Degradation of phenols in olive oil mill wastewater by biological,enzymatic, and photo-Fenton oxidation

Background, aim, and scope  

Olive oil mill wastewater (OOMW) environmental impacts minimization have been attempted by developing more effective processes, but no chemical or biological treatments were found to be totally effective to mitigate their impact on receiving systems. This work is the first that reports simultaneously the efficiency of three different approaches: biological treatment by two fungal species (Trametes versicolor or Pleurotus sajor caju), enzymatic treatment by laccase, and chemical treatment by photo-Fenton oxidation on phenols removal.     

Evaluation of olive oil mill wastewater toxicity on spinach

Background, aim, and scope

Olive oil mill wastewater (OMW), a by-product of the olive oil extraction process, is annually produced in huge amounts in olive-growing areas and represents a significant environmental problem in Mediterranean areas. We studied the impact of OMW dilutions (1:20 and 1:10) on spinach plants in order to evaluate OMW dilutions as a low-cost alternative method for the disposal of this waste.

Materials and methods

The effects of OMW dilutions were evaluated on seed germination, shoot and root elongation, biomass production, nutrient uptake and translocation, ascorbic acid content, polyphenols, photosynthetic pigments, and photosynthetic performance of spinach.

Results

Plant biomass was more affected than plant height and total chlorophyll; carotenoid and ascorbic acid content progressively decreased with decreasing OMW dilution. Exposure to both OMW dilutions resulted in overaccumulation of total polyphenols, which were negatively correlated to plant biomass and nutrients. Nutrient (Fe, Ca, and Mg) content was insufficient leading to reduced growth. Water use efficiency decreased mainly due to decreased CO₂ assimilation rate rather than to a decline of transpiration rate. Disturbances in photosystem II (PSII) photochemical efficiency could be better envisaged by the ratio between variable fluorescence and initial fluorescence (Fv/Fo), which showed much greater amplitude than the maximal photochemical efficiency of PSII photochemistry (Fv/Fm).

Conclusions

From the data obtained, it is suggested that 1:20 OMW dilutions are still phytotoxic and that higher OMW dilutions should be used in order to use this waste for the irrigation of spinach plants.     

吸附冷凝回收与生物氧化联合工艺对炼油污水废气的处理

大气污染防治的形势日益严峻,为实现废气的达标排放,采用吸附冷凝回收与生物氧化联合工艺对炼油污水废气进行处理。结果表明,对污水构筑物进行加罩密封后,将废气收集及输送,采用分区收集、分类处理的工艺方法,先对废气收集系统的高浓度废气采用脱硫、吸附冷凝原理进行预处理,再与低浓度废气混合进入生物氧化滴滤段与过滤段进行处理,可有效去除炼油污水处理过程中各池体构筑物逸散出的H2S、有机硫化物、酚类、烃类等有害气体,实现废气的达标排放。其中,通过吸附冷凝回收工艺,高浓度段非甲烷总烃的去除率可稳定在60%以上,通过生物氧化联合处理工艺,低浓度段非甲烷总烃的去除率可稳定在40%以上,且氨、硫化氢、甲苯、二甲苯的总去除效果良好,可以有效改善周边区域的大气环境,满足国家标准规范排放要求及地方环境法规的要求。     

Decolourization and removal of some organic compounds from olive mill wastewater by advanced oxidation processes and lime treatment

