH (TOC) were obtained by low-pH lime treatment (pH
As previously noted, flocculation at high pH achieves 9.5); however, even better efficiency was attained by
efficient removal of particles, colloids and certain dis- the high-pH lime treatment (pH 11.0–11.5), apparently
solved materials present in the wastewater. However, due to both CaCO3 and Mg(OH)2 precipitation. On
alkaline flocculation was found to be most effective in average, 45% of TOC and 85% of the extinction were
matrices containing relatively high concentrations of removed by CaCO3 formation; an additional 16% of
magnesium ions (Minton and Carlson, 1976; Leentvar TOC and 7% of suspended solid extinction were
and Rebhun, 1982; Elmaleh et al., 1996). When mag- removed by Mg(OH)2 precipitation. The experiments
nesium is initially present in wastewater, an increase in showed that, in practice, coagulation–flocculation with
pH upon alkalization will result in the precipitation of lime give better removal when the initial magnesium
magnesium hydroxide: content in the wastewater is high. Also, as the magne-
sium concentration in the wastewater increases, the pH
Mg2qq2OHy°MgŽOH.2x (7)
value needed for precipitation of colloidal particles with
Magnesium precipitation begins at approximately pH Mg(OH)2 is reduced (Vrale, ¨ 1978).
9.5, becomes significant above pH 10.5, and is essen- A high-pH lime–magnesium process was also used
tially complete at pH 11.0–11.5. Good clarification is by Dollof et al. (1972) for the treatment of municipal
usually not achieved until pH 11.0–11.5 is reached wastewaters. The process yielded reductions of 31%,
(Merril and Jordan, 1975; Dziubek and Kowal, 1984). 91% and 97% for total nitrogen, suspended solids and
The resulting magnesium hydroxide is a gelatinous total phosphorus, respectively, and 80% for each of
precipitate, which was found to serve as an efficient TOC, COD and BOD.
coagulant and flocculant aid (Vrale,
¨ 1978). Therefore, Dubose (1973), in his raw municipal wastewater
in order for the treatment process to operate efficiently, treatment studies, concurrently used lime and recycled
either lime or NaOH should be used to increase the pH magnesium ions. Compared to treatment with lime
of the original wastewater to pH 11.0–11.5 (Dziubek alone, better removal efficiency was obtained for COD,
and Kowal, 1989; Ayoub, 1994). At such a high pH, phosphates, TSS and color.
two major reactions are effective in liquid–solid sepa- In a pilot-plant study, the high-pH lime–magnesium
ration: CaCO3 and Mg(OH)2 precipitation. Both the process (pH 11.5) also proved efficient in the removal
CaCO3 precipitate (point-of-zero-charge at approximate- of most pollutants from secondary effluents by the
ly pH 8–9, Parks, 1967) and the primary particles are mechanisms of coagulation–flocculation and sedimen-
negatively charged. The formation of CaCO3 induces a tation (Idelovitch, 1978). The process led to a reduction
sweep coagulation process, whereby only the larger in suspended solids (including algae), colloidal and
particles are entrapped. On the other hand, the soluble organic matter, bacteria, viruses and some inor-
Mg(OH)2 precipitate (point-of-zero-charge of magnesi- ganic dissolved solids. In addition, phosphorus, partic-
um oxide is approximately at pH 12.4, Parks, 1967; ulate organic nitrogen, boron and fluoride concentrations
Stumm and Morgan, 1981) has a large adsorptive were reduced by 91%, 33%, 53% and 67% in the
surface area and a positive superficial charge, which summer (20–30 8C) and 75%, 30%, 35% and 55% in
attracts the negatively charged colloidal particles, winter (10–20 8C), respectively.
including the CaCO3 flocs, thus inducing adsorption Finally, suspensions of lime were used by Dziubek
and agglomeration. This explains the significant effi- and Kowal (1984) as coagulant for the chemical treat-
ciency achieved when Mg(OH)2 is precipitated. In fact, ment of secondary wastewater effluent. Precipitation of
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403 393

Table 1 MgSO4qCaŽOH.2°MgŽOH.2xqCaSO4 (8)

