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.     

Fenton氧化法深度处理抗生素废水二级出水

采用Fenton氧化法对青霉素和土霉素混合废水二级处理出水进行深度处理,通过正交和单因素实验研究了废水初始反应pH值、H2O2投加量、Fe2+/H2O2摩尔比及反应时间等因素对废水处理效果的影响。实验结果表明,Fenton氧化法处理的最佳反应条件为:初始pH值4、H2O2(30%)投加量50 mL/L、Fe2+/H2O2摩尔比1/20和反应时间60 min,处理后出水COD小于120 mg/L,COD去除率在75%以上,急性毒性(HgCl2毒性当量)小于0.07 mg/L,满足《发酵类制药工业水污染物排放标准》(GB21903-2008)表2标准要求。     

制浆造纸废水生化出水的混凝处理研究

研究了硫酸铝和三氯化铁对制浆造纸废水生化出水的处理效果.研究发现,不调节原水pH值,硫酸铝投加量为600 mg/L或三氯化铁投加量为300mg/L时,混凝后废水的COD＜150 mg/L,色度＜50倍,出水均符合现阶段排放标准.混凝剂比较发现,在最佳反应条件下,2种混凝剂的处理效果相当,但硫酸铝混凝的成本低于三氯化铁....     

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.     

Complexation parameters of heavy metals by olive mill wastewater determined by a cation exchange resin

Abstract

Complexing parameters in aqueous systems containing heavy metals and wastewater from olive‐oil mill (WOM) have been estimated using a cation exchange resin method. The parameters estimated were the maximum complexing ability (MCA), the stability constant (Kc) and a parameter indicating the stoichiometrical characteristics of the complex (a).

MCA of WOM for Cu, Zn, Pb and Mn was 0.470, 0.314, 0.068 and 0.300 mmol (g WOM)^‐1 respectively, and was related with the ionic radii of the various metal ions. The log Kc values followed the sequence: Cu>Pb>Zn>Mn in agreement with their respective electronegativities. In the case of Cu and Pb, data obtained here was compared with that determined in other work.     

Chemical oxidation of sulfadiazine by the Fenton process: Kinetics,pathways, toxicity evaluation

This paper investigated sulfadiazine oxidation by the Fenton process under various reaction conditions. The reaction conditions tested in the experiments included the initial pH value of reaction solutions, and the dosages of ferrous ions and hydrogen peroxide. Under the reaction conditions with pH 3, 0.25 mM of ferrous ion and 2 mM of hydrogen peroxide, a removal efficiency of nearly 100% was achieved for sulfadiazine. A series of intermediate products including 4-OH-sulfadiazine/or 5-OH-sulfadiazine, 2-aminopyrimidine, sulfanilamide, formic acid, and oxalic acid were identified. Based on these products, the possible oxidation pathway of sulfadiazine by Fenton's reagent was proposed. The toxicity evaluation of reaction solutions showed increased antimicrobial effects following the Fenton oxidation process. The results from this study suggest that the Fenton oxidation process could remove sulfadiazine, but also increase solution toxicity due to the presence of more toxic products.     

Baseline study of methane emission from open digesting tanks of palm oil mill effluent treatment

Anthropogenic release of greenhouse gases, especially CO₂ and CH₄ has been recognized as one of the main causes of global warming. Several measures under the Kyoto Protocol 1997 have been drawn up to reduce the greenhouse gases emission. One of the measures is Clean Development Mechanisms (CDM) that was created to enable developed countries to cooperate with developing countries in emission reduction activities. In Malaysia, palm oil industry particularly from palm oil mill effluent (POME) anaerobic treatment has been identified as an important source of CH₄. However, there is no study to quantify the actual CH₄ emission from the commercial scale wastewater treatment facility. Hence, this paper shall address the CH₄ emission from the open digesting tanks in Felda Serting Hilir Palm Oil Mill. CH₄ emission pattern was recorded for 52 weeks from 3600 m³ open digesting tanks. The findings indicated that the CH₄ content was between 13.5% and 49.0% which was lower than the value of 65% reported earlier. The biogas flow rate ranged between 0.8 l min⁻¹ m⁻² and 9.8 l min⁻¹ m⁻². Total CH₄ emission per open digesting tank was 518.9 kg day⁻¹. Relationships between CH₄ emission and total carbon removal and POME discharged were also discussed. Fluctuation of biogas production was observed throughout the studies as a result of seasonal oil palm cropping, mill activities, variation of POME quality and quantity discharged from the mill. Thus only through long-term field measurement CH₄ emission can be accurately estimated.     

