Micellar enhanced ultrafiltration process for the treatment of olive mill wastewater

Olive mill wastewater (OMW) is an important environmental pollution problem, especially in the Mediterranean, which is the main olive oil production region worldwide. Environmental impact of OMW is related to its high organic load and particularly to the phytotoxic and antibacterial action of its phenolic content. In fact, polyphenols are known as powerful antioxidants with interesting nutritional and pharmaceutical properties. In the present work, the efficiency of OMW Micellar Enhanced Ultrafiltration (MEUF) treatment for removal and concentration of polyphenols was investigated, using an anionic surfactant (Sodium Dodecyl Sulfate salt, SDS) and a hydrophobic poly(vinyldene fluoride) (PVDF) membrane. The effects of the process experimental conditions on the permeate flux were investigated, and the secondary membrane resistance created by SDS molecules was evaluated. The initial fluxes of OMW processing by MEUF using SDS were 25.7 and 44.5 l/m² h under transmembrane pressures of 3.5 and 4.5 bar, respectively. The rejection rate of polyphenols without using any surfactant ranged from 5 to 28%, whereas, it reached 74% when SDS was used under optimum pH (pH 2). The MEUF provides a slightly colored permeate (about 88% less dark), which requires clearly less chemical oxygen demand (COD) for its oxidation (4.33% of the initial COD). These results showed that MEUF process can efficiently be applied to the treatment of OMW and for the concentration and recovery of polyphenols.     

Impacts of operating conditions on reverse osmosis performance of pretreated olive mill wastewater

Management of the effluent from the olive oil industry is of capital importance nowadays, especially in the Mediterranean countries. Most of the scarce existing studies concerning olive mill wastewater (OMW) treatment by means of membrane processes not only do fix their aims simply on achieving irrigation standards, but lack suitable pretreatments against deleterious fouling issues. With the target of achieving the parametric requirements for public waterways discharge or even for reuse in the production process, a bench-scale study was undertaken to evaluate the feasibility of a thin-film composite reverse osmosis (RO) membrane (polyamide/polysulfone) for the purification of OMW. Previously, OMW was pretreated by means of chemical oxidation based on Fenton’s reagent, flocculation-sedimentation and biosorption through olive stones. Impacts of the main operating parameters on permeate flux and pollutants rejection of the RO process, as well as fouling on the membrane surface, were examined for removing the significant ionic concentration and remaining organic matter load of the pretreated OMW. Combining operating parameters adequately in a semibatch operating regime ensured high and sustainable permeate flux, yielding over 99.4% and 98.5% removal efficiencies for the chemical oxygen demand and ionic content respectively, as well as complete rejection of phenols, iron and suspended solids.     

荆门市竹皮河流域水环境综合治理之生态修复工程设计

竹皮河为季节性雨源型城市河流,存在污水直排、底泥淤积、季节性干涸等诸多水环境问题,导致其水质恶化严重,水生态系统受损,自净能力较弱。为恢复竹皮河生态系统多样性,提升水体自净能力,实现水质长效保持,在控源截污的基础上,采用人工湿地、原位微生物修复、生态砾石河床、水生植物恢复等多种生态治理技术集成,实施河道生态补水、生态净化、生态修复三大工程,重建生态系统多样性,实现水质自然净化。通过流域综合治理,竹皮河城区段下游水体水质逐步达到地表Ⅳ类水标准。工程设计为雨源型城市河流的生态治理提供了参考。     

Effects of pulp and paper mill effluents on the microplankton and microbial self-purification capabilities of the Biobío River, Chile

Most studies focus on the ecotoxicity of pulp and paper mill effluents, rather than on how they affect the physicochemical and biological structure and the intrinsic ecological capabilities of the receiving watercourses. We investigated the impact of such effluents on the water quality, microplankton system and microbial self-purification capacity (degradation of polymeric organic compounds via extracellular enzymes) of the Biobío River in Chile. The physicochemical impact on the water quality was indicated by raised conductivity, by the pollution of the water body with nitrate, nitrite and soluble reactive phosphorus, by the appearance of tannin and lignin, and by the steady accumulation of inorganic and organic suspended matter (SPM) along the river. From the biological structure of the microplankton system, very low and declining concentrations of chlorophyll a and heterotrophic flagellate densities were determined. The pulp and paper mill effluents introduced high bacterial abundances and biomass concentrations into the river water. This reflects the effective use made of the abundantly available inorganic and organic nutrients within this industrial and municipal process water by bacteria adapted to these extreme environments, additionally supported by concomitant low grazing pressure derivable from low heterotrophic flagellate abundances. Indeed, in one section of the river affected by a pulp mill, the plant was found to significantly contribute to the self-cleaning capacity of the river. However, this elevated degradation capacity was not enough to compensate for the additionally discharged organic material which, together with the toxic effects of the paper plant effluents, significantly interferes with the ecological status of the Biobío River.     

