The annual olive oil production in Cyprus is in the range of 2700–3100?t?y?1, resulting in the generation of significant amount of waste. The cocomposting of the olive oil solid residue (OOSR) and the treated wastewaters (with Fenton) from the olive oil production process with the application of reed beds has been studied as an integrated method for the treatment of wastewater containing high organic and toxic pollutants under warm climate conditions. The experimental results indicated that the olive mill wastewater (OMW) is detoxified at the end of the Fenton process. Specifically, COD is reduced up to 65% (minimum 54.32%) by the application of Fenton and another 10–28% by the application of red beds as a third stage. The final cocomposted material of OOSR with the treated olive mile wastewater (TOMW) presents optimum characteristics and is suitable for agricultural purpose. 1. Introduction Olive oil production is considered one of the oldest agricultural industries in the Mediterranean countries. Approximately of olive oil is produced annually worldwide, where the majority of it is produced in the Mediterranean basin [1–3]. The average amount of olive mill wastewater (OMW) produced during the milling process is 1.2–1.8?m3?t?1. OMW resulting from the production processes in the Mediterranean region surpasses 30 million t per year [2, 3]. The treatment of liquid wastes produced from olive oil production is still a major challenge facing this industry. The main problem is attributed to its dark colour, high organic content, and toxicity, which are due to the presence of phenolic compounds [3, 4]. Chemical oxidation demand (COD) values of OMW may reach 150?g?L?1, most of which are in a particulate form. Suspended solids up to 190?g?L?1 have been recorded [3, 5]. A common way of dealing with the OMW in many Mediterranean countries is to discharge it directly into sewer network, convey it to a central lagoon, or store it in a small pond beside the mill, where it is left to evaporate until the next season. These ponds often leak causing ground water pollution and unpleasant odours problems. Since the setting up of more stringent regulations concerning public waste disposal, there is a growing interest in the development of new technologies and procedures for the purification of this wastewater. Today, olive tree in Cyprus is grown in compact groves or, more often, mixed with other crops such as fruit trees, carobs, and cereals. It is also found scattered on uncultivated land, steep slopes, rocky ground, or in residential areas. Some 12000 families are
References
[1]
I. Sabbah, T. Marsook, and S. Basheer, “The effect of pretreatment on anaerobic activity of olive mill wastewater using batch and continuous systems,” Process Biochemistry, vol. 39, no. 12, pp. 1947–1951, 2004.
[2]
S. Khoufi, F. Aloui, and S. Sayadi, “Treatment of olive oil mill wastewater by combined process electro-Fenton reaction and anaerobic digestion,” Water Research, vol. 40, no. 10, pp. 2007–2016, 2006.
[3]
F. A. El-Gohary, M. I. Badawy, M. A. El-Khateeb, and A. S. El-Kalliny, “Integrated treatment of olive mill wastewater (OMW) by the combination of Fenton's reaction and anaerobic treatment,” Journal of Hazardous Materials, vol. 162, no. 2-3, pp. 1536–1541, 2009.
[4]
F. Cabrera, R. López, A. Martinez-Bordiú, E. De Dupuy Lome, and J. M. Murillo, “Land treatment of olive oil mill wastewater,” International Biodeterioration and Biodegradation, vol. 38, no. 3-4, pp. 215–225, 1996.
[5]
P. Ca?izares, J. Lobato, R. Paz, M. A. Rodrigo, and C. Sáez, “Advanced oxidation processes for the treatment of olive-oil mills wastewater,” Chemosphere, vol. 67, no. 4, pp. 832–838, 2007.
[6]
“Agricultural Statistics, (2006),” Department of Statistics and Research, Ministry of Finance. Rebublic of Cyprus, July 2006.
[7]
“Imports and Exports Statistics 1985–1999,” Department of Statistics and Research, Ministry of Finance, Cyprus, 2000.
