Accepted Manuscript Title: Treatment of winery wastewater by physicochemical, biological and advanced processes: A review Author: L.A. Ioannou G.Li Puma D. Fatta-Kassinos PII: DOI: Reference:
S0304-3894(14)01027-9 http://dx.doi.org/doi:10.1016/j.jhazmat.2014.12.043 HAZMAT 16478
To appear in:
Journal of Hazardous Materials
Received date: Revised date: Accepted date:
29-10-2014 18-12-2014 22-12-2014
Please cite this article as: L.A.Ioannou, G.Li Puma, D.Fatta-Kassinos, Treatment of winery wastewater by physicochemical, biological and advanced processes: A review, Journal of Hazardous Materials http://dx.doi.org/10.1016/j.jhazmat.2014.12.043 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Treatment of winery wastewater by physicochemical, biological and advanced processes: A review L.A. Ioannoua, G. Li Pumab, D. Fatta-Kassinosa*
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Department of Civil Engineering and Environmental Engineering and Nireas-International Water Research Centre, School of Engineering,
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University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus b
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Environmental Nanocatalysis and Photoreaction Engineering, Department of Chemical Engineering, Loughborough University,
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Loughborough LE11 3TU, United Kingdom
Abstract
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Corresponding author: *Despo Fatta-Kassinos: [email protected]
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Winery wastewater is a major waste stream resulting from numerous cleaning operations that occur during the production stages of wine. The resulting effluent contains various organic and inorganic contaminants and its environmental impact is notable, mainly due to its high organic/inorganic load, the large volumes produced and its seasonal variability. Several processes for the treatment of winery wastewater are currently available, but the development of alternative treatment methods is necessary, in order to (i) maximize the efficiency and flexibility of the treatment process to meet the discharge requirements for winery effluents, and (ii) decrease both the environmental footprint, as well 1
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as the investment/operational costs of the process. This review, presents the state-of-the-art of the processes currently applied and/or tested for the treatment of winery wastewater, which were divided into five categories: i.e. physicochemical, biological, membrane filtration and separation, advanced oxidation processes, and combined biological and advanced oxidation processes. The advantages and disadvantages,
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as well as the main parameters/factors affecting the efficiency of winery wastewater treatment are discussed. Both bench- and
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pilot/industrial-scale processes have been considered for this review.
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Keywords: winery wastewater; biological processes; physicochemical processes; membranes; advanced oxidation processes
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1. Why winery wastewater requires sustainable management
Wine production, traditionally and among the population, is perceived to be an environmentally friendly process and it is widely practiced in
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many agricultural and rural regions opening onto the Mediterranean and the Atlantic seas including France, Italy, Spain, Portugal, Greece and Turkey, Central and East Europe including Germany, Hungary, Romania and Bulgaria, the New World regions including Australia, New
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Zealand, South Africa, USA, Chile and Argentina and finally China in which the production of wine is predicted to soar. However, wine production requires a considerable amount of resources such as water, energy, fertilizers and organic supplements, and produces large volumes of waste streams [1,2]. These waste streams include solid organic waste (e.g. grape marc, skins, pips, etc.), wastewater, greenhouse gases (e.g. CO2, volatile organic compounds, etc.), and packaging waste [3].
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Winery wastewater, is a major waste stream resulting from a number of activities that includes cleaning of tanks, washing of floors and equipment, rinsing of transfer lines, barrel cleaning, off wine and product losses, bottling facilities, filtration units and rainwater diverted into, or captured in the wastewater management system. The effluent produced contains various contaminants, such as ethanol, sugars,
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organic acids, phenolic compounds, etc. [4-7].
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Both the volumes and the pollution load of winery effluents vary greatly in relation to the working period (i.e. vintage, racking, bottling),
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and the kind of the wine produced (e.g. red, white, sparkling, etc.) [8,9]. It is estimated that a winery produces between 1.3 and 1.5 kg of residues per liter of wine produced, 75% of which is winery wastewater [3]. Due to the seasonal operation of wine industries unique
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problems arise for the treatment processes in terms of wastewater volume and composition [10]. As a result, treatment plants must be
[11].
