Recovery and concentration of polyphenols from olive mill wastewaters by integrated membrane system

The purpose of this work was to analyse the potentialities of an integrated membrane system for the recovery, purification and concentration of polyphenols from olive mill wastewater (OMW). The proposed system included some well-known membrane operations such as microfiltration (MF) and nanofiltration (NF), as well as others not yet investigated for this specific application, such as osmotic distillation (OD) and vacuum membrane distillation (VMD).The OMW was directly submitted to a MF operation without preliminary centrifugation. This step allowed to achieve a 91% and 26% reduction of suspended solids and total organic carbon (TOC), respectively. Moreover, 78% of the initial content of polyphenols was recovered in the permeate stream.The MF permeate was then submitted to a NF treatment. Almost all polyphenols were recovered in the produced permeate solution, while TOC was reduced from 15 g/L to 5.6 g/L.A concentrated solution enriched in polyphenols was obtained by treating the NF permeate by OD. In particular, a solution containing about 0.5 g/L of free low molecular weight polyphenols, with hydroxytyrosol representing 56% of the total, was produced by using a calcium chloride dihydrate solution as brine. The obtained solution is of interest for preparing formulations to be used in food, cosmetic and pharmaceutical industry. Besides the OD process, VMD was applied as another way for concentrating the NF permeate and the performance of both processes was compared in terms of evaporation fluxes.     

Comparison of the performance of UF membranes in olive mill wastewaters treatment

Olives are known to contain an appreciate amount of phenols with good antioxidant properties which are lost in large part in olive mill wastewaters (OMWs) during olive oil production.Membrane technology offers several advantages (low energy consumption, no additive requirements, no phase change) over traditional techniques to recover phenolic compounds from OMWs.The aim of this work was to evaluate the performance of different UF membranes in the treatment of OMWs finalized to the recovery of polyphenols. For this purpose, OMWs were processed, in selected operating conditions, with four flat-sheet UF membranes characterized by different molecular weight cut-off (MWCO) (4, 5 and 10 kDa) and polymeric material (regenerated cellulose and polyethersulphone). Permeate fluxes, fouling index and retention coefficients towards phenolic compounds, total antioxidant activity (TAA) and total organic carbon (TOC) were evaluated.Regenerated cellulose membranes exhibited lower rejections towards phenolic compounds, higher permeate fluxes and lower fouling index if compared with PES membranes.     

Strategies for lipids and phenolics degradation in the anaerobic treatment of olive mill wastewater

Strategies are proposed for the anaerobic treatment of lipid and phenolic-rich effluents, specifically the raw olive mill wastewater (OMW). Two reactors were operated under OMW influent concentrations from 5 to 48 g COD L⁻¹ and Hydraulic Retention Time between 10 and 5 days. An intermittent feeding was applied whenever the reactors showed a severe decay in the methane yield. This strategy improved the mineralization of oleate and palmitate, which were the main accumulated Long-Chain Fatty Acids (LCFA), and also promoted the removal of resilient phenolic compounds, reaching remarkable removal efficiencies of 60% and 81% for two parallel reactors at the end of a feed-less period. A maximum biogas production of 1.4 m³ m⁻³ d⁻¹ at an Organic Loading Rate of 4.8 kg COD m⁻³ d⁻¹ was obtained. Patterns of individual LCFA oxidation during the OMW anaerobic digestion are presented and discussed for the first time. The supplementation of a nitrogen source boosted immediately the methane yield from 21 and 18 to 76 and 93% in both reactors. The typical problems of sludge flotation and washout during the anaerobic treatment of this oily wastewater were overcome by biomass retention, according to the Inverted Anaerobic Sludge Blanket (IASB) reactor concepts. This work demonstrates that it is possible to avoid a previous detoxification step by implementing adequate operational strategies to the anaerobic treatment of OMW.     

