Preparation of activated carbon from olive mill solid residue

A process was developed for producing high quality activated carbon from Algerian mill waste. The solid olive mill residue was carbonized at 800 °C and physically activated with CO₂, air or steam. An optimum activation temperature of about 850 °C was determined for all the activation agents used. Steam appeared to be the most efficient activator as compared with air and CO₂. An optimal activation time of about 2 h was then determined with steam as the optimum activation agent. The porous structure of the activated carbon was characterized by nitrogen adsorption at −196 °C, and in all cases the surface areas, calculated by DR and BET methods, confirmed the production of a material with good microstructural characteristics and specific surfaces exceeding 1500 m² g⁻¹ for the carbon prepared by steam activation. Phenol adsorption isotherms gave the adsorption properties and the adsorption capacity of about 11.24 mg of phenol per gram of the activated carbon produced. The kinetics of the phenol adsorption onto the porous material was evaluated by means of two models: the external resistance model and the linear model. The second model appeared to constitute a more appropriate fit for the experimental data. © 2000 Society of Chemical Industry     

Microbial and toxic evaluation of raw and treated olive oil mill wastewaters

BACKGROUND: Olive oil mill wastewaters (OMW) from a three‐phase system were treated in a laboratory‐scale continuous stirred tank reactor (CSTR) for hydrogen production. Microbiological and physicochemical characterizations of raw and anaerobically treated olive oil mill effluents were performed. Toxicity assessment was also conducted in order to determine the impact of residual waters on the aquatic environment. RESULTS: Pseudomonas aeruginosa that has the ability to utilize phenolic compounds was isolated in raw OMW, along with several gram‐negative bacteria (Serratia odorifera, Enterobacter cloacae and Aeromonas hydrophila). The dominant species in the untreated effluent appears to be Enterobacter cloacae, whereas in the treated effluent it is Citrobacter braakii. Phenols, pH, NO^?₂, total dissolved solids (TDS) and conductivity were the main parameters related to the observed toxicity. CONCLUSION: A significant differentiation in the microbiological flora was detected between treated and untreated effluents whereas the microbial communities were correlated to the toxicity test results, pointing to the need for further research regarding identification of the microbial flora. This can improve the treatment processes to optimize management of OMW for environmentally safe discharge. Copyright © 2010 Society of Chemical Industry     

Citric acid,biomass and cellular lipid production by Yarrowia lipolytica strains cultivated on olive mill wastewater‐based media

BACKGROUND: Olive mill wastewaters (OMWs) are an important residue and several physico‐chemical and/or biotechnological methods have been proposed for their treatment. RESULTS: The ability of three Yarrowia lipolytica strains to grow on and convert glucose‐enriched OMWs into added‐value compounds in carbon‐ and nitrogen‐limited shake‐flask cultures was assessed. Remarkable decolorization (up to 63%) and non‐negligible removal of phenolic compounds (up to 34%, w/w) occurred. In nitrogen‐limited cultures, the accumulation of cellular lipids was favored by OMW addition into the medium. In contrast, although remarkable quantities of citric acid (Cit) were produced in control experiments (cultures without OMW addition), in which Cit up to 18.9 g L^?1 was produced with yield of Cit synthesized per sugar consumed ～0.73 g g^?1), adaptation of cultures to media supplemented with OMWs reduced the final Cit quantity and conversion yield values achieved. In OMW‐based media, the highest concentration of citric acid produced was 18.1 g L^?1, with conversion yield ～0.51 g g^?1. In carbon‐limited cultures, despite the presence of inhibitory compounds in the medium (e.g. phenols), biomass production was enhanced with the addition of OMWs. The highest biomass concentration achieved was 12.7 g L^?1, with biomass conversion yield per sugar consumed ～0.45 g g^?1. Fatty acid analysis of cellular lipid produced demonstrated that adaptation of all strains in OMW‐based media favored the synthesis of cellular lipids that contained increased concentrations of cellular oleic acid. CONCLUSIONS: The Y. lipolytica strains tested can be regarded as possible candidates for simultaneous OMWs remediation and production of added‐value compounds. Copyright © 2011 Society of Chemical Industry     