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flexible to changes in the loading regime and must quickly adapt to sequences of start-ups and closedowns, and also intervals of inactivity
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The environmental impact of wastewater from the wine industry is notable (i.e. pollution of water, degradation of soil and damage to vegetation arising from wastewater disposal practices, odors and air emissions resulting from the management of wastewater) mainly due to the high organic load and the large volumes produced [12]. Each winery is unique with regard to the volume of wastewater generated (highly variable, 0.5-14 L per litre of wine produced) and the disposal practices applied [13]. Winery wastewater can cause eutrophication (nutrient enrichment) of water resources (i.e. natural streams, rivers, dams and wetlands). If high levels of biological oxygen demand (BOD) in 3
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untreated winery wastewater are allowed to flow into streams, rivers and lakes, the dissolved oxygen (DO) in the waterways may be quickly consumed, leading to the suffocation of aquatic and amphibious life [14]. In addition, application of winery effluent to soil without an appropriate monitoring programme, can alter the physicochemical properties of groundwater by affecting color, pH and electrical
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conductivity from the leaching of organic and inorganic ions [15]. The high acidity of winery wastewater can affect plant vigor by reducing
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the availability of plant nutrients (particularly phosphorous and calcium) and decreasing populations of useful microbes [16]. In addition, the
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high percentage of organic compounds and salts contained in winery effluents can cause significant inhibitory effects on plant growth, while
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the high electrical conductivity causes retardation of germination, since it makes the water uptake by seeds difficult [11]. In addition,
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numerous phenolic compounds are present in wines and winery wastewater, as a result of their extraction from the skin, the flesh and seeds of grapes. Although, phenolic compounds form a relatively small portion of the organic load of winery effluents, they can cause significant
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environmental damage if released untreated in the environment [17] since some of these compounds are toxic to human, animals and many
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microorganisms, even at relatively low concentrations [18], and they are also particularly resistant to degradation [11].
Winery effluents are in general biodegradable and the period during which the ratio BOD5/COD is higher is during the vintage period, because of the presence of molecules, such as sugars and ethanol [19]. Part of the organic load contained in the winery effluents is however, biorecalcitrant and potentially toxic to various microorganisms and plant species. The COD concentration of winery effluents ranges from 320 to 49105 mg L-1 (mean value: 11886 mg L-1), while the BOD5 ranges from 203 to 22418 mg L-1 (mean value: 6570 mg L-1). A summary of the qualitative characteristics of the effluents from a number of wineries, according to the literature, is presented in Table 1. 4
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2. Processes currently applied for the treatment of winery wastewater
Even though the main qualitative characteristics of winery wastewater are well known, it is quite difficult to establish a criterion to define in advance the pollution load, since it depends on the winemaking mode and the technologies adopted [20]. There are several options for their
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treatment, aiming to achieve not only a high degree of organic/inorganic load reduction, but also a significant reduction of suspended solids
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[21].
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The processes that are used currently for the treatment of winery wastewater are for the purpose of this review divided into five categories:
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physicochemical, biological, membrane filtration and separation, advanced oxidation processes (AOPs), and combined biological + advanced chemical processes. For each category the main findings are discussed along with the parameters used for assessing their treatment
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efficiency. The physicochemical and biological processes are already applied at industrial scale, while the advanced processes are mostly applied at smaller scales (i.e. bench and pilot scale) and detailed knowledge for their upscaling is still missing. To the authors’ knowledge
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only one industrial-scale application of an advanced chemical process for the treatment of winery effluents is currently available in the literature [22].
Figure 1 presents the number of journal publications regarding the winery wastewater treatment during the period 1995-2014. According to the literature, the treatment of winery effluents started timidly more than forty years ago, with the study of Haynes et al. [23], where a longterm activated sludge system followed by tertiary sand filter was constructed and operated at a winery in New York. As shown in Figure 1, 5
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winery wastewater treatment showed a modest increase by the middle of 2000s, followed by a much more robust upward trend since ca. 2009. It is apparent that the evolution of the number of studies related to the different treatment technologies abovementioned, is constantly increasing, with the aim to bridge the various knowledge gaps associated with (i) the increase of the treatment efficiency of each process (i.e.
