Advances in Environmental Research 7 (2003) 389403

High-pHmagnesium coagulationflocculation 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, coagulationflocculation 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 highpHmagnesium coagulationflocculation 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-pHmagnesium coagulation flocculation in relation to various sources of magnesium ions. The characteristics of sludges produced from limebased chemical wastewater treatment processes are also discussed. Finally, factors impacting the economics of the process are considered to estimate the costs incurred. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Wastewater; Chemical treatment; Coagulationflocculation; Industrial wastewater; Seawater; Bittern; Magnesium; Metals; Lime; Caustic

1. Introduction 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). Nevertheless, 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-biodegradable 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).

control and rising construction and energy costs, substantial interest has developed in chemically enhanced wastewater treatment methods. This has evolved mostly in response to several operational and regulatory obstacles 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 treatment method, or as a pre-treatment stage prior to biological treatment (Morrissey and Harleman, 1990; degaard, 1992). Moreover, various existing conventional 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).

1093-0191/03/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved. PII: S 1 0 9 3 - 0 1 9 1 0 2 . 0 0 0 0 9 - 6

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The rationale for the increasing popularity of chemical treatment plants pertains to the following associated advantages (Poon and Brueckner, 1975; Stuckenberg, 1975; Forstner and Van Leirde, 1981; Eilbeck and Mattock, 1987; Harleman et al., 1991; degaard, 1987, 1992): They proceed rapidly, are more predictable, more subject to control by simple techniques, and are most frequently amenable to automatic control. They are relatively tolerant to toxic compounds and temperature changes, and can be operated on an on off basis without the need for an acclimatization period. In contrast to biological systems, they can accommodate variable input loads and flows, such as seasonal flows, as well as intermittent and complex discharges, as in the case of industrial wastewaters. When needed, chemical plants are flexible and can be readily modified without necessity for a change in the basic structure. Chemical treatment systems generally have lower space requirements and substantially lower installation costs. However, it is noteworthy to mention that operation costs can be high, especially with largescale plants. Chemically enhanced wastewater treatment can handle higher hydraulic loads compared to conventional treatment methods. When used as a pre-treatment stage, subsequent biological systems become more efficient in dealing with lowered biochemical oxygen demand influents. Moreover, following advanced primary treatment, subsequent secondary biological systems occupy a considerably smaller land area and handle higher hydraulic loadings compared to conventional biological systems. Almost complete removal of phosphorus and limited quantities of nitrogen may be achieved at sites where eutrophication is a problem. Significant particle removal, and consequently effective removal of micro-pollutants, heavy metals, bacteria and viruses, may be achieved. Usually, chemical processes can be designed to provide useful by-products. On the other hand, a number of disadvantages may accompany chemical treatment processes. For instance, relatively larger quantities of inorganic sludge are produced, in addition to the higher salinity in the effluent discharged on account of the additive nature of the process (Eilbeck and Mattock, 1987; Tchobanoglous and Burton, 1991; Van Nieuwenhuiyzen et al., 1999). Conventional chemical treatment processes produce between 1.5- and 2.0-fold more sludge than is produced by conventional primary treatment, whereas biological treatment produces approximately 1.9-fold more sludge

than is produced by conventional primary treatment (Harleman and Morrissey, 1990). However, with reduced chemical costs and feasible sludge disposal, chemically enhanced treatment could prove to be one of the most appropriate technologies in wastewater treatment, particularly when coastal waters are the final destination of treated effluents (Ayoub, 1994). As previously stated, coagulationflocculation has always attracted considerable attention for yielding high removal efficiency in wastewater treatment. Over the past years, a wide array of laboratory- and pilot-scale experiments were conducted to investigate the effect of both calcium and magnesium precipitation on the chemical clarification of wastewater. This paper presents a comprehensive review of the coagulation of alkalized wastewaters by high-pHmagnesium coagulationflocculation processes and describes the chemical aspects of applied treatment strategies. It also reveals and compares the contribution of such treatment strategies to the chemical clarification of various wastewaters. 2. Background information on chemical treatment of wastewater Generally, wastewater colloidal suspensions consist of negatively charged particles. When particles are similarly charged, the resulting repulsive forces tend to stabilize the suspension and prevent particle agglomeration. The process of coagulation is complex and may involve several mechanisms to achieve destabilization, which allows particle agglomeration and enhances subsequent particle removal. Coagulation is typically accomplished through chemical addition and mixing. The process is used to enhance the degree of removal of total suspended solids (TSS), biochemical oxygen demand (BOD), chemical oxygen demand (COD), and bacterial population in primary settling facilities, as well as to improve the performance of secondary treatment processes (Tchobanoglous and Burton, 1991). Flocculation is the physical process of bringing the destabilized particles in contact to form larger flocs that can be more easily removed from suspension. Flocculation is almost always used in conjunction with and preceded by coagulation. The process is generally accomplished by slow mixing of the destabilized suspension to provide an opportunity for the particles to come into contact with one another and bridge together. Therefore, flocculation enhances subsequent sedimentation or the performance of filtration systems by increasing particle size, resulting in increased settling and filter-capture rates. The most commonly used coagulantsflocculants in wastewater treatment are: the trivalent salts of iron wFeCl3, Fe2(SO4)3x and aluminum wAl(SO4)3 x; ferrous sulfate (FeSO4); and calcium hydroxide wCa(OH)2x. These are often used with various coagulant aids, such