Background Olive mill wastewater (OMW) generated by the olive oil extracting industry is a major pollutant, because of its high organic load and phytotoxic and antibacterial phenolic compounds which resist biological degradation. Mediterranean countries are mostly affected by this serious environmental problem since they are responsible for 95% of the worldwide oliveoil production. There are many methods used for OMW treatment, such as adsorption, electro coagulation, electro-oxidation, biological degradation, advanced oxidation processes (AOPs), chemical coagulation, flocculation, filtration, lagoons of evaporation and burning systems, etc. Currently, there is no such economical and easy solution. The aim of this study was to evaluate the feasibility of decolourization and removal of phenol, lignin, TOC and TIC in OMW by UV/H₂O₂ (AOPs). The operating parameters, such as hydrogen peroxide dosage, times, pH, effect of UV and natural sunlight were determined to find the suitable operating conditions for the best removal. Moreover, there is no study reported in the literature related to the use of UV/H₂O₂ and lime together in OMW treatment. Methods OMW was obtained from an olive-oil producing plant (Muğla area of Turkey) which uses a modern production process. No chemical additives are used during olive oil production. This study was realised by using two different UV sources, while taking the time and energy consumption into consideration. These two sources were mercury lamps and natural sunlight. Before starting AOPs experiments, one litre of OMW was treated by adding lime until a pH of 7.00. Then, 100 ml was taken from each sample, and 1 to 10 ml of a 30% H₂O₂ (Riedel-deHaen) solution was added. These solutions in closed vessels were laid in the natural sunlight for a week and their compositions and colour changes were analysed daily by UV-Vis spectrophotometer. At the end of the one-week period, they were treated with lime. In this study, the effect of changes in the initial pH, times and H₂O₂ concentrations on removal was investigated. At the end of all experiments, changes in colour, phenol, lignin, TOC and TIC concentrations were analysed according to standard methods. Results and Discussion In the samples exposed to natural sunlight and having an H₂O₂/OMW ratio of 3 ml/100 ml, a significant colour removal was achieved approximately 90% of the time at the end of 7 days. When the same samples were treated with lime (pH: up to 7), 99% efficiency was achieved. When phenol and lignin removals were examined in the same concentration, phenol and lignin removal were found 99.5%, 35%, respectively. However, for maximum lignin removal, more use of H₂O₂ (10 ml H₂O₂/100 ml OMW) was found to be necessary. Under these conditions, it was found that lignin can be removed by 70%, but to 90% with lime, at the end of a seven-day period. Rate constants obtained in the experiments performed with direct UV were found to be much higher than those of the samples exposed to natural sunlight (k^a _lignin = 0.3883 ≫ k^b _lignin = 0.0078; k^a _phenol = 0.5187 ≫ k^b _phenol = 0.0146). Moreover, it should be remembered in this process that energy consumption may induce extra financial burden for organisations. Conclusions It was found, in general, that colour, lignin, total organic carbon and phenol were removed more efficiently from OMW by using H₂O₂ UV and lime OMW. Moreover, in the study, lime was found to contribute, both initially and after radical reactions, to the efficiency to a great extent. Recommendations and Perspectives Another result obtained from the study is that pre-purification carried out with hydrogen peroxide and lime may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

Advanced oxidation treatment of physico-chemically pre-treated olive mill industry effluent

In this study, the applicability of physico-chemical methods was investigated for the pre-treatment of the olive mill effluents prior to the discharge into the common sewerage ending with a municipal wastewater treatment plant. The samples were taken from an olive oil industry operated as three-phase process located in Turkey. Various pre-treatment methods including acid craking, polyelectrolyte and lime additions were applied. Advanced oxidation study using Fenton's process was also investigated following pre-treatment by acid cracking and cationic polyelectrolyte. Acid cracking alone gave satisfactory treatment efficiencies and polyelectrolite additions to the acid-cracked samples enhanced treatment efficiency. Since a complete treatment plant is available at the end of the sewer system, results indicated that the effluents of the investigated industry could be discharged into the municipal sewerage in the case of total chemical oxygen demand (COD(tot)), suspended solid (SS) and volatile suspended solid (VSS) concentrations according to the Turkish Water Pollution Control Regulation after pre-treatment with 5 ppm anionic polyelectrolyte following acid cracking. The minimum COD(tot), SS and VSS removals were observed when raw wastewater was pre-treated with lime and the discharge standards to the municipal sewer system could not be met. Advanced oxidation with Fenton's process was applied after acid cracking and cationic polyelectrolyte treatment in order to investigate further reduction in chemical oxygen demand (COD) concentration for minimizing the influence of this industrial discharge on the existing municipal wastewater treatment plant. Results indicated that COD(tot) removal increased up to 89% from 74% after Fenton's oxidation for the acid cracked samples in which cationic polyelectrolite (10 ppm) was added.     

Advanced oxidation treatment of physico-chemically pre-treated olive mill industry effluent