Effects of anthropogenic inputs on the organic quality of urbanized streams

Due to arid conditions, population growth, and anthropogenic impacts from agricultural and urban development, wastewater effluent makes up an increasingly large percentage of surface water supplies promoting concerns about the potential ecological and human health effects associated with the organic quality of surface waters receiving treated wastewater discharge. Anthropogenic inputs alter the quality and quantity of organic carbon and also affect the ability of aquatic ecosystems to retain or transform carbon and other nutrients. In this paper, we use pyrolysis-GC/MS (Py-GC/MS) as a tool to examine whether the dissolved organic carbon (DOC) in suburban streams influenced by anthropogenic inputs displays an organic signature that is structurally different from natural organic material (NOM). Py-GC/MS was not only able to differentiate among stream sites that received discharge from upstream wastewater treatment plants and those that did not, but also distinguished stream sites influenced significantly by storm water. Distinct organic signatures were evident in stream waters with upstream wastewater treatment plant discharges regardless of the distance from effluent discharge, indicative of the persistent nature of effluent-derived organic material (EfOM). The pyrolysis fragments of 3-methyl-pyridine, 2-methyl-pyridine, pyrrole, and acetamide were identified as indicators of EfOM, supporting previous research that has suggested that protein and aminosugar derivitives are possible wastewater markers. Furthermore, pyrolysis fragments associated with soil polycarboxylic acids correlated highly with stream sites having the least anthropogenic influences.     

Characterization and lime treatment of olive mill wastewater

Seventeen olive mill wastewater (OMW) samples were characterized. For characterization of the samples, amount of total, fixed, volatile, suspended, volatile-suspended solids, COD, oil-grease, polyphenol, volatile phenol, nitrogen and reducing sugar were determined. Effects of lime treatment on the waste samples were investigated. Reduction of contents of the samples treated with the lime was described. The effect of the addition of lime on an artificial phenolic mixture was also examined.     

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.     

Anaerobic digestion of olive mill wastewaters in biofilm reactors packed with granular activated carbon and "Manville" silica beads

Anaerobic digestion is one of the most promising technologies for disposing olive mill wastewaters (OMWs). The process is generally carried out in the conventional contact bioreactors, which however are often unable to efficiently remove OMW phenolic compounds, that therefore occur in the effluents. The possibility of mitigating this problem by employing an anaerobic OMW-digesting microbial consortium passively immobilized in column reactors packed with granular activated carbon (GAC) or "Manville" silica beads (SB) was here investigated. Under batch conditions, both GAC- and SB-packed-bed biofilm reactors exhibited OMW COD and phenolic compound removal efficiencies markedly higher (from 60% to 250%) than those attained in a parallel anaerobic dispersed growth reactor developed with the same inoculum; GAC-reactor exhibited COD and phenolic compound depletion yields higher by 62% and 78%, respectively, than those achieved with the identically configured SB-biofilm reactor. Both biofilm reactors also mediated an extensive OMW remediation under continuous conditions, where GAC-reactor was much more effective than the corresponding SB-one, and showed a tolerance to high and variable organic loads along with a volumetric productivity in terms of COD and phenolic compound removal significantly higher than those averagely displayed by most of the conventional and packed-bed laboratory-scale reactors previously proposed for the OMW digestion.     

