Evaluation of rapid methods for in-situ characterization of organic contaminant load and biodegradation rates in winery wastewater.

Rapid methods for the in-situ evaluation of the organic load have recently been developed and successfully implemented in municipal wastewater treatment systems. Their direct application to winery wastewater treatment is questionable due to substantial differences between municipal and winery wastewater. We critically evaluate the use of UV-VIS spectrometry, buffer capacity testing (BCT), and respirometry as rapid methods to determine organic load and biodegradation rates of winery wastewater. We tested three types of samples: actual and treated winery wastewater, synthetic winery wastewater, and samples from a biological batch reactor. Not surprisingly, respirometry gave a good estimation of biodegradation rates for substrate of different complexities, whereas UV-VIS and BCT did not provide a quantitative measure of the easily degradable sugars and ethanol, typically the main components of the COD in the influent. However, our results strongly suggest that UV-VIS and BCT can be used to identify and estimate the concentration of complex substrates in the influent and soluble microbial products (SMP) in biological reactors and their effluent. Furthermore, the integration of UV-VIS spectrometry, BCT, and mathematical modeling was able to differentiate between the two components of SMPs: substrate utilization associated products (UAP) and biomass associated products (BAP). Since the effluent COD in biologically treated wastewaters is composed primarily by SMPs, the quantitative information given by these techniques may be used for plant control and optimization.     

Photo-Fenton processes assisted by solar light used as preliminary step to biological treatment applied to winery wastewaters.

Winery wastewaters are difficult to treat by conventional biological processes, because they are seasonal and experience substantial flow variations. Photocatalytic advanced oxidation is a promising technology for wastewaters containing high amounts of organic matter. In this research work, solar assisted photo-Fenton processes of both heterogeneous and homogeneous phase are used in the pre-treatment of winery wastewaters. The results of these experiments have confirmed the suitability of the photo-Fenton processes, due to these treatments achieving purification levels of up to 50% (measured as total organic carbon). The intermediate effluents are treated adequately by aerobic biological treatment (activated sludge process), due to the decrease in organic matter concentration present in winery wastewaters. The possibility of a combined photo-Fenton process, based on the use of sunlight, and aerobic biological treatment (activated sludge) is suggested.     

Treatment of winery wastewater in a conventional municipal activated sludge process: five years of experience.

A full-scale wastewater treatment plant where municipal and winery wastewaters were co-treated was studied for five years. The experimental results showed that suspended solids, COD, nitrogen and phosphorous were effectively removed both during the treatment of municipal wastewater and the cotreatment of municipal and winery wastewater. The sludge production increase from 4 tons to 5.5 tons per day during the harvesting and wine making period. In any case the specific sludge production was 0.2 kgMLVSS per kgCOD(removed) despite the organic loading increasing. About 70% of the COD was removed through respiration. Also the energy demand increased from 6,000 to 7,000 kWh per day. The estimated costs for the treatment of the winery wastewater was 0.2-0.3 Euros per m3 of treated wastewater. With reference to the process efficiency, the nitrogen removal was just 20%. The co-treatment of municipal and winery wastewater in conventional activated sludge processes can be a feasible solution for the treatment of these streams at relatively low costs.     

Re-use of winery wastewaters for biological nutrient removal.

The aim of this study was to evaluate the feasibility of the re-use of the winery wastewater to enhance the biological nutrient removal (BNR) process. In batch experiments it was observed that the addition of winery wastewater mainly enhanced the nitrogen removal process because of the high denitrification potential (DNP), of about 130 mg N/g COD, of the contained substrates. This value is very similar to that obtained by using pure organic substrates such as acetate. The addition of winery wastewater did not significantly affect either phosphorus or COD removal processes. Based on the experimental results obtained, the optimum dosage to remove each mg of N-NO3 was determined, being a value of 6.7 mg COD/mg N-NO3. Because of the good properties of the winery wastewater to enhance the nitrogen removal, the viability of its continuous addition in an activated sludge pilot-scale plant for BNR was studied. Dosing the winery wastewater to the pilot plant a significant increase in the nitrogen removal was detected, from 58 to 75%. The COD removal was slightly increased, from 89 to 95%, and the phosphorus removal remained constant.     

Heavy metal removal from winery wastewater in the case of restrictive discharge regulation.