Most abundant solutes in seawater (Garrison, 1996)
MgCl2qCaŽOH.2°MgŽOH.2xqCaCl2 (9)
Ion Seawater Dissolved ions MgSO4q2NaOH°MgŽOH.2xqNa2SO4 (10)
(wt.%) (wt.%)
MgCl2q2NaOH°MgŽOH.2xq2NaCl (11)
Chloride (Cly) 1.9 55.04
Sodium (Naq) 1.1 30.61 The minimum seawater concentration needed for
Sulfate (SO2y
4 ) 0.3 7.68 effective flocculation will be a function of the hydroxyl
Magnesium (Mg2q) 0.1 3.69 ion concentration, the solubility of magnesium ions in
Calcium (Ca2q) 0.04 1.16 equilibrium with solid Mg(OH)2 and the minimum
Potassium (Kq) 0.04 1.10
amount of Mg(OH)2 that must be precipitated (Ayoub
Bicarbonate (HCOy
3 ) 0.01 0.41
Bromide (Br-) 0.0065 0.19 et al., 1992).
Seawater flocculation at high pH levels was investi-
gated by Ayoub et al. (1986, 1992) for the removal of
magnesium was strongly correlated with the removal of algae from stabilization pond effluents, as well as
color, turbidity, COD and phosphates. Removal curves emulsified oil and suspended solids from wastewaters.
showed a characteristic inflection at pH 10.5, above It was demonstrated that a reduction in algal concentra-
which the degree of removal rapidly increased. The tions by 95% or more might be achieved at different
highest degree of removal was obtained at a pH seawater concentrations and under alkaline conditions.
approaching 11.5 with a lime dose of 200 g CaOym3. In addition, high oil removal (94–97%) was achieved
To determine the actual contribution of Mg(OH)2, sup- at seawater concentrations of 5% and greater, in the
plements of magnesium ions in the form of Mg(OH)2 presence of either lime or caustic soda. Various types
suspension were added to the secondary effluent. Com- of highly alkaline industrial wastewaters were also
pared to coagulation with lime alone, the removal studied to assess the removal of selected pollutants. TSS
efficiency increased by 42%, 24% and 13% for phos- removal was in the range of 90–95%, whereas COD,
phates, TOC and COD, respectively. Moreover, in other total Kjeldahl nitrogen (TKN) and total phosphorus
studies, Dziubek and Kowal (1983, 1989) used calcined removal averaged approximately 80%, 65% and 95%,
dolomite to act as the coagulant in a novel high-pH respectively, at an optimal seawater dose of 10% and
surface water treatment technology. The optimum cal- without the need for a supplemental source of OHy
cined coagulant dose was found to be 300 gym3, ions. These findings would allow great cost savings to
yielding a colorless and clear effluent, displaying high industries, especially in coastal regions.
removal of organic matter (60% COD and 65% TOC) Full-scale operation and laboratory studies have been
and heavy metals, as well as partial inactivation of carried out to assess the chemical precipitation of
viruses and bacteria. The primary mechanism governing municipal wastewater with lime and seawater (Vrale, ¨
the removal of organic matter is adsorption on both the ¨ 1984; Ødegaard, 1989). Both
1978; Ferguson and Vrale,
precipitating CaCO3 and the Mg(OH)2 flocs. The opti- experiences revealed that seawater addition as low as
mum pH for the new technology approaches 10.5, and 1–2% can considerably improve phosphorus removal
thus is much lower than the value required for high efficiency in the presence of lime as the precipitant
lime–magnesium treatment. (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
3.2. High-pHyseawater process phosphorus removal and a lower lime requirement, thus
improving the performance and economics of lime use.
Coagulation–flocculation of alkalized wastewaters, Experimentation shows that the lime dosage needed to
using seawater as an inexpensive source of magnesium reach a specific residual total phosphate or TSS is
ions, was reported to be effective for the removal of a reduced by 20–40% in the presence of seawater. The
wide range of impurities. Seawater is composed of process represents a feasible alternative for phosphorus
various cations and anions, as summarized in Table 1. removal in coastal areas because of proximity to sea-
However, only magnesium cations, which result from water (Vrale,
¨ 1978; Ferguson and Vrale, ¨ 1984). In fact,
the presence of magnesium sulfate and magnesium Norway operates numerous lime–seawater plants for
chloride, serve as effective coagulants at high pH levels wastewater treatment, especially in coastal tourist areas.
of 11.0–11.5. Operational data from such Norwegian plants reveal
In the course of coagulation with seawater, average reductions of 67%, 70%, 92% and 93% for
Mg(OH)2 precipitation may occur by any of the follow- COD, BOD, total phosphorus and suspended solids,
ing chemical reactions, depending on the alkalizing respectively, for seawater additions of 2–5% and lime
agent employed: 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) 389–403 399