Phenolic removal in a model olive oil mill wastewater using Pleurotus ostreatus in bioreactor cultures and biological evaluation of the process

Pleurotus ostreatus grown in bioreactor batch cultures in a model phenolic wastewater (diluted and sterilized olive oil mill wastewater-OMW), caused significant phenolic removal. Laccase, the sole ligninolytic enzyme detected in the growth environment, was produced during primary metabolic growth. The bioprocess was simulated with the aid of a mathematical model and the parameters of growth were determined. When the fungal biomass was increased in the reactor (during repeated batch experiments) the rate of reducing sugars consumption progressively increased, but a phenolic fraction seemed of being strongly resistant to oxidation. The toxicity of OMW against the seeds of Lepidium sativum and the marine Branchiopoda Artemia sp. was significantly decreased after biotreatment. On the contrary, the toxicity against the freshwater Branchiopoda Daphnia magna was not affected by the treatment, whereas on the soil and freshwater sediments Ostracoda Heterocypris incongruens was slightly decreased. Both treated and untreated OMWs, used as water for irrigation of lettuce and tomato plants, did not significantly affect the uptake of several nutrients by the cultivated plants, but resulted in a decrease in the plant yields, which was minimized when high OMW dilutions were used. As a conclusion, P. ostreatus is able to reduce phenolic content and toxicity of sterilized OMW, in bioreactor cultures. However, high OMW dilutions should be used, and/or additional treatment should be applied before use of the OMW in the environment, e.g. as water for irrigation. Further research should be done in order to transfer this technology under industrial conditions (e.g. by using unsterilized OMW).     

Synergetic effect between photocatalytic degradation and adsorption processes on the removal of phenolic compounds from olive mill wastewater

The photocatalytic degradation of two phenolic compounds, p-coumaric acid and caffeic acid, was performed with a suspended mixture of TiO₂ and powdered activated carbon (PAC) (at pH = 3.4 and 8). Adsorption, direct photolysis and photocatalytic degradation were studied under different pH and UV light sources (sunlight vs. 365 nm UV lamps). The potential for reusing this catalyst mixture in sequential photocatalytic runs was examined as well. Quantum yields for the direct photolysis of caffeic acid under solar and artificial 365 nm light were calculated (for the first time) as 0.005 and 0.011, respectively.A higher removal rate of contaminants by either adsorption or photocatalysis was obtained at a low pH (pH 4). Furthermore, the addition of PAC increased the removal efficiency of the phenolic compounds. Fast removal of the pollutants from the solution over three sequential runs was achieved only when both TiO₂ and PAC were present. This suggests that at medium phenolic concentrations, the presence of PAC as a co-sorbent reduces surface poisoning of the TiO₂ catalyst and hence improves photocatalysis degradation of phenolic pollutants.The adsorption equilibrium of caffeic acid or p-coumaric acid on TiO₂, PAC and the combined mixture of TiO₂ and PAC follows the Langmuir isotherm model. Experiments with PAC TiO₂ mixture and olive mill wastewater (anaerobically treated and diluted by a factor of 10) showed higher removal of polyphenols than of chemical oxygen demand (COD). 87% removal of total polyphenols, compared to 58% of COD, was achieved after 24 h of exposure to 365 nm irradiation (7.6 W/m²) in the presence of a suspended mixture of TiO₂ and PAC, indicating “self-selectivity” of polyphenols.     

Solar photocatalytic thin film cascade reactor for treatment of benzoic acid containing wastewater