[8]
M. Gotsi, N. Kalogerakis, E. Psillakis, P. Samaras, and D. Mantzavinos, “Electrochemical oxidation of olive oil mill wastewaters,” Water Research, vol. 39, no. 17, pp. 4177–4187, 2005.
[9]
M. Stoller, “On the effect of flocculation as pretreatment process and particle size distribution for membrane fouling reduction,” Desalination, vol. 240, no. 1–3, pp. 209–217, 2009.
[10]
D. Mantzavinos and N. Kalogerakis, “Treatment of olive mill effluents: part I. Organic matter degradation by chemical and biological processes—an overview,” Environment International, vol. 31, no. 2, pp. 289–295, 2005.
[11]
A. J. Fiestas Ros, “Reuse and complete treatment of vegetable water: current situation and prospects in Spain,” in Proceedings of International Conference in Olive Oil Processing Wastewater Treatment Methods, Crete, Greece, 1991.
[12]
A. A. Zorpas, A. G. Vlyssides, G. A. Zorpas, P. K. Karlis, and D. Arapoglou, “Impact of thermal treatment on metal in sewage sludge from the Psittalias wastewater treatment plant, Athens, Greece,” Journal of Hazardous Materials, vol. 82, no. 3, pp. 291–298, 2001.
[13]
Y. M. Zhang, G. H. Huang, L. He, and Y. P. Li, “Quality evaluation for composting products through fuzzy latent component analysis,” Resources, Conservation and Recycling, vol. 52, no. 10, pp. 1132–1140, 2008.
[14]
A. A. Zorpas, A. G. Vlyssides, and M. Loizidou, “Dewatered anaerobically-stabilized primary sewage sludge composting: metal leachability and uptake by natural clinoptilolite,” Communications in Soil Science and Plant Analysis, vol. 30, no. 11-12, pp. 1603–1613, 1999.
[15]
E. Marinos, “Lagooning concentration of olive oil processing wastewaters,” in Proceedings of International Conference in Olive Oil Processing Wastewater Treatment Methods, pp. 165–175, Crete, Greece, 1991.
[16]
G. Boari, A. Brunetti, R. Passino, and A. Rozzi, “Anaerobic digestion of olive oil mill wastewaters,” Agricultural Wastes, vol. 10, no. 3, pp. 161–175, 1984.
[17]
A. A. Zorpas, “Sewage sludge compost evaluation in Oats, Pepper and Eggplant cultivation,” Dynamic Soil, Dynamic Plant - Global Science Books, vol. 2, no. 2, pp. 103–109, 2008.
[18]
R. Haug, Compost Engineering: Principles and Practice, Technomic Publishing Company, Lancaster, Pa, USA, 1980.
[19]
A. A. Zorpas, Development of a methodology for the composting of sewage sludge using zeolite, Ph.D. thesis, National Technical University of Athens, Athens, Greece, 1999.
[20]
A. A. Zorpas, V. Stamatis, G. A. Zorpas, A. G. Vlyssides, and M. Loizidou, “Compost characteristics from sewage sludge and organic fraction of municipal solid waste,” Fresenius Environmental Bulletin, vol. 8, no. 3-4, pp. 154–162, 1999.
[21]
A. A. Zorpas, E. Kapetanios, G. A. Zorpas et al., “Compost produced from organic fraction of municipal solid waste, primary stabilized sewage sludge and natural zeolite,” Journal of Hazardous Materials, vol. 77, no. 1–3, pp. 149–159, 2000.
[22]
A. A. Zorpas, T. Constantinides, A. G. Vlyssides, I. Haralambous, and M. Loizidou, “Heavy metal uptake by natural zeolite and metals partitioning in sewage sludge compost,” Bioresource Technology, vol. 72, no. 2, pp. 113–119, 2000.
[23]
C. P. Huang, C. Dong, and Z. Tang, “Advanced chemical oxidation: its present role and potential future in hazardous waste treatment,” Waste Management, vol. 13, no. 5–7, pp. 361–377, 1993.