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as synthetic polyelectrolytes (anionic, cationic, or nonionic 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; McGhee, 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 industrial 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 introduced long ago. Lime, as a general term, includes quicklime (CaO), hydrated lime wCa(OH)2 x, and dolomitic 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 bacteria, and as a coagulant for the removal of suspended and colloidal material in municipal wastewater. Achievable percentage removals of BOD, COD, TSS and total phosphorus are in the range 6475%, 5772%, 75 91% and 7193%, respectively (Black and Lewandowski, 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): CaOH.2qH2CO3CaCO3xq2H2O CaOH.2qCaHCO3.22CaCO3xq2H2O
3y 3CaOH.2q2PO4 Ca3PO4.2xq6OHy

y 4CaOH.2q3PO3 4 qH2O Ca4HPO4.3xq9OHy

(4)

The calcium carbonate formed according to Eq. (1) and Eq. (2) precipitates out of solution at a pH range of 9.19.5, 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 10.511.0 (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 11.011.5 and a contact time of 4 h, bacterial organisms are completely inactivated (Riehl et al., 1952). Grabow et al. (1978) noted that lime flocculationsedimentation 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 microbial content attained in the effluent is due to the combined effects of exposure to high pH and simultaneous flocculation of microorganisms by the coagulating particles, as 60100% of viruses in wastewater are 1978; degaard, 1989). adsorbed to particles (Vrale, 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 attributable 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 1050% 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: MgHCO3.2q2NaOHMgOH.2xq2NaHCO3 CaHCO3.2q2NaOHCaOH.2xq2NaHCO3 (5) (6)

(1) (2) (3)

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

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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 510% seawater. On the other hand, almost complete algae removal ()95%) was attained at pH 11.0 and 1015% 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 (9497%) when using either lime or NaOH to raise the pH to similar levels in the presence of 510% 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 dissolved 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 magnesium is initially present in wastewater, an increase in pH upon alkalization will result in the precipitation of magnesium hydroxide: Mg2qq2OHyMgOH.2x (7)

Magnesium precipitation begins at approximately pH 9.5, becomes significant above pH 10.5, and is essentially complete at pH 11.011.5. Good clarification is usually not achieved until pH 11.011.5 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 1978). Therefore, coagulant and flocculant aid (Vrale, 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 11.011.5 (Dziubek and Kowal, 1989; Ayoub, 1994). At such a high pH, two major reactions are effective in liquidsolid separation: CaCO3 and Mg(OH)2 precipitation. Both the CaCO3 precipitate (point-of-zero-charge at approximately pH 89, 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 magnesium 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 efficiency 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 compounds 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 carbonate, magnesium hydroxide, processed dolomite, seawater, seawater liquid bittern and marine dried bittern. In a study by Leentvar and Rebhun (1982), significant 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 11.011.5), 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, coagulationflocculation with lime give better removal when the initial magnesium content in the wastewater is high. Also, as the magnesium concentration in the wastewater increases, the pH value needed for precipitation of colloidal particles with 1978). Mg(OH)2 is reduced (Vrale, A high-pH limemagnesium 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 limemagnesium process (pH 11.5) also proved efficient in the removal of most pollutants from secondary effluents by the mechanisms of coagulationflocculation and sedimentation (Idelovitch, 1978). The process led to a reduction in suspended solids (including algae), colloidal and soluble organic matter, bacteria, viruses and some inorganic dissolved solids. In addition, phosphorus, particulate organic nitrogen, boron and fluoride concentrations were reduced by 91%, 33%, 53% and 67% in the summer (2030 8C) and 75%, 30%, 35% and 55% in winter (1020 8C), respectively. Finally, suspensions of lime were used by Dziubek and Kowal (1984) as coagulant for the chemical treatment of secondary wastewater effluent. Precipitation of