In this study, the applicability of physico-chemical methods was investigated for the pre-treatment of the olive mill effluents prior to the discharge into the common sewerage ending with a municipal wastewater treatment plant. The samples were taken from an olive oil industry operated as three-phase process located in Turkey. Various pre-treatment methods including acid craking, polyelectrolyte and lime additions were applied. Advanced oxidation study using Fenton's process was also investigated following pre-treatment by acid cracking and cationic polyelectrolyte. Acid cracking alone gave satisfactory treatment efficiencies and polyelectrolite additions to the acid-cracked samples enhanced treatment efficiency. Since a complete treatment plant is available at the end of the sewer system, results indicated that the effluents of the investigated industry could be discharged into the municipal sewerage in the case of total chemical oxygen demand (COD_tot), suspended solid (SS) and volatile suspended solid (VSS) concentrations according to the Turkish Water Pollution Control Regulation after pre-treatment with 5 ppm anionic polyelectrolyte following acid cracking. The minimum COD_tot, SS and VSS removals were observed when raw wastewater was pre-treated with lime and the discharge standards to the municipal sewer system could not be met. Advanced oxidation with Fenton's process was applied after acid cracking and cationic polyelectrolyte treatment in order to investigate further reduction in chemical oxygen demand (COD) concentration for minimizing the influence of this industrial discharge on the existing municipal wastewater treatment plant. Results indicated that COD_tot removal increased up to 89% from 74% after Fenton's oxidation for the acid cracked samples in which cationic polyelectrolite (10 ppm) was added.     

A mild photochemical approach to the degradation of phenols from olive oil mill wastewater

Photooxidation of cathecol (1) is carried out in aqueous solution at lambda > 300 nm using different sensitizers: rose bengal (RB), 9,10-dicyanoanthracene (DCA), 2,4,6-triphenylpyrylium tetrafluoroborate (Pyryl). The highest degradation is observed in the UV/RB-sensitized reaction (66% after 15 h of irradiation), mineralization and formation of dimers are the final events. This procedure has been extended to tyrosol (2), caffeic acid (3), vanillic acid (4), 4-hydroxycinnamic acid (5) and 4-hydroxybenzoic acid (6) as well as to a mixture of all phenols. A reduced toxicity of the UV/RB-irradiated solutions of cathecol and tyrosol towards alga Ankistrodesmus braunii is also verified.     

Valorization of treated olive mill wastewater in fertigation practice

Olive mill wastewater (OMW) brings about a major environmental problem in Tunisia as well as in the other Mediterranean countries. Its strong organic load and its toxicity due to the presence of complex phenolic compounds have dire effects when applied to soil. To overcome this difficulty, the OMW pretreatment was investigated in the present work using the Fenton oxidation reaction with zero-valent iron. Then, this pretreated wastewater was valorized in fertigation practice. The effects of the addition of different concentrations of both treated and raw OMW on soil and cropping system were investigated. The treatment by Fenton oxidation with zero-valent iron could reduce 50 % of COD and decrease 53 % of phenolic compounds. OMW application had a temporary effect on the soil pH and EC. The results showed that the evolution of soil pH and EC was related to the organic matter of the soil which depends on the spread concentrations of raw or treated OMW. After 15-day incubation period, the soil pH and EC tended to stabilize and return to the control level. Moreover, this stabilization is faster in treated OMW than that in raw OMW especially for concentrations as high as 3 and 4 %. Plants cultivated with treated OMW showed an increase in their germination. The results pointed an improvement in the stem length of plants which is almost similar to that of the control for both pea and tomato, especially for high concentrations of 3 and 4 %.     

Membrane filtration of olive mill wastewater and exploitation of its fractions.

Olive mill wastewater (OMW) produced from small units scattered in rural areas of Southern Europe is a major source of pollution of surface and subsurface water. In the present work, a treatment scheme based on physical separation methods is presented. The investigation was carried out using a pilot-plant unit equipped with ultrafiltration, nanofiltration, and reverse osmosis membranes. Approximately 80% of the total volume of wastewater treated by the membrane units was sufficiently cleaned to meet the standards for irrigation water. The concentrated fractions collected in the treatment concentrates were characterized by high organic load and high content of phenolic compounds. The concentrates were tested in hydroponic systems to examine their toxicity towards undesired herbs. The calculations of the cost of the overall process showed that fixed and operational costs could be recovered from the exploitation of OMW byproducts as water for irrigation and/or as bioherbicides.     

ClO2氧化/TiO2复合吸附剂协同体系处理印染废水的实验研究

利用ClO2 氧化/TiO2 复合吸附剂协同体系对处理实际印染废水进行了实验研究.结果表明,对于COD为750 mg/L、色度为250倍、SS为100 mg/L的1 000 mL印染废水,当溶液pH为4.0、ClO2 用量20 mg/L、TiO2 复合吸附剂用量2.5 g、反应时间和吸附时间分别为2、8 min时,处理后的废水COD＜100 mg/L、色度＜40倍、SS＜70 mg/L,达到了《纺织染整工业水污染物排放标准》(GB 4287-92)排放要求.并对两者的协同机理进行了理论上的探讨.     