[24]
K. Swaminathan, S. Sandhya, A. C. Sophia, K. Pachhade, and Y. V. Subrahmanyam, “Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system,” Chemosphere, vol. 50, no. 5, pp. 619–625, 2003.
[25]
T. H. Kim, C. Park, J. Yang, and S. Kim, “Comparison of disperse and reactive dye removals by chemical coagulation and Fenton oxidation,” Journal of Hazardous Materials, vol. 112, no. 1-2, pp. 95–103, 2004.
[26]
S. Meri?, D. Kaptan, and T. ?lmez, “Color and COD removal from wastewater containing Reactive Black 5 using Fenton's oxidation process,” Chemosphere, vol. 54, no. 3, pp. 435–441, 2004.
[27]
S. Meri?, H. Sel?uk, and V. Belgiorno, “Acute toxicity removal in textile finishing wastewater by Fenton's oxidation, ozone and coagulation-flocculation processes,” Water Research, vol. 39, no. 6, pp. 1147–1153, 2005.
[28]
R. J. Bidga, “Consider Fenton’s chemistry for wastewater treatment,” Chemical Engineering Progress, vol. 91, no. 12, pp. 62–66, 1995.
[29]
Y. W. Kang and K. Y. Hwang, “Effects of reaction conditions on the oxidation efficiency in the Fenton process,” Water Research, vol. 34, no. 10, pp. 2786–2790, 2000.
[30]
X. R. Xu, Z. Y. Zhao, X. Y. Li, and JI. D. Gu, “Chemical oxidative degradation of methyl tert-butyl ether in aqueous solution by Fenton's reagent,” Chemosphere, vol. 55, no. 1, pp. 73–79, 2004.
[31]
M. Altinbas, A. F. Aydin, M. F. Sevimli, and I. Ozturk, “Advanced oxidation of biologically pretreated baker's yeast industry effluents for high recalcitrant COD and color removal,” Journal of Environmental Science and Health, Part A, vol. 38, no. 10, pp. 2229–2240, 2003.
[32]
H. J. H. Fenton, “Oxidation of tartaric acid in presence of iron,” Journal of the Chemical Society, vol. 65, pp. 899–910, 1894.
[33]
A. P. Murphy, W. J. Boegli, M. K. Price, and C. D. Moody, “A fenton-like reaction to neutralize formaldehyde waste solutions,” Environmental Science and Technology, vol. 23, no. 2, pp. 166–169, 1989.
[34]
S. H. Gau and F. S. Chang, “Improved fenton method to remove recalcitrant organics in landfill leachate,” Water Science and Technology, vol. 34, no. 7-8, pp. 455–462, 1996.
[35]
A. A. Burbano, D. D. Dionysiou, M. T. Suidan, and T. L. Richardson, “Oxidation kinetics and effect of pH on the degradation of MTBE with Fenton reagent,” Water Research, vol. 39, no. 1, pp. 107–118, 2005.
[36]
M. I. Badawy, M. Y. Ghaly, and T. A. Gad-Allah, “Advanced oxidation processes for the removal of organophosphorus pesticides from wastewater,” Desalination, vol. 194, no. 1–3, pp. 166–175, 2006.
[37]
E. Epstein, The Science of Composting, Technomic Publishing Company, Lancaster, Pa, USA, 1996.
[38]
USDA, Composting. Part 637, National Engineering Handbook, NRCS, U.S. Department of Agriculture, Washington, DC, USA, 2000.
[39]
A. A. Zorpas and M. Loizidou, “Sawdust and natural zeolite as a bulking agent for improving quality of a composting product from anaerobically stabilized sewage sludge,” Bioresource Technology, vol. 99, no. 16, pp. 7545–7552, 2008.
[40]
M. Fang, J. W. C. Wong, K. K. Ma, and M. H. Wong, “Co-composting of sewage sludge and coal fly ash: nutrient transformations,” Bioresource Technology, vol. 67, no. 1, pp. 19–24, 1999.