光催化氧化深度处理电镀有机废水的工程化实验

采用光催化氧化联用技术对电镀有机废水进行深度处理工程化实验。探讨了uV、uV＋H2O3、uV＋H2O2＋TiO2、uV＋H2O2＋FeSO4、uV＋H2O2＋FeSO4＋TiO2、uV＋O3＋TiO2和uV＋03＋TiO2＋H2O2等体系对废水有机污染物去除率的影响。结果表明,相较于其他反应体系,uV＋O3＋TiO2＋H2O2体系具有更好的氧化效果,经碳滤处理后去除率达到90％以上,最终出水水质满足GB18918-20O2-级标准（A标准）的要求。实际运行项目偿还期5．33年,NPV〉0,内部收益率大于基准值10％。研究表明,uV＋O3＋TiO2＋H2O,体系能降低加药量,工作量及运行成本。可为电镀企业实际废水处理提供现实依据,为优化电镀废水的处理工艺提供参考。     

造纸白泥和粉煤灰的添加对污泥消化液中氮磷回收的影响

污泥厌氧消化液中含有丰富的氮磷,若直接排放到环境中,将会对附近水体造成严重污染。由于消化液中Mg^2＋和Ca^2＋的含量很低,严重影响了氮磷的回收效果。把造纸白泥和粉煤灰引入到污泥厌氧消化液氮磷的回收当中,可以明显地提升消化液pH和提高PO4^3-P和NH3-N回收率。实验结果表明：当造纸白泥添加量为4g／（L·h）时,曝气12h后,pH可达10．19,此时PO4^3-P和NH3-N回收率分别达到64％和45％;而当粉煤灰添加量为4g／（L·h）时,曝气12h后,pH达到9．63,PO4^3-P和NH3-N回收率分别为46％和41％。但仅用曝气方式处理,12h后,pH值仅为8．52,PO4^3-P和NH3-N回收率分别只有20％和18％。实验结果还表明,水力停留时间（HRT）越大,pH上升速度越快,幅度越大,氮磷的回收效果就越好。     

Short-term impact of olive mill wastewater (OMWW) applications on the physico-chemical and microbiological soil properties of an olive grove in Argentina

The purpose of this work was to investigate the effects of spreading olive oil mill wastewater (OMWW) on soil biochemical parameters and olive production in an organically managed olive orchard. The experiment was carried out with three different doses of OMWW (80, 160 and 500 m³ ha^?1) and a control (untreated soil). Three samplings were done at 10, 30 and 90 days after the administration of the byproduct. OMWW application differentially modified the biochemical properties of the soil analyzed. Organic matter, organic carbon, total nitrogen and extractable phosphorus soil contents increased proportionally with each increasing dose. The values of these parameters decreased gradually with time. Total microbial activity was altered and the OMWW 500 m³ ha^?1 treatment proved to be the most active when compared with the other applied doses. OMWW agricultural application also modified the structure of soil microbial communities, particularly affecting Gram positive and negative bacteria, while fungal biomass did not show consistent changes. Although there was a salinity increase in the treated soil, especially at the highest dose, the productive parameters analyzed (fruit and oil tree^?1) were not affected. In light of the obtained results, we consider that low dose of OMWW could be considered an alternative farming practice for semiarid regions.     

Solid state fermentation of olive mill residues by wood- and dung-dwelling Agaricomycetes: Effects on peroxidase production,biomass development and phenol phytotoxicity

The in vivo conversion of dry olive mill residue (DOR) by wood- and dung-dwelling fungi − Auricularia auricula-judae, Bjerkandera adusta and Coprinellus radians − increases peroxidase secretion up to 3.2–3.5-fold (∼1.3, 3.5 and 7.0 U g⁻¹ DOR for dye-decolorizing peroxidase, manganese peroxidase and aromatic peroxygenases, respectively). The incubation of DOR with these fungi produced a sharp decrease in total phenolic content (100% within 4 wk), a reduction in phytotoxicity as well as a certain degree of plant growth caused by the stimulating effect of fungal-treated DOR. These findings correlate with a characteristic shift in the fragmentation pattern of water-soluble aromatics (detected at 280 nm) from low (0.2, 1.5 and 2.2 kDa, respectively) to high molecular mass (35 to >200 kDa), which demonstrates the presence of a polymerization process. Phenol-rich agricultural residues are a useful tool for enzyme expression and production studies of peroxidase-producing Agaricomycetes which could make DOR a valuable organic fertilizer.     