Conversions of olive mill wastewater‐based media by Saccharomyces cerevisiae through sterile and non‐sterile bioprocesses

BACKGROUND: Olive mill wastewaters (OMWs) are an important residue and several methods have been proposed for their treatment. RESULTS: Remarkable decolorization (~63%) and phenol removal (~34% w/w) from OMW was achieved. In glucose‐based flask sterile cultures, enrichment with OMWs increased ethanol and biomass production compared with cultures without OMWs added. Flask sterile and un‐sterilized cultures demonstrated similar kinetic results. Batch‐bioreactor trials performed showed higher ethanol and lower biomass quantities compared with the respective shake‐flask experiments, while cultures used under un‐sterilized conditions revealed equivalent results to the sterile ones. In non‐sterile bioreactor cultures, OMWs addition enhanced biomass production in comparison with culture with no OMWs added, whereas ethanol biosynthesis was not affected. The maximum ethanol quantity achieved was 52 g L^?1 (conversion yield per sugar consumed of 0.46 g g^?1) in a batch bioreactor non‐sterilized trial with OMW–glucose enriched medium used as substrate, that presented initial reducing sugars concentration at ~115 g L^?1. Fatty acid analysis of cellular lipids demonstrated that in OMW‐based media, cellular lipids containing increased concentrations of oleic and linoleic acid were produced in comparison with cultures with no OMWs added. CONCLUSIONS: S. cerevisiae simultaneously produced bio‐ethanol and biomass and detoxified OMWs, under non‐sterile conditions. © 2012 Society of Chemical Industry     

Toxic effect of coloured olive compounds on the anaerobic digestion of olive oil mill effluent in UASB-like reactors

Anaerobic sludge digestion of olive oil mill effluent (OOME) in Upflow Anaerobic Sludge Blanket (UASB) reactors was shown to be unstable as a result of both chemical and biological parameters. The study was complicated by the fact that Chemical Oxygen Demand (COD) was removed by growth and maintenance of active biomass and by adsorption in and on the sludge. Coloured compounds caused an inhibition effect on the anaerobic digestion of the wastewater. This inhibition, shown at low COD concentrations of diluted OOME, was due to accumulation of recalcitrant coloured compounds in the sludge, inducing irreversible inhibition of bacterial growth. Partial decolourization of OOME through resin (Duolite XAD 761) treatment reduced the toxic effect.     

Sustainability analysis and benchmarking of olive mill wastewater treatment methods

A large number of publications are available in the literature regarding olive mill wastewater treatment methods. However, none of the proposed methods can be considered as a best available method in terms of its effectiveness, and its environmental and economic impact. Using a literature survey, data were collected and evaluated in order for a sustainability and benchmarking analysis to be developed. Physicochemical, biological and advanced oxidation methods were evaluated and judged in terms of their effectiveness, environmental impact and cost. Effectiveness of each method was estimated in terms of COD and phenolic compounds reduction, environmental impact in terms of CO₂ production, while for the economic impact the operational costs were taken into account. Finally, a procedure is suggested for selection of the most appropriate method based on user preferences (in terms of effectiveness, environmental impact and cost). The present analysis showed that the most effective processes in terms of organics reduction are membrane filtration, electrolysis, supercritical water oxidation and photo‐Fenton. Lower environmental impact was found with anaerobic digestion, coagulation and lime processes, while the lowest cost category involves biocomposting and membrane filtration, thanks to the exploitation of byproducts (biocompost and phenolic compounds, respectively). © 2013 Society of Chemical Industry     

Isolation of a yeast,Trichosporon cutaneum,able to use low molecular weight phenolic compounds: application to olive mill waste water treatment