Table 11
Process advantages and disadvantages of various sources of Mg2q ions

Source of Mg2q Advantages Disadvantages

Seawater Readily available May induce the growth of algae and
No need for evaporation marine organisms in inlet pipes
No additional space requirements Significant increase in TDS
for evaporation basins of effluent (405%)
Acceptable removal of algae, May contain bacteria
emulsified oil, turbidity, TSS Bulky if transported inland
and nutrients Lower treatment removal efficiency
when compared to liquid bittern
Seawater Very high treatment efficiency Needs further evaporation of seawater
liquid bittern for TSS, turbidity, color, Use of additional land area for
COD, metals and nutrients evaporation process
Higher magnesium content More corrosive than seawater
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 Moderate TDS increase in effluent
dry bittern TSS and turbidity when compared to liquid bittern
Less bulk volume for transportation (102% vs. 53%)
inland Needs further processing of seawater
Low TDS increase in effluent liquid bittern
when compared to seawater Lower TSS and turbidity removal
(102% vs. 405%) efficiency when compared
to liquid bittern
Certified Pure products Relatively expensive
magnesium salts Moderate TDS increase Not readily available to many
and hydroxides Very high removals of nutrients communities
Requires proper storage areas

It is noteworthy to mention that the pollutant removal experiments discussed were conducted under controlled
efficiency achievable is greatly affected by the initial laboratory conditions, the coagulant requirements and
physico-chemical composition of the wastewater, mainly process efficiency may vary under actual operational
in terms of the concentration of magnesium ions, sus- conditions, such as large-scale wastewater treatment
pended solids, bicarbonate alkalinity, total hardness and plants. It is advisable that optimum conditions and
the presence of organic complexes or chelating agents. achievable performance in the treatment of wastewaters
The type and dosage of coagulant employed, the pres- produced under different environmental conditions be
ence of flocculants or coagulant aids, the type and separately evaluated.
structure of the particles, the pH and the temperature
may also alter process efficiency. Physical operational 4.2. Sludge characteristics of lime based treatment
variables, most notably mean velocity gradient and processes
mixing time, are also important determinants of the
performance of coagulation–flocculation processes. Oth- The increased volume of sludge generated in chemical
er operational factors, such as overflow rate, settling wastewater treatment has mostly hindered the adoption
time and recirculation ratio, should also be taken into of the process as a wastewater treatment strategy. How-
account (Lee et al., 1994). Therefore, since most of the 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 Regarding operation and maintenance costs, the lime–
and possess certain advantageous qualities over other LB process introduces appreciable savings in chemical
chemical sludges. Improved sludge settling, compacti- costs, especially since lime is readily available in most
bility and dewatering characteristics; bacterial inactiva- countries and LB can be easily obtained in coastal
tion capability; recirculation and recycling potentiality; regions. Table 12 compares the cost of treatment chem-
and sludge stability comprise the major advantages of icals associated with the lime–LB process to those used
lime-based sludges. Such advantages could partly offset in currently operating secondary chemical treatment
the burden of increased sludge volumes (Minton and facilities.
¨
Carlson, 1976; Ramirez and Malina, 1980; Forstner and Additional savings resulting from the lime–LB treat-
Van Leirde, 1981; Westphal and Christensen, 1983; ment process include the costs associated with disinfec-
¨
Ferguson and Vrale, 1984; Teringo, 1987; Che et al., tion. The high pH of the process induces almost
1988; Ødegaard, 1989; Suthaker et al., 1993; Guldner complete disinfection, thus eliminating the need for a
et al., 1994; Poon and Boost, 1996; Boost and Poon, separate disinfection process in the treatment system
1998; Ayoub and Merhebi, in press). (Ayoub et al., 1999, 2000). Bacterial inactivation is not
However, further research and experimentation are achieved in either the ferric chloride (pH 5.5–6.5) or
highly recommended for more comprehensive and crit- the alum (pH 5.0–6.0) coagulation–flocculation pro-
ical quantification and characterization of sludge in cesses. On the other hand, such high-pH effluents are
chemical wastewater treatment systems. not suitable for direct discharge into inland waters.
Therefore, a recarbonation stage becomes necessary with
4.3. Factors impacting the economics of the lime–LB the lime–LB treatment process when the receiving water
treatment process bodies are inland waters. However, when discharging to
sea, the high effluent pH does not pose any adverse
The lime–LB chemical treatment process bears a effect, since it will be rapidly neutralized when dis-
great resemblance to a conventional primary chemical charged through an efficient outfall diffuser (Ferguson
treatment strategy in terms of system configuration, and ¨ 1984; Ødegaard, 1989).
and Vrale,
thus capital costs. The components of the system include Another advantage of the lime–LB system, which
a chemical feed system, a rapid mix tank, a flocculating translates into long-term cost-effectiveness, is the poten-
tank, a clarifier and sludge handling units, which are tial of the system to be more heavily loaded hydrauli-
typical for any chemical coagulationyprecipitation treat- cally than primary precipitation plants operating with
ment scheme. Additional land areas, and thus capital alum, ferric chloride or lime alone as the coagulant.
costs, may be needed if seawater is to be evaporated The reason given for this potential is that flocs in the
on-site for the production of concentrated liquid bittern. lime–seawater process flocculate and settle very well;
Otherwise, the liquor can be transported from nearby however, this has not yet been scientifically demonstrat-
salt production works. ed (Ødegaard, 1989).
 L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389–403 401