L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389403 Table 1 Most abundant solutes in seawater (Garrison, 1996) Ion Chloride (Cly) Sodium (Naq) y Sulfate (SO2 4 ) Magnesium (Mg2q) Calcium (Ca2q) Potassium (Kq) Bicarbonate (HCOy 3 ) Bromide (Br-) Seawater (wt.%) 1.9 1.1 0.3 0.1 0.04 0.04 0.01 0.0065 Dissolved ions (wt.%) 55.04 30.61 7.68 3.69 1.16 1.10 0.41 0.19

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MgSO4qCaOH.2MgOH.2xqCaSO4 MgCl2qCaOH.2MgOH.2xqCaCl2 MgSO4q2NaOHMgOH.2xqNa2SO4 MgCl2q2NaOHMgOH.2xq2NaCl

(8) (9) (10) (11)

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, supplements of magnesium ions in the form of Mg(OH)2 suspension were added to the secondary effluent. Compared to coagulation with lime alone, the removal efficiency increased by 42%, 24% and 13% for phosphates, 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 calcined 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 optimum pH for the new technology approaches 10.5, and thus is much lower than the value required for high limemagnesium treatment. 3.2. High-pHyseawater process Coagulationflocculation 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 11.011.5. In the course of coagulation with seawater, Mg(OH)2 precipitation may occur by any of the following chemical reactions, depending on the alkalizing agent employed:

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 investigated 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 concentrations by 95% or more might be achieved at different seawater concentrations and under alkaline conditions. In addition, high oil removal (9497%) 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 9095%, 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; degaard, 1989). Both 1978; Ferguson and Vrale, experiences revealed that seawater addition as low as 12% can considerably improve phosphorus removal efficiency in the presence of lime as the precipitant (pH)11). This phenomenon is attributable to the addition of magnesium contained in seawater to the wastewater. 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 2040% in the presence of seawater. The process represents a feasible alternative for phosphorus removal in coastal areas because of proximity to sea 1978; Ferguson and Vrale, 1984). In fact, water (Vrale, Norway operates numerous limeseawater 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 25% and lime dosage of 158300 mg Ca(OH)2 yl (degaard, 1989).

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L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389403 Table 2 Average chemical composition of marine bittern as a function of density (Arshad Ali Beg et al., 1986a,b) Density (20 8C) (gyml) 1.020 1.027 1.030 1.037 1.069 1.095 1.139 1.169 1.202 1.222 1.241 1.251 1.260 1.270 1.281 1.295 1.302 1.315 1.321 Compound (% w yw) NaCl 3.05 3.05 3.30 4.06 7.37 9.66 14.23 11.69 14.99 16.62 14.93 8.37 8.31 6.49 7.37 4.94 2.79 2.55 0.91 KCl 0.19 0.19 0.19 0.19 0.38 0.32 0.57 1.33 1.52 1.86 1.37 2.42 2.41 2.86 2.56 3.46 3.87 4.16 1.42 MgCl2 0.51 0.43 0.61 0.52 1.27 0.30 1.79 4.96 6.09 5.36 6.26 10.46 11.04 13.55 11.86 14.73 18.03 19.28 25.50 MgSO4 0.26 0.30 0.31 0.42 0.74 1.01 1.23 1.09 2.48 5.69 4.09 6.52 6.85 7.18 7.30 7.78 5.90 6.38 4.54