The application of solar distillation technique as a mean for olive mill wastewater management

The present study was conducted on a pilot scale level using a solar still unit to separate olive mill wastewater (OMW) into condensate and solid residue. The prevailing conditions inside the solar still, rates of distillation and a number of quality parameters for condensate [pH, electrical conductivity (EC), turbidity, chemical oxygen demand (COD), total organic carbon (TOC), total nitrogen (TN) and total‐phenols] were evaluated to assess the system performance. The solid residue was evaluated as well for its utility as a potential biofuel. The condensate is acidic (pH 3.8), colourless, transparent and free of suspended solids. The turbidity and EC were reduced in the condensate by 100 and 99%, respectively, while the loads of COD, TOC, TN and T‐phenols were reduced by 90, 98, 99.9 and 99.96%, respectively. Almost 0.04% of initial total phenols found in OMW were recovered in the condensate. High calorific value (23.5 kJ/g) and combustible portion (84%) of solid residue suggests its applicability as a potential biofuel     

Xanthomonas campestris strain selection for xanthan production from olive mill wastewaters

Four Xanthomonas campestris strains were tested in olive mill wastewaters (OMW) for xanthan production. Differences among strains were found in the range of tolerance to OMW concentration and xanthan amount obtained. X. campestris NRRL B-1459 S4LII was chosen by its capability for xanthan production from 50-60% OMW as the sole nutrient source.     

Treatment of olive oil mill wastewater by combined process electro-Fenton reaction and anaerobic digestion

In this work, we investigated an integrated technology for the treatment of the recalcitrant contaminants of olive mill wastewaters (OMW), allowing water recovery and reuse for agricultural purposes. The method involves an electrochemical pre-treatment step of the wastewater using the electro-Fenton reaction followed by an anaerobic bio-treatment. The electro-Fenton process removed 65.8% of the total polyphenolic compounds and subsequently decreased the OMW toxicity from 100% to 66.9%, which resulted in improving the performance of the anaerobic digestion. A continuous lab-scale methanogenic reactor was operated at a loading rate of 10 g chemical oxygen demand (COD)l(-1) d(-1) without any apparent toxicity. Furthermore, in the combined process, a high overall reduction in COD, suspended solids, polyphenols and lipid content was achieved by the two successive stages. This result opens promising perspectives since its conception as a fast and cheap pre-treatment prior to conventional anaerobic post-treatment. The use of electro-coagulation as post-treatment technology completely detoxified the anaerobic effluent and removed its toxic compounds.     

Effect of Fenton's oxidation on the particle size distribution of organic carbon in olive mill wastewater

The study evaluated the effect of Fenton's oxidation on the particle size distribution (PSD) of significant parameters reflecting the organic carbon content of olive oil mill wastewater (OMW). The organic carbon content of the studied OMW was characterized by a COD level of around 40,000 mg/L, with 13,500 mg/L of TOC and 1670 mg/L of total phenols. The corresponding antioxidant activity (AOA) was determined as 33,400 mg/L. PSD of the selected organic carbon parameters was investigated using a sequential filtration/ultrafiltration procedure. COD fractionation based on PSD revealed two major components, a soluble fraction below 2 nm and a particulate fraction above 1600 nm representing 49% and 20% of the total COD, respectively. The remaining COD was distributed in the colloidal and supracolloidal zones. The PSD of TOC, total phenols and AOA exhibited similar profiles with peaks at the two ends of the studied size range. Overall COD removals achieved via Fenton's oxidation both at pH = 3.0 and pH = 4.6 (the original pH of the OMW) remained in the range of 40-50%. As anticipated, the effect of Fenton's treatment was more pronounced in the soluble size range. Fenton's oxidation at pH = 3.0 resulted in 46% and 63% removals for total phenols and AOA, respectively. The results obtained indicated that Fenton's process could only be useful as an alternative preliminary treatment option of the required full treatment scheme that could involve a sequence of filtration, oxidation and/or biological treatment steps.     

Effect of combined physico-chemical processes on the phytotoxicity of olive mill wastewaters