A solar photocatalytic cascade reactor was constructed to study the photocatalytic oxidation of benzoic acid in water under various experimental and weather conditions at HKUST. Nine stainless steel plates coated with TiO(2) catalyst were arranged in a cascade configuration in the reactor. Photolytic degradation and adsorption were confirmed to be insignificant total organic carbon (TOC) removal mechanisms. A turbulent flow pattern and, hence, improved mixing in the liquid film were achieved due to the unique cascade design of the reactor. The photoinduced consumption of oxygen during reactions was demonstrated in a sample experiment. The proposed rate equations provided good fits to 90 data points from 17 experiments. The regression results showed that the TOC removal rates averaged over 30 min intervals did not illustrate significant dependence on TOC(0) and that I(mean) was more important in affecting the photocatalytic process within the ranges of the data examined. The percentage removal of TOC in 7 l of 100 mg/l (or 100 ppm) benzoic acid solutions increased from 30% to 83% by adding 10 ml of hydrogen peroxide solution (30 wt%). Hydrogen peroxide was also shown to enhance the efficiency of the degradation process at elevated temperatures. Ortho-, meta- and para-hydroxybenzoic acids were identified by HPLC analysis as the intermediates of benzoic acid during reactions without the addition of hydrogen peroxide solutions.     

Advanced water treatment with manganese oxide for the removal of 17alpha-ethynylestradiol (EE2)

Municipal wastewater is supposed to be one of the most important sources of endocrine-disrupting compounds (EDCs) in water. Therefore, advanced treatments and cost-efficient techniques should be developed to prevent the spread of this type of pollution into the environment. In this view, experiments were conducted in which the removal of 17alpha-ethynylestradiol (EE2), a synthetic and persistent estrogen, from water was monitored in three upstream bioreactors (UBRs), filled with, respectively, sand, granulated activated carbon (GAC) and MnO(2) granules. Tap water, spiked with 15,000ngEE2/L was filtered through the reactors with a hydraulic retention time of approximately 1h. The removal of EE2 in the sand, GAC and MnO(2) reactors was, respectively, 17.3%,>99.8% and 81.7%. The removal in the GAC reactor was mainly due to adsorption. The MnO(2) reactor, however, removed significantly more EE2 than could be predicted from its adsorption capacity, probably thanks to its catalytic properties. These catalytic properties could make it a cost-efficient technique for the removal of EE2, but further research at more environmentally relevant concentrations is needed.     

Fine particle collection of an electrostatic precipitator in CO2-rich gas conditions for oxy-fuel combustion

The collection of particles in CO₂-enriched environments has long been important for the capture of CO₂ in order to clean gases via oxy-fuel combustion. We here report on the collection characteristics of fine and ultrafine particles using an electrostatic precipitator (ESP) in a CO₂-enriched atmosphere. In order to understand the characteristics of particle collection in CO₂-rich gas mixtures, the ionic properties of a CO₂-enriched atmosphere was also investigated. The electrical mobility of the ions in a CO₂-enriched atmosphere was found to be about 0.56 times that found in a conventional air atmosphere, due to the higher mass of CO₂ gas compared to that of air. The low electrical mobility of ions resulted in a low corona current under CO₂-enriched conditions. The collection efficiency of particles in a CO₂-rich atmosphere for a given power consumption was thus somewhat lower than that found in air, due to the low quantity of particle charging in CO₂-enriched air. At the same time, higher temperatures led to the higher electrical mobility of ions, which resulted in a greater collection efficiency for a given power. The presence of a negative corona also led to a greater collection efficiency of particles in an ESP than that achieved for a positive corona.     

Photoassisted reduction of metal ions and organic dye by titanium dioxide nanoparticles in aqueous solution under anoxic conditions

The photoassisted reduction of metal ions and organic dye by metal-deposited Degussa P25 TiO₂ nanoparticles was investigated. Copper and silver ions were selected as the target metal ions to modify the surface properties of TiO₂ and to enhance the photocatalytic activity of TiO₂ towards methylene blue (MB) degradation. X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) were used to characterize the crystallinity, chemical species and morphology of metal-deposited TiO₂, respectively. Results showed that the particle size of metal-deposited TiO₂ was larger than that of Degussa P25 TiO₂. Based on XRPD patterns and XPS spectra, it was observed that the addition of formate promoted the photoreduction of metal ion by lowering its oxidation number, and subsequently enhancing the photodegradation efficiency and rate of MB. The pseudo-first-order rate constant (k_obs) for MB photodegradation by Degussa P25 TiO₂ was 3.94 × 10^− 2 min^− 1 and increased by 1.4-1.7 times in k_obs with metal-deposited TiO₂ for MB photodegradation compared to simple Degussa P25 TiO₂. The increase in mass loading of metal ions significantly enhanced the photodegradation efficiency of MB; the k_obs for MB degradation increased from 3.94 × 10^− 2 min^− 1 in the absence of metal ion to 4.64-7.28 × 10^− 2 min^− 1 for Ag/TiO₂ and to 5.14-7.61 × 10^− 2 min^− 1 for Cu/TiO₂. In addition, the electrons generated from TiO₂ can effectively reduce metal ions and MB simultaneously under anoxic conditions. However, metal ions and organic dye would compete for electrons from the illuminated TiO₂.     