The addition of seawater has also proven to be advantageous at treatment plants that use coagulation with ferric chloride (FeCl3 ). In fact, it is claimed that the addition of 12% seawater has reduced FeCl3 dosages by 2030% (Berge and Sther, 1985). The beneficial effects of seawater addition in terms of particle destabilization, aggregation and improved settling are explained by the increased formation of insoluble Mg(OH)2 and the abundance of electrolytes, leading to a compaction of the colloidal double layer, thus resulting in improved coagulation (degaard, 1989). Additional benefits of the limeseawater process include the lower E. coli content achieved, as well as the lower total operational costs. It was found that coagulation with the limeseawater process would be 28% cheaper in operation than FeCl3 coagulation (degaard, 1989). In another study, seawater was used as an anolyte, while wastewater served as the catholyte. As a current was applied to the electrolytic cell, the hydrogen ions present in the seawater were reduced to hydrogen gas. This resulted in the formation of excess OHy ions, and consequently to an increase in pH. Under these alkaline conditions, magnesium ions in the seawater precipitate 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 phosphates (98%), ammonia-nitrogen (90%), total nitrogen (80%), BOD (85% after 60 min of operation) and TSS (87% after 60 min of operation) (Poon and Brueckner, 1975). Finally, a study carried out by Shin and Lee (1997) revealed 62% removal of ammonia and 95% removal of phosphorus from alkalized wastewater in the presence of seawater. 3.3. High-pHyseawater liquid bittern process Seawater liquid bittern is defined as the residual concentrated liquor remaining after the complete deposition of calcium salts (CaSO4 and CaCO3 ) and crystallizing out most of the sodium chloride (NaCl) upon the solar evaporation of seawater (Lozano, 1993; Abdallah, 1996). This concentrate is known to contain valuable chemicals. However, this rich ore is seldom appropriately exploited, and is often allowed to be discharged back into the sea, thus significantly augmenting magnesium salts at the discharge area. The chemical composition of liquid bittern is a function of its density. Table 2 presents the average chemical composition of marine liquid bittern obtained from a solar salt factory. The enriched magnesium content (1.322.85 molykg at 1.2521.319 gyml), as well as the high ionic strength (4.05=10y2 salinity0.8), encouraged several investigators to utilize marine bitterns as coagulants for the treatment of various wastewaters. Wang and Chen

(1983) found liquid bitterns to be effective and economical coagulants for color removal in pulp and textile industries. A color reduction of 85% was achieved in both alkaline and acid bleach-pulp industrial effluents with the addition of 2% liquid bittern when maintained at the optimum pH level using lime. In addition, color removal of approximately 80% was obtained with 2% liquid bittern added to a textile waste stream containing acid and direct azo dyes. The vital reaction in achieving color clarification is the development of chemical interactions between magnesium and color-causing compounds, leading to the formation and settling of insoluble aggregates. The high ionic strength of liquid bittern induces the destabilization of colloids. This can be explained on the basis of the GouyChapman theory of the electric double layer, where the thickness of the double layer decreases with the increasing ionic strength in a way that is consistent with the rise in efficiency of colloid removal corresponding to the rise in the ionic strength (Sundstorm and Klei, 1980; degaard, 1989; Casey, 1997). In another study, in which liquid bittern was used as the coagulant, nutrient removal of 72% and 99% for ammonia and phosphorus, respectively, was reported. Percentage removals dropped to 62% and 95% when seawater served as the coagulant (Shin and Lee, 1997). Several other laboratory studies were conducted to determine the efficacy of seawater bittern as a coagulant for the chemical purification of alkalized municipal and industrial wastewaters. In the case of municipal waste-

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water, turbidity and suspended solids removal was found to exceed 95% and COD reduction was in excess of 75%, while dissolved organic carbon (DOC) removal averaged approximately 30%. The mode of alkalization, whether by the addition of slaked lime or caustic soda, had a very limited effect on the efficiency of treatment. However, the addition of lime resulted in a lower percentage increase in TDS and EC, in contrast to the addition of NaOH. This is attributed to the precipitation of both Mg(OH)2 and CaCO3 in the former, while the latter induces the formation of soluble sodium carbonate 2y (Na2CO3), which remains dissolved as Naq and CO3 in the effluent and contributes to an increase in TDS (Merhebi, 1996; Ayoub et al., 1999, 2000). For municipal wastewater, the limeLB treatment process resulted in better phosphorus, COD and TSS removal efficiency when compared to the corresponding efficiency obtained in conventional preliminary, primary and secondary wastewater treatment schemes, as reported in Table 3. In the case of industrial wastewater effluents, optimum magnesium requirements and pollutant removal percentages varied, depending on the type of industry. At matrix-specific optimum conditions, the respective TSSyturbidity and COD reductions were in excess of 95% for the ceramic tile manufacturing industry; 95% and 80.4% for the paper and cardboard industry; 95% and 61.4% for the dairy products industry; 95% and ) 95% for the marble tiles industry; )98% and 43% for the leather tanning industry; and finally, approximately 90% and 83% for the ready-mix concrete industry (Merhebi, 1996; Ayoub et al. 2000). In all the experiments performed, liquid bittern demonstrated an added advantage over seawater and dried bittern by contributing to the least increase in total dissolved solids (TDS) in the treated effluent. This is attributable to crystallizing out most of the NaCl during the solar evaporation process. In fact, sodium and chloride ions comprise the highest percentage by weight of dissolved ions in the seawater (Table 1). Thus, their removal will significantly reduce needless TDS increase in the treated effluent. Additional advantages of liquid bittern are its reduced bulk when compared to seawater as a source of magnesium ions, as well as its 10-fold