A pool of laboratory experiments is planned with the aim of evaluating the possibility to reduce the phytotoxicity of olive mill wastewater (OMW) with combined physico-chemical processes (centrifugation-ozonation, centrifugation-solar photolysis, centrifugation-solar modified photoFenton, centrifugation-solar modified photoFenton-ozonation). A moderate COD removal of an OMW is reached by using ozonation or solar modified photoFenton separately or solar modified photoFenton/O(3) combined process even for prolonged treatment times. The O(3)-treated OMWs are still toxic towards algal growth (Pseudokirchneriella subcapitata) and only for dilutions equal to or higher than 1:160 a stimulation of algal growth is observed. The sole ozonation does not reduce significantly the phytotoxicity of tested OMW measured through the GI calculation of Raphanus sativus L., Cucumis sativus L. and Lactuca sativa L. A marked reduction of OMW inhibition, higher than 50%, is evidenced for 1:8 dilution OMW samples ozonated for 2h. The long-term storage of OMW associated with solar irradiation without or with Fe(III) ions under continuous aeration is less efficient than ozonation, and the combined action of the two former treatments does not significantly contribute to enhance both COD removal and germination index. Better results are obtained on seed germination and root elongation of plantlets of the three selected species, which germinated on OMW-free solidified medium and were then transferred on a solidified culture medium containing O(3)-treated OMW diluted 1:2 and 1:4. The operating costs are estimated for the solar modified photoFenton-ozonation process.     

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).     

Identification and chemical characterization of specific organic constituents of petrochemical effluents

Based on extensive GC/MS screening analyses, the molecular diversity of petrochemical effluents discharged to a river in North Rhine-Westphalia was characterised. Within a wide spectrum of organic wastewater constituents, specific compounds that might act as source indicators have been determined. This differentiation was based on (i) the individual molecular structures, (ii) the quantitative appearance of organic compounds in treated effluents and (iii) the information on their general occurrence in the technosphere and hydrosphere. Principally, site-specific indicators have been distinguished from candidates to act as general petrochemical indicators. Further on, monitoring the environmental behaviour of target organic contaminants in an aquatic system shortly after their release into the river allowed a first evaluation of the impact of the petrogenic emission in terms of the quantity and spatial distribution.The identification of petrogenic contaminants was not restricted to constituents of the effluents only, but comprised the compounds circulating in the wastewater systems within a petrochemical plant. A number of environmentally relevant and structurally specific substances that are normally eliminated by wastewater treatment facilities were identified. Insufficient wastewater treatment, careless waste handling or accidents at industrial complexes are potential sources for a single release of the pollutants.This study demonstrates the relevance of source specific organic indicators to be an important tool for comprehensive assessment of the potential impact of petrochemical activities to the contamination of an aquatic environment.     

Isotopic exchangeability as a measure of the available fraction of the human pharmaceutical carbamazepine in river sediment

Cabamazepine (CBZ), an antiepileptic pharmaceutical compound, is a pollutant of aquatic ecosystems entering via wastewater treatment plants that is considered to be persistent to degradation. An isotope exchange technique was employed using radiolabelled CBZ as a model compound, to determine the amount of isotopic exchangeability of CBZ in river sediment. The amount of isotopically exchangeable CBZ was used as an estimate of the extent of desorption hysteresis in solution from river sediment, including a treatment where the sediment was amended with black carbon. The isotopically exchangeable CBZ was measured by equilibrating ¹²C-CBZ with sediment for 0 to 28 days followed by a 24 hour equilibration with ¹⁴C-CBZ at the end of the incubation period. The isotopically exchangeable fraction of CBZ decreased over time in the sediment, particularly following amendment with black carbon. This has important implications for the fate of CBZ, which, apart from being resistant to degradation, is constantly released into aquatic ecosystems from wastewater treatment plants. This study demonstrates the availability of a relatively quick and simple alternative to batch desorption techniques for the assessment of the available fraction of organic compounds in sediments following their release into aquatic ecosystems.     

Aquatic and terrestrial invertebrate community responses to drying in chalk streams

Temporary streams are dynamic ecosystems that shift between wet and dry states and include the ‘winterbourne’ chalk streams of south England. Our understanding of temporary stream biodiversity is biased, with most research to date exploring aquatic invertebrate communities in benthic sediments during flowing phases. We surveyed the invertebrate communities of the Candover Brook chalk stream, comparing aquatic (benthic, hyporheic) and terrestrial communities in reaches with different flow permanence regimes. We used kick and Bou–Rouch sampling methods to collect aquatic invertebrates, and compared the terrestrial communities characterised by pitfall traps and ground searches and in different seasons. Although aquatic taxa richness was lower in temporary compared to perennial reaches, the total biodiversity of temporary stream channels was enhanced by contributions from both aquatic and terrestrial species, including several of conservation interest. We recommend that both aquatic and terrestrial communities should be considered in research and monitoring to characterise the biodiversity and ecological quality of temporary streams.     