[41]
J. L. De Maeseneer, “Constructed wetlands for sludge dewatering,” Water Science and Technology, vol. 35, no. 5, pp. 279–285, 1997.
[42]
J. De Jong, “Purification of wastewater with the aid of rush or reed ponds,” in Biological Conrrol of Water Pollution, J. Tourbier and R. W. Pierson, Eds., pp. 133–139, University of Pennsylvania Press, Philadelphia, Pa, USA, 1976.
[43]
P. F. Cooper, State of Knowledge on Reed Bed Treatmenr Systems, Water Research Centre Processes, Stevenage, UK, 1987.
[44]
K. Bucksteeg, “Treatment of domestic sewage in emergent helophyte beds. German experiences and ATV Guidelines H 262,” in Proceedings of the International Conference on the Use of Constructed Wetlands in Water Pollution Conrrol, pp. 505–515, Cambridge, UK, September 1990.
[45]
L. Mandi, B. Houhoum, S. Asmama, and J. Schwartzbrod, “Wastewater treatment by reed beds: an experimental approach,” Water Research, vol. 30, no. 9, pp. 2009–2016, 1996.
[46]
S. M. Haslam, “Some aspects of the life history and autecology of Phragmites communis Trin.: a review,” Polish Archives of Hydrobiology, vol. 20, no. 1, pp. 79–100, 1973.
[47]
C. Den Hartog, J. Květ, and H. Sukopp, “Reed. A common species in decline,” Aquatic Botany, vol. 35, no. 1, pp. 1–4, 1989.
[48]
A. Lienard, C. Boutin, and D. Esser, “Domestic wastewater treatment with emergent helophyte beds in France,” in Advances in Water Pollution Conrrol, pp. 183–192, Pergamon Press, 1990.
[49]
R. Haberl and R. Perfler, “Nutrient removal in a reed bed system,” Water Science and Technology, vol. 23, no. 4–6, pp. 729–737, 1991.
[50]
H. Brix and H. H. Schiereup, “Danish experience with sewage treatment in wetlands,” in Compte rendu de conferences: Constructed Wetlands for Wastewater Treatment Municipal, Industrial and Agricultural, D. A. Hammer, Ed., pp. 565–573, CRC Press, Chelsea, Mich, USA, 1990.
[51]
J. Puigagut, J. Villase?or, J. J. Salas, E. Bécares, and J. García, “Subsurface-flow constructed wetlands in Spain for the sanitation of small communities: a comparative study,” Ecological Engineering, vol. 30, no. 4, pp. 312–319, 2007.
[52]
M. Hardej and T. Ozimek, “The effect of sewage sludge flooding on growth and morphometric parameters of Phragmites australis (Cav.) Trin. ex Steudel,” Ecological Engineering, vol. 18, no. 3, pp. 343–350, 2002.
[53]
R. H. Kadlec and R. L. Knight, Treatment Wetlands, CRC Press, Boca Raton, Fla, USA, 1996.
[54]
R. G. Wetzel, “Fundamental processes within natural and constructed wetland ecosystems: Short-term vs. Longterm objectives,” in Proceedings of the 7th International Conference on Wetland Systems for Water Pollution Control, pp. 3–12, Lake Buena Vista, Fla, USA, November 2000.
[55]
E. Meers, D. P. L. Rousseau, N. Blomme et al., “Tertiary treatment of the liquid fraction of pig manure with Phragmites australis,” Water, Air, and Soil Pollution, vol. 160, no. 1–4, pp. 15–26, 2005.
[56]
M. Bayley, “Nitrogen removal from domestic effluent using subsurface flow constructed wetland: influence of depth, hydraulic residence time and pre-nitrification,” in Proceedings of 8th International Conference on Wetland Systems for water Pollution Control, p. 304, Dar Es Salam, Tanzania, 2002.
