Treatment of boron-containing optoelectronic wastewater by adsorption and precipitation processes was investigated in this study. Adsorption process for boron removal by water treatment residuals (WTRs) was applied to dilute synthetic wastewater (ca. 20 mg/L), while precipitation process by lime (calcium hydroxide, Ca(OH)2) was applied to concentrated wastewater (ca. 750 mg/L) using both synthetic and optoelectronic wastewater.
Four samples of WTRs (Al-WTR1, Al-WTR2, Al-WTR3, and Fe/Mn-WTR) were assessed as an adsorbent for boron removal. The Al-WTRs were mainly composed of Al2O3, Fe2O3, and SiO2, while Fe2O3, MnO2, Al2O3, and SiO2 were the dominant component for Fe/Mn-WTR. The adsorption reaction could be approximated by a pseudo-second-order kinetic model. The equilibrium pH (pHe) affected boron adsorption and the optimum pHe was found at pHe of 8.3±0.2 and 8.2±0.2 for Al-WTRs and Fe/Mn-WTR, respectively. The Langmuir isotherm model described the adsorption data satisfactory (R2 value average ≧ 0.990) and the batch maximum capacities were found as 0.980, 0.700, 0.190, and 0.440 mg/g using four samples, respectively at optimum pHe. Thermodynamic analysis revealed that the adsorption reaction by the WTRs was spontaneous and exothermic. The low ∆Ho value of -1.58 kJ/mol for Al-WTR1 and -8.20 kJ/mol for Fe/Mn-WTR suggested that was indicative of a physical adsorption. Electrostatic interactions and van der Waals force were proposed as major driving forces of adsorption under different pH condition. The BET specific surface area, aluminum content of Al-WTRs, and iron oxide content of Fe-WTR affected boron adsorption, as judged by the fact that Al-WTRs that have high BET surface area and aluminum content than other showed higher adsorption capacity than the others. On the other hand, the iron oxide content of Fe-/Mn-WTR also showed the same trend by using Fe-based sludge. The results of this study show that WTRs can be used as an alternative adsorbent for boron removal.
Removal of high concentrated of boron from synthetic and optoelectronic wastewater by precipitation with lime (Ca(OH)2) was studied under moderate temperature (45–80oC). Pseudo-first order kinetic model fits the reaction satisfactorily. The activation energy (Ea) of the reaction was 45.1 kJ/mol, implying the reaction rate was controlled by surface chemical reaction. The calcium borate precipitate formed at 60oC was cooled to room temperature gradually and no re-dissolution of boron was found, indicating that calcium borate was a stable compound. The precipitates were characterized by SEM, XRD, and XPS, and confirmed that it was calcium borate (Ca2B2O5.H2O). Boron removal in both synthetic wastewater and optoelectronic wastewater increased with increasing pHe and stabilized at equilibrium pH of 12.4±0.1. The optimum dose of Ca(OH)2 was 10 g/L, at which 87% of boron was removed at 60oC. Experimental results showed that precipitation process using Ca(OH)2 was very effective and efficient for high concentration of boron.

Agabekov, V., Ariko, N., Ivanova, N., Filippovich, L., Shahab, S., Matusevich, V.,
Pismennaya, K., Kiessling, A., and Kowarschik, R., 2004. Chemical and optical
investigations of film polarizers with azodyes, Proceedings of SPIE - The
International Society for Optical Engineering Vol. 5464, 292–297.
Aldaco, R., Garea, A., Irabien, A., 2007. Calcium fluoride recovery from fluoride
wastewater in a fluidized bed reactor, Water Research Vol. 41 (4), 810–818.
APHA, AWWA, WEF, 1995. Standard methods for the examination of water and
wastewater, 19th edition, APHA: Washington, DC, USA, pp. (1–1)–(1–3); (3–16)
Ayyildiz, H. F., Kara, F., 2005. Boron removal by ion exchange membranes, Desalination
Vol. 180 (1–3) 99–108.
Banasiak, L. J., Schafer, A. I., 2009. Removal of boron, fluoride and nitrate by
electrodialysis in the presence of organic matter, Journal of Membrane Science Vol.
334 (1–2), 101–109.