In most cases of winery effluent, the heavy metal content, especially zinc (Zn) and copper (Cu), does not meet the limits for the discharge as imposed by the most restrictive regulations at international level (0.4 mgCu/L and 1.0 mgZn/L in the Italian regulations). An alternative for the reduction of Cu and Zn is the on-site pre-treatment of wastewater at the winery in order to meet the limits for the discharge into the public sewerage. The purpose of this study is to evaluate the effectiveness of a pre-treatment based on chemical precipitation with chelating agents (TMT: 2,4,6-trimercaptotriazine), for the reduction of Cu and Zn from raw winery wastewater. The chemical precipitation was optimised at lab-scale through jar tests in order to evaluate the optimal dosages. An average dosage equal to 0.84 mL of TMT (15%) for 1 mg of Cu removed was estimated. Furthermore, the efficiency of the on-site chemical pre-treatment was investigated at pilot scale. The results confirmed the feasibility of using TMT treatment for the reduction of Cu and Zn in order to meet the limits for discharge into the sewerage. Contextually to the removal of heavy metals, the chemical pre-treatment allowed us to obtain the reduction of particulate COD and TSS. Finally, the costs for the operation and the management of the on-site pre-treatment were evaluated.     

The efficacy of ozone as a pre- and post-treatment option for UASB-treated food processing wastewaters.

The efficiency of ozone as a pre- and post-treatment to UASB treatment was investigated, followed by a study into UASB reactor performance with ozonated wastewater as substrate. Combinations of pre- and/or post-ozonation with UASB treatment gave better results than ozonation or UASB alone and COD reductions of 53.0-98.9% were achieved for treatment of canning and winery wastewaters. A UASB reactor was fed with pre-ozonated cannery wastewater for over 70 d. COD removal improved from between 58.8 and 64.4% to between 85.3 and 91.8% after pre-ozonated substrate feed commenced. Subsequent increases in organic loading rate (OLR) from 2.4 to 3.4 kgCOD m(-3) x d(-1) did not affect reactor performance. By including a final post-ozonation treatment to this UASB effluent a total COD reduction of 99.2% was achieved.     

Uses of winery and distillery effluents in agriculture: characterisation of nutrient and hazardous components.

Twenty-one samples of winery and distillery effluents were collected from different Spanish winery and distillery industries. Electrical conductivity, pH, redox potential, density, organic charge (chemical oxygen demand, biological oxygen demand, total, volatile and suspended solids, oxidisable organic C and polyphenols) and contents of plant nutrients and heavy metals were analysed. The aim of this work was to study the composition of these effluents and to find relationships which would make it possible to use easily determined parameters to estimate their composition. The winery wastewater (WW) and vinasse (V) showed an acidic pH, a high organic load and notable polyphenol, macronutrient, micronutrient and heavy metal contents. Some of these properties are not compatible with agricultural requirements; therefore, conditioning treatment of these liquid wastes is necessary to produce a safe, stable and easily manageable end product. Generally, in both effluent types, significant correlations were found between easily analysable parameters, such as suspended, volatile and total solids, pH, electrical conductivity, density and redox potential, and most of the parameters studied. The linear regression equations obtained permitted an immediate characterisation of the WW and V samples using these parameters.     

Winery and distillery wastewater treatment by anaerobic digestion.

Anaerobic digestion is widely used for wastewater treatment, especially in the food industries. Generally after the anaerobic treatment there is an aerobic post-treatment in order to return the treated water to nature. Several technologies are applied for winery wastewater treatment. They are using free cells or flocs (anaerobic contact digesters, anaerobic sequencing batch reactors and anaerobic lagoons), anaerobic granules (Upflow Anaerobic Sludge Blanket--UASB), or biofilms on fixed support (anaerobic filter) or on mobile support as with the fluidised bed. Some technologies include two strategies, e.g. a sludge bed with anaerobic filter as in the hybrid digester. With winery wastewaters (as for vinasses from distilleries) the removal yield for anaerobic digestion is very high, up to 90-95% COD removal. The organic loads are between 5 and 15 kgCOD/m3 of digester/day. The biogas production is between 400 and 600 L per kg COD removed with 60 to 70% methane content. For anaerobic and aerobic post-treatment of vinasses in the Cognac region, REVICO company has 99.7% COD removal and the cost is 0.52 Euro/m3 of vinasses.     

An innovative technology based on aerobic granular biomass for treating municipal and/or industrial wastewater with low environmental impact.