The main disadvantage presented by the lime–mag- Economically, the lime–LB process appears to impose
nesium process remains the large amounts of sludge moderately higher total operation and maintenance
generated compared to the amounts produced in con- costs, mostly due to sludge handling and processing.
ventional secondary chemical processes employing alum However, the various advantages associated with the
or ferric chloride as coagulants. Fortunately, sludges lime–magnesium process, such as: (a) local availability
resulting from lime treatment possess superior thicken- of treatment chemicals; (b) marine discharge of resulting
ing and dewatering characteristics and are suitable for effluents; (c) simplicity, flexibility and reliability of the
filter pressing at lower cost than sludges generated from system; (d) enhanced efficiency for TSS, total phos-
ferric chloride or alum (Forstner
¨ and Van Leirde, 1981). phates and metal removal; (e) savings incurred in
In practice, the thickened sludge production is only 0.6– coagulant and disinfection chemicals costs; and finally,
1% of the wastewater flow (Ferguson and Vrale, ¨ 1984). (f) enhanced sludge characteristics, will offset the costs
Another advantageous characteristic of the sludge pro- resulting from handling and treatment of the increased
duced is that it can be efficiently dewatered without the sludge volumes. However, in-depth economic assess-
addition of polymers or more lime, which are necessary ment is highly recommended as further research for a
for the conditioning of sludges produced from ferric more accurate and comprehensive evaluation of the
chloride or alum coagulation processes. This character- capital, operation and maintenance costs incurred by the
istic results in further savings in treatment chemicals. high-pH–magnesium treatment process.
Because of its high lime content and high pH, the sludge Further research is also highly recommended to over-
produced is chemically ‘stabilized’, does not decompose come the burden of handling and treating increased
rapidly, and causes few odor problems (Ødegaard, sludge volumes. Sludge reuse and recycling into eco-
1989). Although sludge generation is higher for the nomically viable products may help in minimizing the
lime–magnesium process, the quality of the sludge impact of increased sludge production.
partly offsets equivalent escalations in sludge handling
and treatment costs. Moreover, the increased metal References
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