Bao, L., Xu, Z. -H., Li, R., Li, X., 2010. Catalyst-free synthesis and structural and
mechanical characterization of single crystalline Ca2B2O5·H2O nanobelts and
stacking faulted Ca2B2O5 nanogrooves, Nano Letterst Vol. 10 (1), 255–262.
References
94∣Page
Bektas, N., Oncel, S., Akbulut, H. Y., Dimoglo, A., 2004. Removal of boron by
electrocoagulation, Environmental Chemistry Letters Vol. 2 (2), 51–54.
Blais, J. F., Djedidi, Z., Cheikh, R. B., Tyagi, R. D., and Mercier G., 2008. Metals
precipitation from effluents: Review, Practice Periodical of Hazardous, Toxic, and
Radioactive Waste Management, Vol. 12 (3), 135–149.
Blanchard, G., Maunaye, M., and Martin, G., 1984. Removal of heavy metals from waters
by means of natural zeolites, Water Research Vol. 18 (12), 1501–1507.
Bouguerra, W., Mnif, A., Hamrouni, B., and Dhahbi, M., 2008. Boron removal by
adsorption onto activated alumina and by reverse osmosis, Desalination Vol. 223
(1–3), 31–37.
Bothe Jr, J. V., and Brown, P. W., 1999. Arsenic immobilization by calcium arsenate
formation, Environmental Science and Technology Vol. 33 (21), 3806–3811.
Butt, H. -J., 1991. Measuring electrostatic, van der Waals, and hydration forces in
electrolyte solutions with an atomic force microscope, Biophysical Journal Vol. 60 (6),
1438–1444.
Cengeloglu, Y., Tor, A., Arslan, G., Ersoz, M. and Gezgin, S., 2007. Removal of boron
from aqueous solution by using neutralized red mud, Journal of Hazardous Materials
Vol. 142 (1–2) 412–417.
Chang, M. F. and Liu, J. C., 2007. Precipitation removal of fluoride from semiconductor
References
95∣Page
wastewater, Journal of Environmental Engineering Vol 133 (4), 419–425.
Cheng, Y. C. and Huang, H. Y., 1993. van der Waals interaction between a molecule and a
solid surface, Chinese Journal of Physics Vol. 31 (1), 137–145.
Chong, M. F., Lee, K. P., Chien, H. J., and Ramli, I. I. S. B., 2009. Removal of boron from
ceramic industry wastewater by adsorption–flocculation mechanism using palm oil
mill boiler (POMB) bottom ash and polymer, Water Research Vol. 43 (13),
3326–3334.
Chu, W., 2001. Dye removal from textile dye wastewater using recycled aluminum-based
water treatment residual, Water Research Vol. 35 (13) 3147–3152.
Do, D., 1998. Adsorption analysis: Equilibria and kinetics, Imperial College Press:
London.
Environmental Protection Agency, Taiwan, 2007. Industrial effluent standard, Taiwan
Environmental Library, R.O.C., Taiwan.
http://law.epa.gov.tw/en/laws/480770486.html, Latest accessed on April 18, 2011.
Environmental Protection Department, Hong Kong, 1997. Technical memorandum -
Standards for effluents discharged into drainage and sewerage systems, Inland and
coastal waters. The Government of the Hong Kong: Special Administrative Region.
Fogler, H. S., 2006. Element of chemical reaction engineering, 4th edition, Prentice Hall
International, Inc. New Jersey, USA, pp. 849.
References
96∣Page
Garcıa-Soto, M. M. F., and Camacho, E. M., 2009. Boron removal by means of adsorption
with magnesium oxide – Modelization and mechanism, Desalination Vol. 249 (2),
626–634.
Shitole, S. J., and Saraf, K. B., 2002. Growth, structural and microtopographical studies of
calcium iodate, monohydrate crystals grown in silica gel, Crystal Research
Technology Vol. 37 (5), 440 – 445.
Gemici, U., Tarcan, G., 2002. Distribution of boron in thermal waters of Western Anatolia,
Turkey, and examples of their environmental impacts, Environmental Geology 43
(1–2), 87–98.
Goldberg, S., and Glaubic, R. A., 1985. Boron adsorption on aluminum and iron oxide
minerals, Soil Science Society of America Journal Vol. 49 (6), 1374–1379.