Dose and frequency dependent effects of olive mill wastewater treatment on the chemical and microbial properties of soil

Olive mill wastewater (OMW) is a problematic by-product of olive oil production. While its high organic load and polyphenol concentrations are associated with troublesome environmental effects, its rich mineral and organic matter contents represent valuable nutrients. This study aimed to investigate the valorization of this waste biomass as a potential soil conditioner and fertilizer in agriculture. OMW was assayed at three doses 50, 100, and 200 m³ ha⁻¹ year⁻¹) over three successive years in olive fields. The effects of the effluent on the physico-chemical and microbial properties of soil-layers were assessed. The findings revealed that the pH of the soil decreased but electrical conductivity and organic matter, total nitrogen, sodium, and potassium soil contents increased in proportion with OMW concentration and frequency of application. While no variations were observed in phosphorus content, slow increases were recorded in calcium and magnesium soil contents. Compared to their control soil counterparts, aerobic bacteria and fungi increased in proportion with OMW spreading rates. The models expressing the correlation between progress parameters and OMW doses were fitted into a second degree polynomial model. Principal component analysis showed a strong correlation between soil mineral elements and microorganisms. These parameters were not related to phosphorus and pH.     

Industrial wastewater treatment using a bubble photo-Fenton reactor with continuous gas supply

Environmental Science and Pollution Research - The present study assesses the treatability of a real industrial wastewater (WW) with a high organic load (chemical oxygen demand (COD) above 5800...     

Advanced oxidation of a pulp mill bleaching wastewater.

The degradation, by several advanced oxidation reactions, of a pulp mill ECF bleaching effluent, was studied. The initial biodegradability of the organic matter present in the effluent, estimated as the BOD5/COD, was low (0.3). When the effluent was submitted to ozonation and to five different advanced oxidation systems (O3/UV, O3/UV/ZnO, O3/UV/TiO2, O2/UV/ZnO, O2/UV/TiO2), the biodegradability increase significantly. After five minutes of reaction, the O3/UV system appears as the most efficient in to transform the organic matter to more biodegradable forms. A similar effect was observed when the effluent was submitted to an activated sludge treatment. The COD, TOC and toxicity reduction correlated well with the biodegradability enhancement after AOPs treatments.     

树脂吸附-NaClO曝气氧化法处理促进剂M废水的研究

研究了苯胺法生产促进剂M废水的治理 ,通过采用树脂吸附 NaClO曝气氧化二级处理工艺 ,分步去除有机污染物和硫化物 ,废水出水可达到国家一级排放标准。根据实验确定了适宜的工艺参数 ,氧化阶段的实验结果还证实Na ClO曝气氧化较NaClO搅拌氧化具有更高的去除效率     

Changes of turbidity during the phenol oxidation by photo-Fenton treatment

Turbidity presented by phenol solutions oxidized with Fenton reagent shows the tendency of a first order intermediate kinetics. Thus, turbidity can be considered a representative parameter of the presence of intermediate oxidation species, which are generated along the decomposition of toxic and reluctant contaminants, such as phenol. Moreover, that parameter presents a linear dependence with the catalyst dosage, but is also determined by the initial contaminant load. When analyzing the oxidation mechanism of phenol, it is found that the maximum turbidity occurs when the treatment is carried out at oxidant to phenol molar ratios R?=?4.0. These oxidation conditions correspond to the presence of a reaction mixture mainly composed of dihydroxylated rings, precursors of the muconic acid formation. The oxidation via “para” comprises the formation reactions of charge transfer complexes (quinhydrone), between the para-dihydroxylated intermediates (hydroquinone) and the para-substituted quinones (p-benzoquinone), which are quite unstable and reactive species, quickly decomposed into hydroxyhydroquinones. Working with oxidant ratios up to R?=?6.0, the maximum observed value of turbidity in the oxidized solutions is kept almost constant. It is found that, in these conditions, the pyrogallol formation is maximal, what is generated through the degradation of ortho-species (catechol and ortho-benzoquinone) and meta-substituted (resorcinol). Operating with ratios over R?=?6.0, these intermediates are decomposed into biodegradable acids, generating lower turbidity in the solution. Then, the residual turbidity is a function of the molar ratio of the ferrous ions vs. moles of oxidant utilized in the essays, that lets to estimate the stoichiometric dosage of catalyst as 20 mg/L at pH?=?3.0, whereas operating in stoichiometric conditions, R?=?14.0, the residual turbidity of water results almost null.     