Preparation and application of TiO2 photocatalytic sensor for chemical oxygen demand determination in water research

In this work, a TiO(2) photocatalytic sensor was prepared and utilized into flow injection analysis (FIA) for chemical oxygen demand (COD) determination. With a positive bias potential of 0.4V (vs. Ag/AgCl) applied to the sensor and a 12-W quartz UV lamp illuminating it, photocurrent, due to the charge transfer at the interface of TiO(2) sensor and the passing solution, was recorded and its change (deltaI(Photo)) caused by the detected sample was calculated to characterize the COD value of the sample. Under the optimizing conditions, the sensor responded linearly to the COD of D-glucose solution in the range of 0.5-235 mg/L, with a linear correlation coefficient of 0.9998. Its application in artificial wastewater analysis has achieved results in good agreement with those from the conventional dichromate method; meanwhile, the process requires no hypertoxic reagents and less analysis time, suggesting that it would be another appropriate method for COD determination in water assessment.     

Dechlorination of endocrine disrupting chemicals using Mg 0/ZnCl 2 bimetallic system

In the present study, Mg⁰/ZnCl₂ bimetallic system was evaluated for its efficiency to dechlorinate endosulfan and lindane in aqueous phase. Presence of acetone in the reaction mixture played an important role by increasing the solubilities of both pesticides and thereby accelerating its mass transfer. Water acetone ratio of 2:1 and 1:1 (v/v) was found optimum for the dechlorination of endosulfan and lindane respectively. Presence of H⁺ ions in the reaction mixture (50 μl ml⁻¹ of glacial acetic acid) accelerated the degradation efficiency of 30 ppm initial concentration of endosulfan (96% removal) and lindane (98% removal) at Mg⁰/ZnCl₂ dose of 5/1 mg ml⁻¹ within 30 min of reaction. Dechlorination kinetics for endosulfan and lindane (10, 30 and 50 ppm initial concentration of each pesticide) with varying Mg⁰/ZnCl₂ doses and the time course profiles of each pesticide were well fitted into the first order dechlorination reaction. The optimum observed rate constant (k_obs’) values for endosulfan (0.2168, 0.1209 and 0.1614 min⁻¹ for 10, 30 and 50 ppm initial concentration respectively) and lindane (0.1746, 0.1968 and 0.2253 min⁻¹ for 10, 30 and 50 ppm initial concentration respectively) dechlorination were obtained when the reactions were conducted with doses of 7.5/1 mg ml⁻¹ and 5/1 mg ml⁻¹ Mg⁰/ZnCl₂ respectively. Endosulfan and lindane were completely dechlorinated into their hydrocarbon skeletons namely, Bicyclo [2,2,1] hepta 2-5 diene and Benzene respectively as revealed by GCMS analysis.     

CFD analysis of ventilation effectiveness in a public transport interchange

A study was conducted into the ventilation effectiveness of a ventilation system within a public transport interchange (PTI) in Hong Kong. A computational fluid dynamics (CFD), steady state computational model of the PTI was used to investigate and predict the typical pollutant emission pattern for buses. In Hong Kong, the displacement ventilation (DV) scheme is often employed for the PTI. The numerical simulation investigates the effectiveness of the DV system in removing pollutants from the occupied zone. An alternative model is proposed where the supply is located at the ceiling and the exhausts are located at the lower part of the columns. It was found that both systems could adequately ventilate the PTI; however, the ceiling based air supply system is able to provide improved thermal comfort and indoor air quality (IAQ).     