Goldberg, S., 1997. Reaction of boron with soils, Plant Soil Vol. 193 (1–2), 35–48.
Hanay, A. Boncukcuoglu, R. Kocakerim, M. M., and Yilmaz, A. E., 2003. Boron removal
from geothermal waters by ion exchange in a batch reactor, Fresenius Environmental
Bulletin Vol. 12 (10), 1190–1194.
Health Canada, 2002. Summary of guidelines for Canadian drinking water quality 2003,
Ottawa: Health Canada.
Ho, Y. S. and McKay, G., 2000. The kinetics of sorption of divalent metal ions onto
sphagnum moss peat, Water Research Vol. 34 (3), 735–742.
References
97∣Page
Hobbs, M. Y. and E.J. Reardon, E. J., 1999. Effect of pH on boron coprecipitation by
calcite: Further evidence for nonequilibrium partitioning of trace elements,
Geochimica et Cosmochimica Acta Vol. 63 (7–8) 1013–1021.
Inglezakis, V. J. and Poulopoulos, S. G., 2006. Adsorption, ion exchange and
catalysis-design: Operations and environmental applications. 1st edition, Elsevier,
Amsterdam, The Netherlands, pp. 32.
Ippolito, J. A., Barbarick, K. A., and Elliott, H. A., 2011. Drinking water treatment
residuals: A review of recent uses, Journal of Environmental Quality Vol. 40 (1)
1–12.
Ippolito, J. A., Barbarick, K. A., Heil, D. M., Chandler, J. P., and Redente, E. F., 2003.
Phosporus retention mechanisms of a water treatment residual, Journal of
Environmental Quality Vol. 32 (5) 1857–1864.
Ippolito, J. A., Scheckel, K. G., and Barbarick, K. A., 2009. Selenium adsorption to
aluminum-based water treatment residuals, Journal of Colloid and Interface Science
Vol. 338 (1), 48–55.
Itakura, T., Sasai, R., and Itoh, H., 2005. Precipitation recovery of boron from wastewater
by hydrothermal mineralization, Water Research Vol. 39 (12), 2543–2548.
Itakura, T., Sasai, R., and Itoh, H., 2006. A novel recovery method for treating wastewater
containing fluoride and fluoroboric acid, Bulletin of the Chemical Society of Japan
References
98∣Page
Vol. 79 (8), 1303–1307.
Itakura, T., Sasai, R., and Itoh, H., 2007. Arsenic recovery from water containing arsenite
and arsenate ions by hydrothermal mineralization, Journal of Hazardous Material,
Vol. 146 (1-2), 328–333.
Jeong, Y., Fan, M., Singh, S., Chuang, C. -L., Saha, B., and Hans van Leeuwen, J., 2007.
Evaluation of iron oxide and aluminum oxide as potential arsenic (V) adsorbents,
Chemical Engineering Processing: Process Intensification Vol. 46 (10), 1030–1039.
Jiang, J. -Q., Xu, Y., Simon, J., Quill, K., and Shettle, K., 2006. Removal of boron (B)
from waste liquors, Water Science and Technology Vol. 53 (11), 73–79.
Jiang, J. -Q., Xu, Y., Simon, J., Quill, K., and Shettle, K., 2007. Laboratory study of boron
removal by Mg/Al double-layered hydroxides, Industrial and Engineering Chemistry
Research Vol. 46 (13), 4577–4583.
Kabay, N., Arar, O., Acar, F., Ghazal, A., Yuksel, U., and Yuksel, M., 2008. Removal of
boron from water by electrodialysis: effect of feed characteristics and interfering ions,
Desalination Vol. 223 (1–3), 63–72
Kabay, N., Sarp, S., Yuksel, M., Arar, O., and Bryjak, M., 2007. Removal of boron from
seawater by selective ion exchange resins, Reactive and Functional Polymers Vol. 67
(12 SPEC. ISS.), 1643–1650.
References
99∣Page
Karaca, S., Gürses, A., Ejder, M., and Açikyildiz, M., 2004. Kinetic modeling of
liquid-phase adsorption of phosphate on dolomite, Journal of Colloid and Interface
Science Vol. 277 (2), 257–263.