吸附氧化/纳滤/吸附组合工艺处理丙烯腈工业废水

针对高浓度丙烯腈工业废水,采用絮凝、吸附氧化、纳滤以及吸附的组合工艺进行处理,考察了不同工艺过程处理高浓度丙烯腈工业废水的效果和费用。结果表明,废水经过絮凝-纳滤-吸附氧化处理工艺,使废水的COD降低到1 000 mg/L以下,氨氮含量低于25 mg/L,CN-含量降低至5 mg/L以下,满足丙烯腈工业废水处理出水指标要求,且操作费用适中,为实现丙烯腈生产工业废水的循环利用奠定了坚实的技术基础。     

生物处理组合工艺用于制革废水处理

针对制革废水高COD、高总氮的问题,提出了基于上流式厌氧污泥床（UASB）、上流式反硝化污泥床（UDNSB）、生物接触氧化池的生物处理组合工艺,进行了为期321 d的现场中试研究。研究结果表明,对于COD、TN、NH4+-N平均浓度分别为2 740、278和193 mg·L-1的制革废水,在硝化液回流比R为300%,UASB反应器、UDNSB反应器、生物接触氧化池的水力停留时间（HRT）分别为11、22和57 h,平均容积负荷分别为5.63 kg COD·（m3·d）-1、0.30 kg TN·（m3·d）-1和0.11 kg NH4+-N·（m3·d）-1的条件下,该组合工艺处理出水COD、TN和NH4+-N的平均浓度分别为190、69.8和4.6 mg·L-1,其平均去除率分别达到92%、73%和97%以上。     

混凝-催化氧化-水解酸化-生物接触氧化法处理染料废水的中试研究

采用混凝-催化氧化-水解酸化-生物接触氧化法处理高浓度难降解分散染料废水.比较分析了O_3、UV/TiO_2/O_3,UV/O_3/H_2O_23种高级氧化法的处理效果.结果表明,UV/TiO_2/O_3对废水COD和色度有较高的去除率.可明显改善废水的可生化性,废水的BOD_5/COD由0.05～0.07升高至0.42～0.46.在混凝沉淀单元HRT为1.5 h.催化氧化单元(UV/TiO_2/O_3)HRT为3.0 h,水解酸化HRT为10.0 h,生物接触氧化HRT为10.0 h的最佳条件下,该组合工艺对废水COD和色度总的去除率分别可达95.0%、99.5%.     

A kinetic study of anaerobic digestion of olive mill wastewater at mesophilic and thermophilic temperatures

The kinetics of the anaerobic digestion of olive mill wastewater (OMW) was studied in the mesophilic and thermophilic ranges of temperature. Two completely mixed continuous flow bioreactors operating at 35 degrees C and 55 degrees C and with an average biomass concentration of 5.45 g VSS litre(-1) were used. The thermophilic reactor worked satisfactorily between hydraulic retention times (HRT) of 10 to 40 days, removing between 94.6 and 84.4% of the initial chemical oxygen demand (COD). In contrast, the mesophilic reactor showed a marked decrease in substrate utilization and methane production at a HRT of 10 days. TVFA levels and the TVFA/alkalinity ratio were higher and close to the suggested limits for digester failure. The yield coefficient for methane production (1 CH(4) STP g(-1) COD(added)) was 28% higher in the thermophilic process than in the mesophilic one. Macroenergetic parameters, calculated using Guiot's kinetic model, gave yield coefficients for the biomass (Y) of 0.18 (mesophilic) and 0.06 g VSS g(-1) COD (thermophilic) and specific rates of substrate uptake for cell maintenance (m) of 0.12 (mesophilic) and 0.27 g COD g(-1) VSS.day(-1) (thermophilic). The experimental results showed the rate of substrate uptake (R(s); g COD g(-1) VSS.day(-1)), correlated with the concentration of biodegradable substrate (S(b); g COD litre(-1)), through an equation of the Michaelis-Menten type for the two temperatures used.     

生物接触氧化法处理稠油污水实验研究

将从稠油污水中筛选出的3株高效烃类降解菌株HD-1、HD-2和HD-3用于稠油污水处理,研究了单一菌株和混合菌株对原油和COD的去除率。实验结果表明,单一菌株对原油和COD具有很好的去除效果,混合菌株对原油和COD去除效果更加显著。室内模拟实验结果表明,在停留时间为6 h时,含油量和COD分别为30 mg/L和300 mg/L时,经过生物接触氧化处理,出水含油量和COD分别降至1 mg/L和50 mg/L以下,达到了反渗透膜组件预处理的要求,为稠油污水热采锅炉用水回用提供了理论基础。