The paper reports the results of an investigation carried out at lab scale to assess the effectiveness of an innovative technology (SUPERBIO) for treating municipal and/or industrial wastewater. When this technology was applied for treating municipal wastewater, the results showed that even at maximum organic load (i.e. 7 kg COD m(-3) d(-1)), the COD in the treated effluent was lower than 50 mg L(-1). In addition, both ammonia and TKN removal efficiencies resulted in higher than 87% up to an organic load of 5.7 kg COD m(-3) d(-1) corresponding to a nitrogen load of 0.8 kg TKN m(-3) d(-1). Very satisfactory process performances also resulted during tannery wastewater treatment, when a chemical oxidation step (i.e. ozonation) was inserted in the treatment cycle of SUPERBIO. In such an instance, at organic and nitrogen loadings of 3 kgCOD m(-3) d(-1) and 0.20 kg N m(-3) d(-1), COD, NH4+ -N and TSS average removals were 96, 99 and 98%, respectively. Finally, during the whole experimentation, SUPERBIO was always characterised by a very low sludge production. Such a result was ascribed mainly to the characteristics of biomass that grew in the form of very dense granules (i.e. 130 gVSS L(Biomass)(-1) allowing a biomass concentration as high as 50-60 gTSS l(bed)(-1) to be achieved.     

Odorous compounds treatment of winery and distillery effluents during natural evaporation in ponds.

During treatment of winery and distillery wastewater by natural evaporation in ponds, formation of malodorous compounds induces harmful olfactory effects. In this work, we studied the origin of malodorous compounds and methods to prevent and treat odours. The formation of volatile fatty acids (VFA) from pure substrates (glycerol, lactic and tartaric acids, ethanol) and complex media (winery and distillery wastewater) was studied. Various anaerobic bacteria ferment the glycerol and produce butyric or propionic acid. Valeric and caproic acids were observed at lower concentrations than butyric and propionic acids, but their malodorous intensities were higher. Microflora produce butyric, valeric, caproic, heptanoic and octanoic acids from ethanol, the main component of winery wastewater. When nitrate (an electron acceptor) is added, catabolism leads to an anaerobic respiration phenomenon (denitrification). The organic compounds are oxidised to CO2 and the nitrate is reduced to N2 (odourless compounds), without VFA formation. The preventive treatment of odours by nitrate addition was tested on an industrial scale in winery and distillery ponds. Furthermore, the study took the effect of nitrate on VFA degradation into consideration. The results make it possible to consider using nitrate for the curative treatment of pond odours.     

Microbiological characterization of winery effluents: an inventory of the sites for different treatment systems.

In a more and more regulated and socially pressured environment, the durable management of winery effluents must take into account their characteristics and their potential impact on their natural setting. The object of this exploratory study is to establish an inventory of the microbiological composition of winery effluents coming from different treatment systems. We have observed that winery effluents are charged with micro-organisms, by a factor that ranges from 10(5) to 10(8) UFC/ml, and that the level of "microbiological pollution" is independent of the type of system. The composition of the flora is closely tied to the time of year and therefore to winery activities, so certain micro-organisms will be favoured in certain periods and others will have a tendency to decrease. We have seen that from one year to another our observations remain identical; the flora equilibrium therefore occurs systematically and naturally. Faecal germs are found in very small quantities in winery effluent treatment systems. They represent minor sanitary risks. Good correlations were observed between some micro-organisms and some physical-chemical parameters (COD). It is, however, difficult to use these "easy-to-measure" parameters as reliable markers of certain microbial populations.     

Possibilities of reduction of recipient loading of tannery wastewater in Slovenia

The leather industry is well known as a high consumer of water (30 to 80 m³ for 1 ton of processed raw skins). At the same time this industry is known for the: high specific pollution of wastewater. The main characteristics of tannery wastewater are: high salinity, high organic loading (COD, BOD₅), high content of ammonia and organic nitrogen. and presence of specific pollutants (sulphide, chromium).The largest Slovenian tannery (IUV Vrhnika) processing 40 to 50 t of pig skins daily has a good system of physico-chemical pre-treatment of their wastewater (coagulation and flocculation with AI-sulfate and anionic polyelectrolyte). In pre-treatment, about 60% of organic substances are removed (COD and BOD₅) and above 95% of sulfide and chromium. Concerning Siovenian regulations and taking into consideration the fact that this tannery is located on the relatively small and slowly running river Ljubljanica such pretreatment is not sufficient. The company would like to supplement pre-treatment with biological treatment.Laboratory and pilot scale feasibility experiments including conventional biological treatment with activated sludge and combined anaerobic-anoxic-aerobic treatment with fixed biomass using mechanical pretreated wastewater and pretreated wastewater with flotation were performed. It became clear that effective biological treatment requires long retention times (several days) for applicable effluent.     