Kavak, D., 2009. Removal of boron from aqueous solutions by batch adsorption on
calcined alunite using experimental design, Journal of Hazardous Materials Vol. 163
(1), 308–314.
Kentjono, L., Liu, J. C., Chang, W. C., and Irawan, C., 2010. Removal of Boron and Iodine
from Optoelectronic Wastewater Using Mg-Al(NO3) Layered Double Hydroxide,
Desalination Vol. 262 (1–3), 280–283.
Kong, L., Lu, X., Bian, X., Zhang, W., and Wang, C., 2011. Constructing carbon-coated
FeO microspheres as antiacid and magnetic support for palladium nanoparticles for
catalytic applications, ACS applied materials & interfaces Vol. 3 (1), 35–42.
Koseoglu, H., Kabay, N., Yüksel, M., and Kitisa, M., 2008. The removal of boron from
model solutions and seawater using reverse osmosis membranes, Desalination 223
(1–3), 126–133.
Kosmulski, M., 2009. Compilation of PZC and IEP of sparingly soluble metal oxides and
hydroxides from literature, Advances in Colloid and Interface Science Vol. 152 (1–2),
14–25.
Lagergren, S., 1898. About the theory of so-called adsorption of soluble substances,
References
100∣Page
Kungliga Svenska Vetenskapsakademiens, Handlingar Band 24 (4), 1–39.
Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and platinum,
The Journal of American Chemical Society Vol. 40 (9), 1361–1403.
Leader, J. W., Dunne, E. J., and Reddy K. R., 2008. Phosphorus sorbing materials:
Sorption dynamics and physicochemical characteristics, Journal of Environmental
Quality Vol. 37 (1), 174–181.
Lemarchand, E., Schott, J., and Gaillardet, J., 2007. How surface complexes impact boron
isotope fractionation: Evidence from Fe and Mn oxides sorption experiments, Earth
and Planetary Science Letters Vol. 260 (1–2), 277–296.
Lide, D.R., 2006. CRC-Handbook of Chemistry and Physics, 87th edition, Taylor and
Francis Group, LLC, U.S., pp. (12–27)–(12–28).
Makris, K. C., Harris, W. G., O’Connor, G. A., and Obreza, T. A., 2008. Phosphorus
immobilization in micropores of drinking-water treatment residuals: Implications for
long-term stability. Environmental Science and Technology Vol. 38 (24), 6590–6596.
Makris, K. C., Sarkar, D., and Datta, R., 2006. Aluminum-based drinking-water treatment
residual: A novel sorbent for perchlorate removal, Environmental Pollution Vol. 140
(1), 9–12.
Matsumoto, M., Kondo, K., Hirata, M., Kokubu, S., Hano, T., and Takada, T., 1997.
Recovery of Boric Acid from Wastewater by Solvent Extraction, Separation Science
References
101∣Page
and Technology Vol. 32 (5), 983–991.
Ministry of Health, New Zealand, 2008. Drinking-water standards for New Zealand 2005
(Revised 2008). Wellington: Ministry of Health.
Ministry of the Environment, Indonesia, 2001. Pengelolaan Kualitas Air dan
Pengendalian Pencemaran Air, Peraturan Pemerintah Republik Indonesia No. 82
Tahun 2001. http://www.menlh.go.id/Peraturan/PP/PP82-2001.pdf, Latest accessed
on April 18, 2011.
Ministry of the Environment, Japan, 2007. Environmental Quality Standard for Water.
http://www.env.go.jp/en/standards/, Latest accessed on May 23, 2011.
Ministry of Environment, Republic of Korea, 2009. Management of Drinking Water
Quality.
http://eng.me.go.kr/content.do?method=moveContent&menuCode=pol_wss_sup_pol
_drinking, Latest accessed on May 23, 2011..
Mohapatra, D., Chaudhury, G. R., and Park, K. H., 2008. Solvent extraction approach to
recover boron from wastewater generated by the LCD manufacturing industry: Part 1,
Minerals and Metallurgical Processing Vol. 25 (4), 175-180.