Biomarker versus environmental factors: seasonal variations and modelling multixenobiotic defence (MXD) transport activity in transplanted zebra mussels

The occurrence of biomarker temporal variations linked to environmental factors makes it difficult to distinguish the specific effect of pollution. The present work aims to investigate the seasonal variations of the transport activity of the multixenobiotic defence (MXD), which is used as a biological tool for the monitoring of pollution in aquatic ecosystems. The MXD transport activity was monitored monthly from August 2001 to October 2002 in zebra mussels (Dreissena polymorpha) transplanted to three sites in the Moselle River. The 'efflux method' was used to evaluate functional activity of MXD by assessing rhodamine B efflux with or without an inhibitor (verapamil). Environmental parameters were provided by a French regulatory agency (Water Agency) that monitors river water quality. The results of a principal components analysis describe the seasonal cycle of water characteristics and demonstrate that MXD activity is subjected to significant temporal variations. These data were described with a generalised linear model that enables it to link MXD variability to the seasonal variations of environmental parameters such as temperature or levels of organic contamination. This work proposes a modelling approach and highlights that the occurrence of seasonal variations in MXD response has to be taken into account in the interpretation of in situ monitoring studies.     

Assessment of seasonal and polluting effects on the quality of river water by exploratory data analysis

22 Physico-chemical variables have been analyzed in water samples collected every three months for two and a half years from three sampling stations located along a section of 25 km of a river affected by man-made and seasonal influences. Exploratory analysis of experimental data have been carried out by box plots, ANOVA, display methods (principal component analysis) and unsupervised pattern recognition (cluster analysis) in an attempt to discriminate sources of variation of water quality. PCA has allowed the identification of a reduced number of “latent” factors with a hydrochemical meaning: mineral contents, man-made pollution and water temperature. Spatial (pollution from anthropogenic origin) and temporal (seasonal and climatic) sources of variation affecting quality and hydrochemistry of river water have been differentiated and assigned to polluting sources. An ANOVA of the rotated principal components has demonstrated that (i) mineral contents are seasonal and climate dependent, thus pointing to a natural origin for this polluting form and (ii) pollution by organic matter and nutrients originates from anthropogenic sources, mainly as municipal wastewater. The application of PCA and cluster analysis has achieved a meaningful classification of river water samples based on seasonal and spatial criteria.     

Anthropogenic contamination and risk assessment of heavy metals in stream sediments influenced by acid mine drainage from a northeast coalfield,India

The total concentrations and chemical partitioning of heavy metals in streambed sediments, collected around the Jaintia Hills coal deposit of northeast India, were studied using pollution indices and multivariate techniques to evaluate the risk and contamination levels from heavy metals and their possible origins. Results show that sediments close to mining sites have low pH (<4), high organic carbon, and contain significant amounts of Fe-oxyhydroxide phases (mainly, goethite and schwertmannite), which implies direct impact of coal mine drainage. The average concentrations of Fe, Cu, Co, Cd, Cr, and Zn exceeded the World average, and in some cases, Cd, Cu, Ni, and Cr concentrations exceeded the threshold effects level, which suggests they will be toxic to aquatic biota. Contamination factors (CF) show that the sediments are low to highly contaminated with Cd, Cu, Mn, Pb, Fe, and Zn and low to moderately contaminated with Co, Cr and Ni. The pollution load index (PLI), degree of contamination index (C _deg) and Nemerow integrated pollution index (NIPI) show that the sediments are moderately to highly contaminated, with the extent of pollution greatest nearest to the collieries. The potential ecological risk index (RI) shows low to considerable ecological risk from heavy metals in the sediments, with Cd having the high potential of risk, which also agrees with the risk assessment code (RAC). Multivariate statistical analysis suggests that the concentrations of the heavy metals in stream sediments are strongly influenced by Fe-oxyhydroxide phases and organic carbon derived from anthropogenic sources, mainly coal mining activities. Although a significant proportion of the Cd, Mn, and Ni in the sediments are partitioned into exchangeable and organic fractions, a sizable amount of metals are also found in the Fe–Mn fraction, suggesting that Fe-oxyhydroxides play a dominant role in controlling metal mobility in these stream sediments.