Table 4 Physico-chemical characteristics of the liquid bittern produced (Semerjian, 2000) Parameter pH Density (20 8C) (gyml) TDS (mgyl) Electrical conductivity (25 8C) (mmhosycm) Mg2q (mgyl) Ca2q (mgyl) Cly (mg yl) Naq (mgyl) Kq y SO2 (mgyl) 4 Value measured 6.78 1.2705 396 000 794 000 53 473 0 279 913 70 883 14 000 46 278

Conversion factors for concentration units in mgyl to meq y l are Mg2qs0.0823; Naqs0.0435; Clys0.0282; and y SO2 4 s0.0208.

higher ionic strength than seawater, a characteristic shown to enhance colloidal destabilization (Wang and Chen, 1983). In another study, the effectiveness of seawater LB to remove heavy metals from alkalized MWW was evaluated. The average physico-chemical composition of the seawater LB harvested is summarized in Table 4. Selected metals were added, either individually or concurrently, to 1 l of MWW alkalized by caustic soda or slaked lime. The optimum Mg2q concentration was established to be approximately 107 mgyl, regardless of the alkalization mode employed. The experimental program covered eight metals, including arsenic, cadmium, chromium, copper, lead, mercury, nickel and zinc. Each metal exhibited a characteristic removal efficiency in relation to its hydroxide solubility properties, as well as its affinity towards the precipitating suspended solids. Lime-treated MWW samples showed higher metal removal efficiency compared to caustic soda treatment. Upon the addition of LB to the alkalized MWW samples, turbidity and metal removal was significantly 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 Preliminary Primary sedimentation Conventional activated-sludge system High-rate trickling filter LimeLB Small 1020 1025 812 99 COD 05 3040 8085 6080 )75 TSS 510 5065 8090 6085 )95

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L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389403 Table 6 Comparison of removal efficiency for various individually added metals from MWW by alkalization and alkalizationLB processes (Semerjian, 2000) Metal Metal removal (%)a NaOH NaOHqLB Ca(OH)2 Ca(OH)2qLB

Table 5 Percentage of total metal concentration bound to suspended solids in raw wastewater (degaard, 1989) Metal Bound (%) Zn 51 Cu 48 Ni 13 Cr 71 Pb 71 Cd 82

soda. The addition of LB increased the initial metal removal efficiency by 14.858.2% when MWW was alkalized with caustic soda, and 1.623.2% when slaked lime was the alkalizing agent. It is apparent that the contribution of LB is greater in the former process, since the sole employment of caustic soda alkalization resulted in lower metal removal efficiency compared to that attained in the lime alkalization process. For the limeLB treatment process, high removal ()90%) was achieved for cadmium, chromium, lead, mercury and zinc, and reasonably good removal (71%, 82% and 75 %) for arsenic, copper and nickel, respectively. As stated earlier, efficiency enhancement can be attributed to the enriched magnesium content, as well as to the high ionic strength of LB. In conclusion, metal removal patterns were directly correlated with suspended solid removal patterns. This is explained by the fact that metals are associated with suspended colloidal particles to a great extent, but with varying affinity, as summarized in Table 5. Table 6 compares the average removal efficiency for various individually added metals by alkalization and alkalizationLB processes. Table 7 compares the average removal efficiency for individually and concurrently added metals during the alkalization and the alkalizationLB treatment processes (Semerjian, 2000; Ayoub et al., 2001). The data in Table 7 suggest that, regardless of the alkalization mode, the concurrent presence of metals does not induce a significant hindrance effect, except for nickel. In fact, in the limeLB treatment process, the percentage removal of nickel increased by 18.5% when the metal was concurrently present with other metals. The same study has also revealed that higher influent concentrations of a single metal showed higher removal efficiency (Semerjian, 2000; Ayoub et al., 2001). On the other hand, when compared to the metal removal efficiency obtained in pilot-scale activatedsludge systems, the limeLB process exhibited higher efficiency. The average removal efficiency of a range of metals attained in various pilot activated-sludge treatment plants are summarized and presented in Table 8. 3.4. High pHyseawater dry bittern Seawater dry bittern (DB) may be prepared by the evaporation of liquid bittern, followed by direct heating