[57]
M. Del Bubba, L. Checchini, C. Pifferi, L. Zanieri, and L. Lepri, “Olive mill wastewater treatment by a pilot-scale subsurface horizontal flow (SSF-h) constructed wetland,” Annali di Chimica, vol. 94, no. 12, pp. 875–887, 2004.
[58]
R. L. Knight, R. H. Kadlec, and H. M. Ohlendorf, “The use of treatment wetlands for petroleum industry effluents,” Environmental Science and Technology, vol. 33, no. 7, pp. 973–980, 1999.
[59]
APHA AWWA-WPCF, Standard Methods for the Examination of Water and Wastewater, American Public Health Association, Washington, DC, USA, 10th edition, 1995.
[60]
V. A. Dean, Water and Wastewater Examination Manual, Lewis Publishers, Chelsea, Mich, USA, 1990.
[61]
A. A. Zorpas, A. G. Vlyssides, and M. Loizidou, “Physical and chemical characterization of anaerobically stabilized primary sewage sludge,” Fresenius Environmental Bulletin, vol. 7, no. 7-8, pp. 502–508, 1998.
[62]
A. A. Zorpas, A. G. Vlyssides, and G. A. Zorpas, “Metal removal from primary sewage sludge by elution with HNO solutions,” Fresenius Environmental Bulletin, vol. 7, no. 11-12, pp. 681–687, 1998.
[63]
D. Atanassova, P. Kefalas, and E. Psillakis, “Measuring the antioxidant activity of olive oil mill wastewater using chemiluminescence,” Environment International, vol. 31, no. 2, pp. 275–280, 2005.
[64]
M. Schnitzer, Methods of Soil Analysis, Part 2, Soil Science Society of America, Madison, Wis, USA, 9th edition, 1982.
[65]
A. F. Gaudy Jr., “Colorimetric Determination of Protein and Carbohydrate,” Industrial Waste Water, vol. 7, pp. 17–22, 1962.
[66]
Handbook of Reference Methods for Soil Analysis, Georgia University Station, Athens, Ga, USA, 1992.
[67]
M. S. Finstein, F. C. Miller, S. T. MacGregor, and K. M. Psarianos, “The Rutgers strategy for composting: process desing and control,” in Proceedings of the International Symposium on Compost Recycling of Waste, Acta Horticulturae 302, pp. 75–86, Athens, Greece, March 1992.
[68]
W. J. Jewell and R. M. Kabrick, “Autoheated aerobic thermophilic digestion with aeration,” Journal of the Water Pollution Control Federation, vol. 52, no. 3, pp. 512–523, 1980.
[69]
Y. P. Alder, E. V. Markova, and Y. V. Granovsky, The Design of Experiments to Find Optimal Conditions, Mir Publisher, Moscow, Russia, 1995.
[70]
W. C. Cochran and G. M. Cox, Experimental Designs, John Wiley & Sons, New York, NY, USA, 1957.
[71]
H. El Hajjouji, N. Fakharedine, G. Ait Baddi et al., “Treatment of olive mill waste-water by aerobic biodegradation: an analytical study using gel permeation chromatography, ultraviolet-visible and Fourier transform infrared spectroscopy,” Bioresource Technology, vol. 98, no. 18, pp. 3513–3520, 2007.
[72]
F. J. Rivas, F. J. Beltrán, O. Gimeno, and J. Frades, “Treatment of olive oil mill wastewater by Fenton's reagent,” Journal of Agricultural and Food Chemistry, vol. 49, no. 4, pp. 1873–1880, 2001.
[73]
A. A. Zorpas, D. Arapoglou, and K. Panagiotis, “Waste paper and clinoptilolite as a bulking material with dewatered anaerobically stabilized primary sewage sludge (DASPSS) for compost production,” Waste Management, vol. 23, no. 1, pp. 27–35, 2003.
[74]
F. Herrera, C. Pulgarin, V. Nadtochenko, and J. Kiwi, “Accelerated photo-oxidation of concentrated p-coumaric acid in homogeneous solution. Mechanistic studies, intermediates and precursors formed in the dark,” Applied Catalysis B, vol. 17, no. 1-2, pp. 141–156, 1998.