This study deals with the degradation of phenolic compounds in olive oil mill waste; a highly polluting material in olive oil‐producing countries because of its abundance and the toxicity of its phenolic compound content. This investigation confirms the ability of an isolated yeast, identified as Trichosporon cutaneum, to degrade phenolic compounds extracted from olive mill waste water (OMW). The yeast was adapted to the OMW by an enrichment culture. The results of this biotransformation were a decrease in the phenolic content and hence a reduction in the phytotoxic effects of the effluent after the yeast treatment. The kinetic growth of the isolated yeast on phenol over a range of concentrations (0.3–3.0 g dm^?3) was studied. The ability of the strain to assimilate simple monomeric phenols and alkyl phenols, at a concentration of 1 g dm^?3, in a synthetic liquid medium used as the sole carbon source was investigated in a batch culture. The aromatic ring cleavage pathway occurred in the yeast through catechol oxidation. Using various concentrations of ethyl acetate extract from OMW as the sole carbon source, the yeast exhibited growth on the substrate up to 7 g dm^?3 equivalent of phenols. A significant reduction of COD after the treatment of the OMW extract by the yeast isolate was noticed. The removal of phenol and COD exceeded 80% of the original loading after 8 days of treatment, for extracts containing initial COD in the range 19 to 72 g dm^?3. Copyright © 2004 Society of Chemical Industry     

Anaerobic digestion of Aegean olive mill effluents with and without pretreatment

BACKGROUND: Olive oil production is an important economical activity in the Aegean region of Turkey. However, the effluents of the olive oil producing mills with their high organic loads and toxic compounds are causing serious environmental problems. The anaerobic biological treatment of olive mill wastewater (OMWW) using the treatment plants of the regional industries could be a method of choice and within the scope of this study floccular and granular sludges were investigated in batch mode for their success in the treatment of OMWW while producing biogas. The major limitation of this treatment is the inhibition of methanogenic bacteria by the phenolic compounds in OMWW. Thus an integrated solution was suggested in which a pre‐treatment step (dephenolization) was also introduced before biological step. RESULTS: The effluents of 27 olive mills out of 47 were found to have total phenolics (TP) less than 3 g L^?1 and could be treated anaerobically after simple dilution. The biogas production for the untreated OMWW was higher for floccular sludge than for the granular sludge (68.5 mL and 45.7 mL respectively). Combined pre‐treatment experiments, first coagulation with polyaluminum chloride, followed by flocculation with cationic polyelectrolyte and finally Fenton's oxidation, could remove 80% of TP and 95% of the total suspended solids. CONCLUSION: OMWW having TP values less than 3 g L^?1 can be treated anaerobically using floccular sludge after simple dilution and biogas can be produced. For OMWW samples having higher TP values pre‐treatment is necessary and the pre‐treatment given in this study may be used effectively. Copyright © 2010 Society of Chemical Industry     

Electrochemical treatment of olive mill wastewaters: Removal of phenolic compounds and decolourization

Olive mill wastewaters (OMW) characterized by their dark brown colour and their very high content of phenolic compounds constitute an environmental concern, particularly in Mediterranean countries where the production of olive oil is important. In this investigation, OMW were electrolyzed at platinized expanded titanium electrodes in a modified Grignard reactor divided into two cylindrical compartments separated by a cation-exchange membrane. Results show better than 90% decolourization and nearly 85% removal of phenols, as established by gas chromatography/mass spectrometry, at high current intensity. This process can easily be monitored by cyclic voltammetry at a boron-doped diamond electrode. A significant reduction of chemical oxygen demand and total organic carbon was observed. The electrodes are not passivated and the ohmic potential drop is very low. Electrochemical oxidation in a modified Grignard reactor is a promising process for the destruction of phenolic compounds present in OMW.     

Development and characterization of a digestion model based on olive oil microemulsions