Nickel Chromium Copper Lead Cadmium Zinc Arsenic Mercury

a

32.5 64.6 43.3 77.4 72.8 46.6 22.8 14.9

75.3 93.0 63.2 92.2 97.5 75.2 70.7 84.0

52.3 87.3 70.8 92.4 82.4 80.0 63.0 77.8

75.5 98.7 82.8 95.9 99.1 91.5 71.1 99.5

Average of triplicate trial experiments.

until a batch of white crystals is obtained. The settled crystals are washed and harvested to be used as DB. Chloride and sulfate are the major anions in DB. The major cation of bittern solids is magnesium, weighing approximately 10.1% of the total bittern solid weight. Thus, the magnesium concentration of this bittern is approximately 40-fold greater than that of seawater (Wang and Chen, 1983). The typical chemical constituents of DB collected from salt production and processing industries are presented in Table 9. Seawater DB was also evaluated as a potential source of magnesium for the coagulation of alkalized wastewaters. Several jar-test experiments were conducted using DB as the coagulant, in an attempt to compare its coagulating power relative to other sources of magnesium ions, such as seawater and LB. Known amounts of seawater, LB or DB were successively added to each of six jars containing 2 l of alkalized municipal wastewater. Table 10 compares the efficiency of seawater, LB and DB in terms of percentage removal of turbidity, TSS and DOC, and the percentage increase in TDS.
Table 7 Comparison of removal efficiency for individually vs. concurrently added metals from MWW by the alkalizationLB process (Semerjian, 2000) Metal Metal removal (%)a NaOH q LB Ca(OH)2 q LB

Individual Concurrent Individual Concurrent Cadmium Chromium Copper Lead Nickel Zinc
a

97.5 93.0 63.2 92.2 75.3 75.2

91.9 94.4 60.8 86.1 74.1 76.3

99.1 98.7 82.8 95.9 75.5 91.5

99.3 98.7 86.8 93.8 94.0 87.3

Average of replicate trial experiments.

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Table 8 Metal removal efficiency in activated-sludge pilot plants (Esmond, 1980; Petrasek and Kugelman, 1983; Lester, 1987; Chino et al., 1991) Parameter Influent concentration (mgyl) 68 21 NR 37 17 000 1 12 21 171 51 83 929 500 76 203 5 89 NR 1373 276 172 NR 570 36 000 79 545 0.06 153 135 831 2440 100 NR 216 18 138 63 580 57 89 69 550 -2000 NR 0.51 NR 715 152 87 92 130 8333 1493 270 6.7 9000 Average removal efficiency (%) 35 39 49 51 54 56 66 67 5 33 44 57 59 61 61 65 65 33 38 43 68 72 75 78 78 83 83 57 59 36 54 56 59 60 76 81 93 25 26 27 0 Negligible 69 Negligible 0 9 18 21 22 28 33 33 36 44 Reference