A study on ruthenium-based catalysts for pharmaceutical wastewater treatment

Ruthenium-based catalysts were prepared by a saturation-dip method. Their catalytic activity was evaluated by a catalytic wet oxidation (CWO) process. The ruthenium-based catalysts were used to purify organic pharmaceutical wastewater with high concentration pyridine and pyridine derivatives that have high chemical oxygen demand (COD). In the CWO process, organic pharmaceutical wastewater was continuously pumped into fixed-bed reactors filled with Ru-based catalysts, while the organic components in wastewater were catalytically degraded by oxygen at high temperatures and pressures (temperature, 170-300 degrees C; pressure, 1.0-10 MPa). The experimental results showed that the prepared catalysts could effectively purify pharmaceutical wastewater with high concentration organic components, which are difficult to degrade biochemically, and that the removal rates of both COD and total nitrogen were over 99%.     

Ammonia recovery from anaerobically digested cattle manure by steam stripping.

Ammonia recovery from anaerobically digested cattle manure effluents through steam stripping was studied at a stripping tower temperature of 98-99 degrees C and a steam-water ratio approximately 56-72 g/L. The digested manure effluents were first treated by microfiltration and then the permeate was used as feed in steam stripping. The stripping performance was evaluated under different feed pH values, ammonia concentrations and temperatures. The increase of the initial feed pH does not significantly improve ammonia stripping efficiency due to the fact that the stripped effluent pH is increased during steam stripping. This suggests that steam stripping of anaerobically digested manure effluents for ammonia recovery may not need pre-raised pH. In contrast, the pH value of the synthetic ammonia wastewater containing NH4Cl dramatically decreases after steam stripping. Increasing the feed temperature slightly improves ammonia stripping efficiency, but reduces the concentration of the recovered ammonia in the condensate due to an increased condensate volume at a higher feed temperature. Therefore, the feed temperature should be controlled at an optimum point that can compromise the condensate ammonia concentration and the ammonia stripping efficiency. Experimental results indicate that recovery of ammonia from anaerobically digested cattle manure effluents as NH4OH is technically feasible.     

Production integrated treatment of textile wastewater by closing raw material cycles.

A method for the in-house treatment of partial wastewater flows and the recycling of treated process water into the textile finishing process was developed in order to recycle effluents from textile finishing industry and feed them back into the production process. The method is based on a two-stage biological anaerobic-aerobic process to split colouring wastewater agents and to degrade organic substances contained in the water as well as a chemical stage to remove the remaining color of the water with the help of ozone. In the framework of a research and development project a demonstration plant for a treatment capacity of 1440 m3 per working day was installed and started in a textile finishing company. At the plant, a wastewater flow and a recycling flow are treated separately in two different treatment lanes. Approximately 40% of the total wastewater flows, i.e. 576 m3/d are treated in the wastewater lane, and a maximum of 60% of total wastewater, i.e. 864 m3/d are treated in the recycling lane. Thanks to the preliminary treatment of wastewater flows, which are discharged into the municipal sewage works, a reduction of average COD levels in the sewage works effluents could be achieved.     

Winery wastewater treatment by constructed wetlands and the use of treated wastewater for cash crop production.

A 45 m long, 4 m wide and 1 m deep wetland was constructed at Goudini in 2002 to treat distillery and winery effluent. After the plants were fully established, the wastewater with an average chemical oxygen demand (COD) of 14,000 mg/l was introduced to the wetland system at a rate of 4,050 litres per day. After treatment, wastewater at the outlet had an average COD of 500 mg/l, indicating more than 90% COD removal. After treatment, the wastewater was used to irrigate cash crops as part of poverty alleviation for farm workers. The experiment consisted of four treatment: clean irrigation water with fertilizer applied (B1); clean irrigation water without fertilizer applied (B2); wastewater irrigation with fertilizer applied (B3); and wastewater irrigation without fertilizer applied (B4). These were replicated seven times. Cabbage was cultivated as a cash crop. The results indicated that cabbage could be irrigated with winery wastewater treated by wetlands. The study found that there was significant difference between treatments that were fertilized compared with those that were not fertilized. The results indicated that wastewater irrigation improved the nutritional status of the soil.     