Olive oil microemulsions were used as biomimetic model to simulate aspects of the digestion process in the small intestine. Hydrolytic activity of trypsin and alkaline phosphatase in microemulsions in the presence and in the absence of squalene and phenolic acids at pH 8.5 and 37°C was examined. In the case of trypsin kinetic constants were calculated and found K_m = 0.080 ± 0.002 mM and V_max = 3.8 × 10^?5 ± 0.06 × 10^?5 mM/s. When gallic acid and squalene were added, hydrolytic activity of trypsin was reduced to 77 ± 2% and 69 ± 3%, respectively. In the presence of o‐, m‐, and p‐coumaric acid, protocatechouic acid, and caffeic acid, enzymatic activity was increased up to 142 ± 6%. Hydrolytic activity of alkaline phosphatase was inhibited in the presence of squalene and phenolic acids. To evaluate the size of the dispersed aqueous droplets in the presence and in the absence of enzymes, substrates, and antioxidants, dynamic light scattering (DLS) measurements were carried out and diameters in the range of 8.9–13.4 nm were observed. Membrane flexibility and micropolarity were studied by electron paramagnetic resonance (EPR) spectroscopy. Rotational correlation time (τ_R), order parameter (S), and hyperfine splitting constant (A₀) of doxyl stearic acid in the microemulsions were calculated and found 2.06 ns, 0.17, and 14.30 G, respectively. These values were slightly affected in the presence of additives. Practical applications: The main aim of the present study is to enhance our understanding on the digestibility of proteins and lipids in the presence of food antioxidants suggesting an in vitro digestion model for hydrolases based on virgin olive oil microemulsions. The information generated in this study could potentially facilitate the design and development of novel functional food formulations based on food‐grade colloidal delivery systems. Since modification or fortification of different food products focusing on different areas of health concern are of growing interest among the various sectors of food industry, the proposed research results could be of particular interest.     

Screening of white rot fungi for the treatment of olive mill waste-waters

Several white rot fungi were evaluated for their ability to decolorize olive mill waste-waters (OMW). Among these, Phanerochaete chrysosporium showed the highest potential for the biological depollution of OMW. Approximately 65% of the color and 73% of the chemical oxygen demand (COD) were removed by P. chrysosporium strain HD. Phlebia radiata, Dichomitus squalens, Polyporus frondosus and Coriolus versicolor could also decolorize the OMW but to a lesser extent. The different abilities of these white rot fungi to decolorize OMW correlated with their rates of depolymerization of high molecular weight aromatics and the degradation of the low molecular weight aromatic compounds. Fourteen strains of P. chrysosporium were compared on the basis of their lignin peroxidase (LiP) production, OMW decolorization and residual material dry weight. High lignin peroxidase producer strains, such as strains HD and BKM-F-1767, showed the highest rates of OMW decolorization, P. chrysosporium strains 79–36 and FP 104297 (low LiP producer strains) did not exhibit any decolorization activity.     

The effect of solids on the electrochemical treatment of olive mill effluents

The electrochemical oxidation of an olive mill effluent over Ti–Pt anodes was studied. The effluent had an average total chemical oxygen demand (COD) value of 234 g L^?1, soluble COD of 61 g L^?1, soluble phenolic content 3.4 g L^?1, total solids of 80 g L^?1 and pH = 5.1. Experiments were conducted in a 10 L vessel with the effluent recirculating at 1 L s^?1. The applied current was varied between 5 and 20 A, the salinity between 1 and 4% NaCl, and experiments were performed with the effluent diluted with water to achieve the desired initial concentration. Emphasis was given to the effect of the presence of solids as well as of varying operating conditions on process performance as assessed in terms of COD, color and phenols removal. In general, degradation of phenols occurred relatively fast with conversion increasing with increasing applied current and decreasing initial organic loading and this was accompanied by low COD removal levels and moderate decolorization. The presence of solids had practically no effect on phenols removal, which, in most cases, was complete in less than about 180 min of reaction. However, oxidation in the presence of solids resulted in a substantial solid fraction being dissolved and this consequently increased sample color and the soluble COD content. The solid content typically found in olive mill effluents may partially impede its treatment by electrochemical oxidation, thus requiring more severe operating conditions and greater energy consumption. Copyright © 2007 Society of Chemical Industry     

Fed‐batch fermentation of olive mill wastewaters for lipase production

In the Mediterranean basin countries, huge amounts of olive mill wastewaters (OMW) are produced by the olive oil industry. It constitutes a serious environmental problem, nevertheless its composition turns OMW into a potential growth medium to lipolytic microorganisms. The aim of this work was to study lipase production as well as OMW degradation in fed‐batch cultures of Candida cylindracea CBS 7869, Candida rugosa CBS 2275 and Yarrowia lipolytica W29 (ATCC 20460). Besides the improvement of lipase production, the fed‐batch approach enhanced the effluent degradation, since it led to good COD and lipids reduction, both higher than 50%. C. rugosa achieved the highest value of lipase productivity (130 U L^?1 h^?1), in parallel with highest lipids reduction (77%). This study demonstrates that OMW are becoming a competitive and valuable growth medium in fermentation processes with lipolytic microorganisms. The fed‐batch strategy used proved to be an efficient approach to enhance lipase production from OMW and to reduce significantly the final organic load of the medium. Copyright © 2012 Society of Chemical Industry     