[75]
M. A. Miranda, F. Galindo, A. M. Amat, and A. Arques, “Pyrylium salt-photosensitized degradation of phenolic contaminants derived from cinnamic acid with solar light correlation of the observed reactivities with fluorescence quenching,” Applied Catalysis B, vol. 28, no. 2, pp. 127–133, 2000.
[76]
M. A. Miranda, F. Galindo, A. M. Amat, and A. Arques, “Pyrylium salt-photosensitised degradation of phenolic contaminants present in olive oil wastewaters with solar light Part II. Benzoic acid derivatives,” Applied Catalysis B, vol. 30, no. 3-4, pp. 437–444, 2001.
[77]
M. A. Miranda, M. L. Marín, A. M. Amat, A. Arques, and S. Seguí, “Pyrylium salt-photosensitized degradation of phenolic contaminants present in olive oil wastewater with solar light Part III. Tyrosol and p-hydroxyphenylacetic acid,” Applied Catalysis B, vol. 35, no. 3, pp. 167–174, 2002.
[78]
A. M. Amat, A. Arques, H. Beneyto, A. García, M. A. Miranda, and S. Seguí, “Ozonisation coupled with biological degradation for treatment of phenolic pollutants: a mechanistically based study,” Chemosphere, vol. 53, no. 1, pp. 79–86, 2003.
[79]
W. Gernjak, T. Krutzler, A. Glaser et al., “Photo-fenton treatment of water containing natural phenolic pollutants,” Chemosphere, vol. 50, no. 1, pp. 71–78, 2003.
[80]
D. Mantzavinos, “Removal of cinnamic acid derivatives from aqueous effluents by fenton and fenton-like processes as an alternative to direct biological treatment,” Water, Air, and Soil Pollution: Focus, vol. 3, no. 3, pp. 211–221, 2003.
[81]
D. Mantzavinos, “Removal of benzoic acid derivatives from aqueous effluents by the catalytic decomposition of hydrogen peroxide,” Process Safety and Environmental Protection, vol. 81, no. 2, pp. 99–106, 2003.
[82]
E. G. Kapetanios, M. Loizidou, and G. Valkanas, “Compost production from Greek domestic refuse,” Bioresource Technology, vol. 44, no. 1, pp. 13–16, 1993.
[83]
A. Parvaresh, M. R. Shahmansouri, and H. Alidadi, “Determination of Carbon/Nitrogen ratio and heavy metals in bulking agents used for sewage composting,” Iranian Journal of Public Health, vol. 33, no. 2, pp. 20–23, 2004.
[84]
E. I. Jimenez and V. P. Garcia, “Composting of domestic refuse and sewage sludge. II. Evolution of carbon and some “humification” indexes,” Resources, Conservation and Recycling, vol. 6, no. 3, pp. 243–257, 1992.
[85]
M. Ros, C. García, and M. T. Hernandez, “Evaluation of different pig slurry composts as fertilizer of horticultural crops: effects on selected chemical and microbial properties,” Renewable Agriculture and Food Systems, vol. 22, no. 4, pp. 307–315, 2007.
[86]
X. T. He, T. J. Logan, and S. J. Traina, “Physical and chemical characteristics of selected U.S. municipal solid waste composts,” Journal of Environmental Quality, vol. 24, no. 3, pp. 543–552, 1995.
[87]
J. A. Alburquerque, J. Gonzálvez, D. García, and J. Cegarra, “Measuring detoxification and maturity in compost made from “alperujo”, the solid by-product of extracting olive oil by the two-phase centrifugation system,” Chemosphere, vol. 64, no. 3, pp. 470–477, 2006.
[88]
European Commission, “Working document: biological treatment of biowaste, 2nd draft,” pp. 1–22, 2001.
[89]
European Commission, “Working document: biological treatment of biowaste, 2nd draft,” pp. 1–22, 2005.