Treatment of winery wastewater in a full-scale fixed bed biofilm reactor.

The treatment of winery wastewater was performed at full-scale applying a two-stage fixed bed biofilm reactor (FBBR) system for the discharge in the sewerage. The results of the first year of operation at the full-scale plant are presented. Values of removed organic loads and effluent concentrations were interpreted on the basis of the COD fractionation of influent wastewater assessed through respirometric tests. The average removal efficiency of total COD was 91 %. It was not possible to reach an higher efficiency because of the unbiodegradable soluble fraction of COD (about 10% of total COD on average during the whole year), that cannot be removed by biological process or settling. Due to the high empty space offered by the plastic carriers, FBBRs did not require backwashing during the seasonal operationing period of the plant (September-March). In comparison with other treatment systems the FBBR configuration allows one to ensure a simple management, to obtain high efficiency also in the case of higher fluctuations of flow and loads and to guarantee a good settleability of the sludge, without bulking problems.     

Application of Activated Sludge Model No. 1 to biological treatment of pure winery effluents: case studies.

The practical applicability of computer simulation of aerobic biological treatment systems for winery effluents was investigated to enhance traditional on-site evaluation of new processes. As there is no existing modelling tool for pure winery effluent, a model widely used for municipal activated sludge (ASM1) was used. The calibration and validation steps were performed on extended on-site data. The global soluble COD, DO and OUR were properly reproduced. Possible causes for the remaining discrepancies between measured and simulated data were identified and suggestions for improvement directions were made to adapt ASM1 to winery effluents. The calibrated model was then used to simulate scenarios to evaluate the plant behaviour for different operation or design. In combination with on-site observations, it allowed us to establish useful and justified improvement suggestions for aeration tank and aeration device design as well as feed, draw and aeration operation.     

Photocatalytical polishing of paper-mill effluents.

Photocatalytic oxidation (PCO) is a promising technology for purification of biological pretreated wastewater or destruction of non-biodegradable compounds. For this reason PCO has been investigated as a last step of purification of biologically pre-treated paper-mill effluents. The influence of the parameters pH, TiO2-modification, TiO2-concentration, catalyst re-use, concentration of substances to be oxidised (wastewater quality) has been determined. The TOC of the biologically pretreated wasterwater was up to 55 mg L(-1). This wastewater was treated with a previously presented aerated cascade photoreactor which was modified for batch experiments. A high specific oxidation rate of up to 0.76 g TOC m(-2) h(-1) as well as a complete TOC mineralization has been achieved after the optimisation of the process parameters. The complete destruction of recalcitrant compounds will offer the opportunity to reuse the wastewater in the production process. The increase of the BOD5/TOC ratio after a short irradiation period indicates the transformation of recalcitrant organic compounds to better biodegradable intermediates. The use of PCO as a pre-treatment step for the enhancement of the biodegradability of wastewater, containing recalcitrant or inhibitory compounds is an alternative to a long and energy-intensive total pollutant mineralization.     

Removal of contaminants and pathogens from secondary effluents using intermittent sand filters

Intermittent infiltration percolation of wastewater through unsaturated sand bed is an extensive treatment technique aimed at eliminating organic matter, oxidizing ammonium and removing pathogens. The main purpose of this study was to determine the depuration efficiencies of a sand filter to remove contaminants from secondary wastewater effluents. Elimination of pathogenic bacteria (total and faecal coliforms, streptococci) and their relationship with the filter depth were investigated. Results showed a high capacity of infiltration percolation process to treat secondary effluents. Total elimination of suspended solids was obtained. Mean removal rate of BOD(5) and COD was more than 97 and more than 81%, respectively. Other water quality parameters such as NH(4)-N, TKN and PO(4)-P showed significant reduction except NO(3)-N which increased significantly in the filtered water. Efficiency of pathogenic bacteria removal was shown to mainly depend on the filter depth. Average reductions of 2.35 log total coliforms, 2.47 log faecal coliforms and 2.11 log faecal streptococci were obtained. The experimental study has shown the influence of the temperature on the output purification of infiltration percolation process.