Recovery and preservation of phenols from olive waste in ethanolic extracts

BACKGROUND: The current trend of upgrading undervalued agricultural by‐products involves the recovery of natural antioxidants. The purpose of this study was to recover phenols from fresh olive mill wastewater (OMW) with their dispersion in 85 mL ethanol per 100 mL and to investigate the effect of processing parameters on the phenol content and antioxidant capacity of the extracts. Moreover, all these characteristics were monitored over a period of 18 weeks in order to examine their preservation inside the ethanolic medium. RESULTS: Extraction time (30–120 min) was not critical for the process, while a pre‐treatment step with the addition of ethanol in lower concentrations (20 mL per 100 mL or less) seems to affect negatively the recovery of the phenols in the final (85 mL per 100 mL) ethanolic medium. A pre‐heating step of OMW at 50–60 °C as well as 80 °C resulted in reduction of the phenol concentrations and antioxidant activities of the extracts, probably due to the generation of enzymatic and non‐enzymatic reactions, respectively. Nevertheless, extracts from the heat treated samples generally preserved their phenol characteristics as well as ferric ions reduction ability and indeed increased their radical scavenging activity during storage. CONCLUSION: Extraction of the phenols was mainly governed by their solubilization in the hydro‐ethanolic mixture as well as the thermal pre‐treatment of OMW. Results can be utilized to optimize the recovery and preservation of phenols from OMW in hydro‐ethanolic mixtures. Copyright © 2010 Society of Chemical Industry     

A full‐scale system for aerobic biological treatment of olive mill wastewater

Olive mill wastewater (OMW) is a major environmental problem in the Mediterranean basin. Although many methods for OMW treatment have been developed, only a few have been adopted in pilot‐ or full‐scale applications. A full‐scale system for aerobic biological treatment of OMW was developed. The system consists of a trickling filter and a recirculation tank. Continuous recirculation of the wastewater was used to provide oxygen concentrations from 0.7 to 1.2 mg L^?1. Low ambient temperatures did not affect system performance since the raw wastewater was warm enough. Nutrient addition was not necessary as raw wastewater contained sufficient nitrogen and phosphorous concentrations. Indigenous olive pulp bacteria proved to be resistant to full‐scale conditions. Feed chemical oxygen demand and phenolic concentrations were about 43 000 and 9500 mg L^?1, respectively. The system reduced more than half of the organic load under continuous operation and a hydraulic retention time of 24 h. The efficiency of this method could be improved by combining it with another technology to further reduce the organic load. The absence of mechanical aeration and the very low hydraulic retention time denotes that the proposed system could be viable and attractive. Copyright © 2011 Society of Chemical Industry     

High level of laccases production by Trametes trogii culture on olive mill wastewater‐based media,application in textile dye decolorization

BACKGROUND: Laccases are receiving increasing attention as potential industrial enzymes in various applications. Therefore, it is important to find inexpensive and optimized media for large‐scale commercial production. The present work aims to valorize olive mill wastewater (OMW) by its use as base media for laccases production by Trametes trogii and use of the laccases produced for decolorizing textile dyes. RESULTS: A high yield of 25 120 U L^?1 of laccases was obtained at an OMW:water ratio of 80:20 enriched with 2 g L^?1 of urea corresponding to initial biochemical oxygen demand (BOD₅), chemical oxygen demand (COD) and total phenol concentrations of 18.4, 46 and 4.6 g L^?1 respectively. The partially purified laccases resulted in 85% decolorization of blue tubantin GLL 300 and black tubantin VSF 600, and 45% decolorization of blue solophenyl after 6 h of incubation. Subsequent additions of the same dye dose to the reaction mixture resulted in a very significant decrease in laccases activity after the third dye addition. CONCLUSION: The use of OMW for laccases production is a cost effective process. The laccases produced can be applied to the decolorization of textile wastewaters. Copyright © 2009 Society of Chemical Industry