高级氧化技术在含酚废水处理中的应用

合理高效地处理含酚废水是工业废水处理的主要任务之一。重点介绍了高级氧化技术 ,如超声波氧化、超临界水氧化、湿式氧化和光催化氧化等在含酚废水处理中的研究近况和应用前景 ,探讨了各种技术的应用和发展趋势     

Fenton氧化法深度处理甲醛废水

采用Fenton氧化法深度处理经生化降解后的甲醛废水,结果表明,Fenton氧化法深度处理甲醛废水是可行的,在合适的反应条件下,降解初始COD为150 mg/L左右的甲醛废水,COD去除率达30%以上;Fe2+与H2O2的投加比例、投加量及投加方式、反应温度、pH、反应时间对处理效果都有不同程度的影响。     

Fenton氧化法深度处理纤维素乙醇废水

采用Fenton氧化法深度处理经生化降解后的纤维素乙醇废水,考察了初始pH值、Fe2+与H2O2的投加比例（物质的量之比）、H2O2投加量与COD的比例（质量之比）以及反应时间对COD和浊度去除的影响,并通过正交实验确定了反应的最佳条件。研究表明：初始pH值、Fe2+/H2O2、H2O2/COD以及反应时间对深度处理效果有不同程度的影响;在初始pH值为3.0、Fe2+/H2O2为2：3、H2O2/COD为2.8、反应时间为3 h的最佳反应条件下,出水COD为45~56 mg·L-1,浊度为2~3 NTU,达到了纤维素乙醇废水的排放标准。     

Fenton组合工艺处理焦化厂生化出水的应用研究

比较了Fenton氧化、Fenton氧化+活性炭及Fenton氧化+生物活性炭工艺对焦化厂生化出水的处理效果.结果表明,Fe2+、H2O2的投加量分别为56、27.2 mg/L时,Fenton氧化工艺对水样的UV254、颜色度(VIS380)、COD和总氰均有较好的去除效果;Fenton氧化+活性炭工艺在有效去除UV254、VIS380、COD和总氰的同时,能强化活性炭的吸附效果,并能显著提高水样的生化性能;Fenton氧化+生物活性炭工艺能有效去除UVM254,VIS380、COD与总氰,使出水达到<污水综合排放标准>(GB 8978-1996)一级标准.     

阳极氧化联合电-Fenton氧化深度处理垃圾渗滤液

采用多孔碳素阴极、Ti/SnO2-Sb2O5-IrO2阳极构建电化学氧化系统用于渗滤液的深度处理。研究结果表明,所构建的电化学氧化系统通过阳极氧化和电-Fenton氧化2种机制降解有机污染物;处理过程中阴极表面形成的沉淀物对TOC和COD的衰减也产生了影响。在阴极电位为-1.0 V、Fe2+ 初始浓度为0.5 mmol/L的条件下,电化学处理120 min获得了58% 的TOC去除;处理480 min COD去除率为55%,NH3-N去除率为99%,TN去除率为60%,色度几乎被完全去除。GC-MS分析结果表明,渗滤液中以腐殖质类物质为主的有机化合物被降解为分子量相对较小的有机物,直至完全矿化。联合阳极氧化和电-Fenton氧化机制的电化学处理方法为垃圾渗滤液深度处理提供了新的选择。     

Oxidative treatment of simulated dyehouse effluent by uv and near-UV light assisted Fenton's reagent

UV/Fenton, near-UV-visible/Fenton, dark Fenton, and H₂O₂/UV reactions have been used to treat simulated dyehouse effluents representing wastewater from the textile dyeing and rinsing process. Experiments were carried out in a lab - scale photochemical reactor using concentrations of 0.5–25 mM H₂O₂, 0.04-0.5 mM Fe²⁺-ion and different dilutions of textile wastewater. To assess the extent of mineralization, decolourization kinetics and the effect of different fight sources on treatment efficiency, DOC, optical density at 254 nm and 600 nm wavelength and residual H₂O₂ concentrations were measured during the course of the advanced oxidation reactions. Comparative evaluation of the obtained results revealed that the decolourization rate increased with applied H₂O₂ and Fe²⁺-ion dose as well as the strength of the synthetic textile wastewater. The best results were obtained by the near - UV/visible/Fenton process with a decolourization rate constant of 1.57 min⁻¹, a UV_254nm reduction of 97% and a DOC removal of 41% at relatively low doses of the H₂O₂ oxidant and Fe²⁺-ion catalyst within 60 min treatment time.     

电催化氧化法处理染料废水的影响因素及动力学

以钛涂膜极板为阳极、石墨极板为阴极、Fe2O3/γ-Al2O3为多相催化剂,构建电-多相催化氧化体系,研究了该体系对酸性大红模拟染料废水中COD的去除效果及其影响因素,优化了实验条件,并初步探讨了COD的降解机理。结果表明,在槽电压20 V,pH 4,曝气量0.24 m3/h,极板间距3 cm的条件下,COD的去除率最高,达到64.5%;COD的降解近似符合一级动力学方程:ln(C0/C)=0.0034t+0.719。在电-多相催化氧化体系中,废水中的有机物被直接矿化或降解为小分子有机物。     

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.