Moulder, J. F., Stickle, W. F., Sobol, P. E., and Bomben, K. D., 1995. Handbook of X-ray
Photoelectron Spectroscopy, Edited by J. Chastain and RC King, Jr., Physical
Electronics, Inc. Minnesota, USA, pp. 39; 41; 45; 69.
References
102∣Page
Myers, D., 1991, Surfaces, Interfaces, and Colloids: Principles and Applications, VCH
Publishers, Inc.: New York, pp. 69-85, 175-185, 299-332.
Nagar, R., Sarkar, D., Makris, K. C., and Datta, R., 2010. Effect of solution chemistry on
arsenic sorption by Fe- and Al-based drinking-water treatment residuals,
Chemosphere Vol. 78 (8) 1028–1035.
National Water Quality Management Strategy, Australia, 2004. Australian Drinking Water
Guidelines 6, pp. 10–22.
Opiso, E., Sato, T., and Yoneda, T., 2009. Adsorption and co-precipitation behavior of
arsenate, chromate, selenate and boric acid with synthetic allophane-like materials,
Journal of Hazardous Materials Vol. 170 (1), 79 – 86.
Ozturk, N. and Kavak, D., 2004. Boron removal from aqueous solution by adsorption on
waste sepiolite and activated waste sepiolite using full factorial design, Adsorption
Vol. 10 (3) 245–257.
Ozturk, N., and Kavak, D., 2005. Adsorption of boron from aqueous solutions using fly ash:
Batch and column studies, Journal of Hazardous Materials Vol. 127 (1–3), 81–88.
Öztürk, N., and Köse, T. E., 2008. Boron removal from aqueous solutions by ion-exchange
resin: Batch studies, Desalination Vol. 22 (1–3), 233–240.
Parks, J. L., and Edwards, M., 2005. Boron in the environment, Critical Reviews in
Environmental Science and Technology Vol. 35 (2), 81 – 114.
References
103∣Page
Patel, G., Pal, U. and Menon, S., 2009. Removal of fluoride from aqueous solution by CaO
nanoparticles, Separation Science and Technology Vol. 44 (12) 2806–2826.
Queste, A., Lacombe, M., Hellmeier, W., Hillermann, F, Bortulussi, B., Kaup, M., Ott, K.,
and Mathy, W., 2001. High concentrations of fluoride and boron in drinking water
wells in the Muenster region – Results of a preliminary investigation, International
Journal of Hygiene and Environmental Health Vol. 203 (3), 221–224.
Rajaković, Lj. V., and Ristić, M. Dj., 1997. Sorption of boric acid and borax by activated
carbon impregnated with various compounds, Carbon Vol. 4 (6), 769–774.
Reardon, E. J., and Wang, Y., 2000. A limestone reactor for fluoride removal from
wastewaters, Environmental Science and Technology Vol. 34 (15), 3247–3253.
Remy, P., Muhr, H., Plasari, E., and Ouerdiane, I., 2005. Removal of boron from
wastewater by precipitation of sparingly soluble salt, Environmental Progress Vol. 24
(1), 105–110.
Saly, M. J., Munnik, F., and Winter, C. H., 2010. Atomic layer deposition of Ca2B2O4 films
using bis(tris(pyrazolyl)calcium as a highly thermally stable boron and calcium
source, Journal of Materials Chemistry Vol. 20 (44), 9995–10000.
Sayiner, G., Kandemirli, F., and Dimoglo, A., 2008. Evaluation of boron by
electrocoagulation using iron and aluminum electrodes, Desalination Vol. 230 (1–3),
205–212.
References
104∣Page
Soto, M. L., Moure, A., Domingues, H., and Parajo, J. C., 2011. Recovery concentration
and purification of phenolic compounds by adsorption : A review, Journal of Food
Engineering Vol. 105 (1), 1–27.
Tsai, H. C., and Lo, S. L., 2011. Boron removal and recovery from concentrated
wastewater using a microwave hydrothermal method, Journal of Hazardous
Materials Vol. 186 (2–3), 1431–1437.
Tu, K. L., Nghiem, L. D., and Chivas, A. R., 2010. Boron removal by reverse osmosis
membranes in seawater desalination applications, Separation and Purification
Technology Vol. 75 (2), 87–101.