Phylogenetic analysis of the bacterial community in a full scale autothermal thermophilic aerobic digester (ATAD) treating mixed domestic wastewater sludge for land spread

The bacterial community associated with a full scale autothermal thermophilic aerobic digester (ATAD) treating sludge, originating from domestic wastewater and destined for land spread, was analysed using a number of molecular approaches optimised specifically for this high temperature environment. 16S rDNA genes were amplified directly from sludge with universally conserved and Bacteria-specific rDNA gene primers and a clone library constructed that corresponded to the late thermophilic stage (t = 23 h) of the ATAD process. Sequence analyses revealed various 16S rDNA gene sequence types reflective of high bacterial community diversity. Members of the bacterial community included α- and β-Proteobacteria, Actinobacteria with High G + C content and Gram-Positive bacteria with a prevalence of the Firmicutes (Low G + C) division (class Clostridia and Bacillus). Most of the ATAD clones showed affiliation with bacterial species previously isolated or detected in other elevated temperature environments, at alkaline pH, or in cellulose rich environments. Several phylotypes associated with Fe(III)- and Mn(IV)-reducing anaerobes were also detected. The presence of anaerobes was of interest in such large scale systems where sub-optimal aeration and mixing is often the norm while the presence of large amounts of capnophiles suggest the possibility of limited convection and entrapment of CO₂ within the sludge matrix during digestion. Comparative analysis with organism identified in other ATAD systems revealed significant differences based on optimised techniques. The abundance of thermophilic, alkalophilic and cellulose-degrading phylotypes suggests that these organisms are responsible for maintaining the elevated temperature at the later stages of the ATAD process.     

Internal convective heat transfer modeling: Critical review and discussion of experimentally derived correlations

Heat is transferred through building envelopes by conduction, radiation, and convection. Of these, convective heat transfer is often the weakest ‘link’ in the overall heat transfer model. While conduction and radiation heat transfer are supported by well-established analytical and numerical models, the treatment of convection is much less rigorous. Convection modeling involves solution of fluid dynamics problems in which the complexity of an enclosed space's geometry and the diversity of indoor airflow patterns require many fit-for-purpose convection correlations. These must take into account specifics of the space and of the heating ventilation and air-conditioning (HVAC) system. This paper provides an overview of the current knowledge on the modeling of convective heat transfer in load calculation and building energy simulation programs. The paper also discusses various issues related to the robustness of convection coefficient correlations, and reports on new experiments conducted to test the sensitivity of existing convection correlations. The discussed issues relate to: (1) the non-uniformity of the indoor temperature field; (2) the selection of a proper characteristic dimension; (3) the effect of adiabatic and non-adiabatic obstructions in the zone; and (4) the impact of airflow disturbance.     

Evaluation of a photocatalytic reactor membrane pilot system for the removal of pharmaceuticals and endocrine disrupting compounds from water

A photocatalytic reactor membrane pilot system, employing UV/TiO₂ photocatalysis, was evaluated for its ability to remove thirty-two pharmaceuticals, endocrine disrupting compounds, and estrogenic activity from water. Concentrations of all compounds decreased following treatment, and removal followed pseudo-first-order kinetics as a function of the amount of treatment. Twenty-nine of the targeted compounds in addition to total estrogenic activity were greater than 70% removed while only three compounds were less than 50% removed following the highest level of treatment (4.24 kW h/m³). No estrogenically active transformation products were formed during treatment. Additionally, the unit was operated in photolytic mode (UV only) and photolytic plus H₂O₂ mode (UV/H₂O₂) to determine the relative amount of energy required. Based on the electrical energy per order (EEO), the unit achieved the greatest efficiency when operated in photolytic plus H₂O₂ mode for the conditions tested.