Cd

Cr

Cu

Fe Pb

Mn

Hg

Ni

Ag

Patterson and Kodukula, 1984 Esmond and Petrasek, 1974 Esmond, 1980 Davis and Jacknow, 1975 Petrasek and Kugelman, 1983 Chino et al., 1991 Stephenson et al., 1985 Rossin et al., 1982 Patterson and Kodukula, 1984 Petrasek and Kugelman, 1983 Barth et al., 1965 Esmond and Petrasek, 1974 Rossin et al., 1982 Davis and Jacknow, 1975 Chino et al., 1991 Stephenson et al., 1985 Esmond, 1980 Esmond and Petrasek, 1974 Patterson and Kodukula, 1984 Davis and Jacknow, 1975 Esmond, 1980 Petrasek and Kugelman, 1983 Barth et al., 1965 McDermott et al., 1963 Chino et al., 1991 Rossin et al., 1982 Stephenson et al., 1985 Chino et al., 1991 Petrasek and Kugelman, 1983 Patterson and Kodukula, 1984 Esmond, 1980 Esmond and Petrasek, 1974 Chino et al., 1991 Davis and Jacknow, 1975 Rossin et al., 1982 Petrasek and Kugelman, 1983 Stephenson et al., 1985 Esmond and Petrasek, 1974 Chino et al., 1991 Petrasek and Kugelman, 1983 Petrasek and Kugelman, 1983 Esmond, 1980 Esmond and Petrasek, 1974 Esmond, 1980 Patterson and Kodukula, 1984 Davis and Jacknow, 1975 Stephenson et al., 1985 Esmond and Petrasek, 1974 Rossin et al., 1982 Barth et al., 1965 McDermott et al., 1965 Petrasek and Kugelman, 1983 Chino et al., 1991 Petrasek and Kugelman, 1983

398 Table 8 (Continued) Parameter

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Influent concentration (mgyl) 612 598 1226 NR 1280 915 554 224 102 273 81 818

Average removal efficiency (%) 16 54 57 62 64 65 65 70 89 89

Reference

Zn

Patterson and Kodukula, 1984 Rossin et al., 1982 Davis and Jacknow, 1975 Esmond, 1980 Petrasek and Kugelman, 1983 Esmond and Petrasek, 1974 Stephenson et al., 1985 Chino et al., 1991 McDermott et al., 1962 Barth et al., 1965

Table 10 reveals that the three sources of Mg2q ions generally produced satisfactory results. Turbidity and TSS removal efficiency was highest (99.6% and 99.4%, respectively) when Mg2q ions were supplied by LB at a concentration of 140150 mgyl. Dried bittern was second in turbidity and TSS removal (98.0% and 96.5%, respectively) at a Mg2q concentration of 130 mgyl, followed by seawater (95.4% and 88.6%) at a Mg2q dose of 165 mgyl. With respect to DOC, the most efficient removal was observed for seawater (55%), whereas approximately similar efficiency (3536%) 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 102% for seawater, LB and DB, respectively. Thus, the use of LB results in an appreciably lower increase in effluent TDS when compared to seawater and DB. An approximate eight-fold increase in TDS is obtained when seawater is used compared to LB, and four-fold when compared to DB. This is attributed to the different ionic compositions of the various sources of Mg2q ions. 4. Discussion 4.1. Operation and process performance As stated earlier, the limemagnesium process has been investigated by various researchers in the past two 1978; Ferguson and Vrale, 1984; Ayoub decades (Vrale, and Koopman, 1986; Ayoub et al., 1986, 1992; degaard, 1992). The process proved to be advantaTable 9 Chemical constituents of seawater dry bittern (Wang and Chen, 1983) Chemical constituent
y Cly SO2 Naq Kq Mg2q H2O 4

geous over other chemically enhanced processes, such as polymerferric chloride or polymeralum treatment. From the standpoint of operation and process performance, all of the experiments discussed earlier suggest that magnesium ions, regardless of their source, can be regarded as an effective coagulant for the purification of wastewater. However, process advantages and disadvantages may vary with varying sources of magnesium ions. Table 11 summarizes such characteristics in relation to the various sources of magnesium ions.

Table 10 Percentage removal of selected parameters from lime-alkalized MWW using different sources of Mg2q ions (Ayoub et al., 1999) Mg2q source Total Mg2q Removal (%) TDS concentration increase Turbidity TSS DOC (%) (mgyl) Seawater 51.0 87.6 126.2 166.8 209.6 255.0 36.5 72.0 107.6 143.2 178.9 214.5 19.4 54.9 90.8 126.5 162.2 197.9 94.2 95.7 91.1 95.4 94.2 93.4 97.6 97.8 98.9 99.6 99.5 99.5 98.3 97.9 97.3 98.0 97.9 97.3 80.7 76.8 76.3 88.6 76.3 72.8 97.7 98.3 97.9 99.4 97.5 97.5 96.5 96.5 94.5 96.5 95.1 94.7 36 50 54 55 56 51 20 25 29 35 36 30 23 16 24 36 43 39 136 234 232 405 527 657 72 53 44 53 104 142 135 121 111 102 95 84