Turek, M., Dydo, P., Trojanowska, J., and Campen, A., 2007.
Adsorption/co-precipitation-reverse osmosis system for boron removal, Desalination
Vol. 205 (1–3), 192 – 199.
Vasudevan, S., Sheela, S. M., Lakshmi, J., and Sozhan, G., 2010. Optimization of the
process parameters for the removal of boron from drinking water by
electrocoagulation – a clean technology, Journal of Chemical Technology and
Biotechnology Vol. 85 (7), 926–933.
Vinitnantharat, S., Kositchaiyong, S., and Chiarakorn, S., 2010. Removal of fluoride in
aqueous solution by adsorption on acid activated water treatment sludge, Applied
Surface Science Vol. 256 (17), 5458–5462.
References
105∣Page
Wang, J., Burken, J. G., Zhang, X., and Surampalli, R., 2005. Engineered Struvite
Precipitation: Impacts of Component-Ion Molar Ratios and pH, Journal of
Environmental Engineering Vol 131(10), 1433–1440.
Weinthal, E., Parag, Y., Vengosh, A., Muti, A., and Kloppmann, W., 2005. The EU
Drinking Water Directive: The Boron standard and scientific uncertainty, European
Environment Vol. 15 (1), 1–12.
World Health Organization, 2006. Guidelines for drinking water quality. Boron. Geneva:
World Health Organization.
Xu, Y., and Jiang, J. -Q., 2007. Technologies for boron removal, Industrial and
Engineering Chemistry Research Vol. 47 (1) 16–24.
Yang, Y., Zhao, Y. Q., Babatunde, A. O., Wang, L., Ren, Y. X., and Han, Y., 2006.
Characteristics and mechanisms of phosphate adsorption on dewatered
aluminum-based water treatment residual, Separation and Purification Technology
Vol. 51 (2), 193–200.
Yazicigil, Z., and Oztekin, Y., 2006. Boron removal by electrodialysis with
anion-exchange membranes, Desalination Vol. 190 (1–3), 71–78.
Yi, W. G., and Lo, K. V., 2003. Phosphate recovery from greenhouse wastewater, Journal
of Environmental Science and Health, Part B: Pesticides, Food Contaminants, and
Agricultural Wastes Vol. 38 (4), 501–509.
References
106∣Page
Yilmaz, A. E., Boncukcuoglu, R., and Kocakerim, M. M., 2007. A quantitative comparison
between electrocoagulation and chemical coagulation for boron removal from
boron-containing solution, Journal of Hazardous Materials Vol. 149 (2), 475–481.
Yuksel, S. and Yurum, Y., 2010. Removal of boron from aqueous solutions by adsorption
using fly ash, zeolite, and demineralized lignite, Separation Science and Technology
Vol. 45 (1), 105–115.
Yurdakoç, M., Seki, Y., Karahan, S., and Yurdakoç, K., 2005. Kinetic and thermodynamic
studies of boron removal by Siral 5, Siral 40, and Siral 80, Journal of Colloid and
Interface Science Vol. 286 (2), 440–446.
Zachara, J. M., Gassman, P. L., Smith, S. C., and Taylor, D., 1995. Oxidation and
adsorption of Co(II)EDTA2- complexes in subsurface materials with iron and
manganese oxide grain coatings, Geochimica et Cosmochimica Acta Vol 59 (21),
4449–4453.
Zhang, G., Qu, J., Liu, H., Liu, R., and Wu, R., 2007. Preparation and evaluation of a novel
Fe-Mn binary oxide adsorbent for effective arsenite removal, Water Reserach Vol. 41
(9), 1921–1928.
Zhang, G., Liu, H., Liu, R., and Qu, J., 2009. Removal of phosphate from water by a
Fe-Mn binary oxide adsorbent, Journal of Colloid and Interface Science Vol. 335 (2),
168–174.
References
107∣Page
Zhang, T., Ding, L., Ren, H., Guo, Z., and J. Tan, J., 2010. Thermodynamic modeling of
ferric phosphate precipitation for phosphorus removal and recovery from wastewater,
Journal of Hazardous Materials Vol. 176 (1 – 3), 444–450.