Liquid bittern

Dried bittern

Total solid weight (%) 33.5 2.3

0.5

0.6 10.1

53

L. Semerjian, G.M. Ayoub / Advances in Environmental Research 7 (2003) 389403 Table 11 Process advantages and disadvantages of various sources of Mg2q ions Source of Mg2q Seawater Advantages Readily available No need for evaporation No additional space requirements for evaporation basins Acceptable removal of algae, emulsified oil, turbidity, TSS and nutrients Very high treatment efficiency 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 Moderate removal efficiency for TSS and turbidity Less bulk volume for transportation inland Low TDS increase in effluent when compared to seawater (102% vs. 405%) Pure products Moderate TDS increase Very high removals of nutrients Disadvantages

399

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

Seawater liquid bittern

Seawater dry bittern

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

Certified magnesium salts and hydroxides

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, suspended solids, bicarbonate alkalinity, total hardness and the presence of organic complexes or chelating agents. The type and dosage of coagulant employed, the presence 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 coagulationflocculation processes. Other 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

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. However, lime-based chemical treatment processes have been

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Table 12 Chemical costs of alternative coagulationflocculation processes (Semerjian, 2000) Coagulant type Coagulant dose (mgyl) Unit price ($ylb) Total cost ($ym3 wastewater) Coagulant aid type Coagulant aid dose (mgyl) Unit price ($ylb) Total cost ($ym3 wastewater) Sludge dewatering polymer type Dewatering polymer dose (mgyt dry solids) Unit price ($ylb) Total cost ($yt dry solids) Total treatment chemical costs ($)
a b

FeCl3a 253 0.13c 0.073 Anionic 0.5 4.69d 0.0051 Organic 2.86 4.69d 0.029 0.078q0.029

Alumb 183 0.13c 0.052 Anionic 2.8 4.69d 0.029 NR 2.86 4.69d 0.029 0.081q0.029

LimeqLB 900 0.036d 0.072 None 0 0 0 None 0 0 0 0.072

Mean data of 50 Norwegian wastewater treatment plants (degaard, 1992). Mean data of nine Norwegian wastewater treatment plants (degaard, 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, compactibility and dewatering characteristics; bacterial inactivation 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; degaard, 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 critical quantification and characterization of sludge in chemical wastewater treatment systems. 4.3. Factors impacting the economics of the limeLB treatment process The limeLB 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 treatment 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 chemicals associated with the limeLB process to those used in currently operating secondary chemical treatment facilities. Additional savings resulting from the limeLB treatment process include the costs associated with disinfection. 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 5.56.5) or the alum (pH 5.06.0) coagulationflocculation processes. 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 limeLB 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 discharged through an efficient outfall diffuser (Ferguson 1984; degaard, 1989). and Vrale, Another advantage of the limeLB system, which translates into long-term cost-effectiveness, is the potential of the system to be more heavily loaded hydraulically 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 limeseawater process flocculate and settle very well; however, this has not yet been scientifically demonstrated (degaard, 1989).

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The main disadvantage presented by the limemagnesium process remains the large amounts of sludge generated compared to the amounts produced in conventional secondary chemical processes employing alum or ferric chloride as coagulants. Fortunately, sludges resulting from lime treatment possess superior thickening 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 1984). 1% of the wastewater flow (Ferguson and Vrale, Another advantageous characteristic of the sludge produced 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 characteristic 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 (degaard, 1989). Although sludge generation is higher for the limemagnesium 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 (degaard, 1989). Sludge recirculation in actual limeseawater 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 economand Vrale, ically viable products, such as cement or other cementitious material, may also help in minimizing the impact of increased sludge production. 5. Summary, conclusions and recommendations High-pHmagnesium 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 coagulationflocculation process, and thus contributes to higher removal efficiency for most pollutants. 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.

Economically, the limeLB 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 limemagnesium 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 phosphates 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 assessment is highly recommended as further research for a more accurate and comprehensive evaluation of the capital, operation and maintenance costs incurred by the high-pHmagnesium treatment process. Further research is also highly recommended to overcome the burden of handling and treating increased sludge volumes. Sludge reuse and recycling into economically viable products may help in minimizing the impact of increased sludge production. References
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L. Semerjian is a research associate at the Environmental Engineering Research Center, Faculty of Engineering and Architecture, American University of Beirut, Lebanon. G.M. Ayoub is a professor of environmental engineering at the Faculty of Engineering and Architecture, American University of Beirut, Lebanon.