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evaluation of the efficiency of the new developed and/or combined processes, upscaling of the various advanced processes, etc.), and (ii) the
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safe disposal of this effluent into the environment (i.e. assessment of the treated effluents’ toxicity and phytotoxicity, etc.).
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Various review papers are available in the scientific literature addressing selected issues regarding the production and management of winery wastewater. The review of Melamane et al. [11] summarizes the efficiency of various processes applied for the treatment of wine-distillery
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wastewater, with emphasis on anaerobic biological processes, as well as membrane bioreactors (MBRs). In this review, the use of winery
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effluents for irrigation, direct discharge on soil or in groundwater, evaporation and discharge to urban wastewater treatment plants (WWTPs) are discussed. Strong and Burgess [17] review the treatment of phenolic compound-rich wastewaters by physicochemical, aerobic biological
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systems and hybrid treatment methods and the valuable products (lignolytic enzymes such as laccase) derived from fungal treatment of winery and distillery wastewater. Andreottola et al. [24] provide an overview on the existing status and advances in the biological treatment of winery wastewater, considering both bench-, pilot- and full-scale studies. Also, the advantages and disadvantages, as well as the removal efficiency of biological processes applied for the treatment of these effluents are presented. Moreover, the review of Mosse et al. [21] describes the processes that are available for the treatment of these effluents in Australia, discussing also advantages and disadvantages of
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their use. Also, the disposal options that are mainly applied (i.e. land disposal and irrigation), as well as impacts induced to the soil by this practice (e.g. increased soil fertility, salinity, changes to the soil microbial community, etc.) are discussed.
The aim of the present paper is to provide a review on the efficiency of different processes for the treatment of winery wastewater, namely
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physicochemical, biological, membrane filtration and separation, advanced oxidation processes, and various integrated processes and
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critically discuss their main findings, regarding (i) the efficiency for the removal of both organic and inorganic loads, (ii) the economic and
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operational feasibility, (iii) effluents’ quality and potential toxicity to various microorganisms and plant species, and (iv) the possible need for further pre- or post-treatment, ensuring thus the safe disposal of the treated wastewater in the environment or for water reuse. According
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to the authors’ knowledge this is the first review paper, where an effort to include all the studies available in the literature, regarding winery
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wastewater treatment, is made.
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3. Physicochemical processes
There are various physicochemical processes that have been successfully applied for the treatment of real winery effluent, such as chemical precipitation with chelating agents [25], sedimentation with the addition of flocculants [26], coagulation/flocculation [27-29] and electrocogualation (EC) [30,31], as shown in Table 2.
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When comparing the efficiencies of the various processes, attention must be paid due to the fact that the qualitative characteristics of the initial effluents used in each study differ substantially (as shown in Tables 2, 4-6 and Table S1). From the studies discussed below, it is obvious, that the most common parameters measured in order to evaluate the efficiency of the various physicochemical processes are the
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total suspended solids (TSS), turbidity and COD removal.
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The effectiveness of a pre-treatment process based on chemical precipitation with chelating agents (i.e. trimercaptotriazine (TMT)) at a pilot
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scale, for the reduction of turbidity, as well as heavy metals (i.e. Cu and Zn) from real winery wastewater (influent COD = 3090-7438 mg L1
) was investigated by Andreotolla et al. [25]. In this study, high removals of TSS, Cu and Zn were achieved, equal to 90%, 96% and 76%,
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respectively, although the COD removal was only 9% of COD. The low COD removal occurred since 92% of winery wastewater was in
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soluble form, for which chemical precipitation is not effective. The treatment cost of the winery wastewater, taking into account the plant management, chemical doses, periodically effluent quality controls, electricity, sludge disposal and taxes for the discharge into the public
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sewerage, was estimated to be 14.6 € m-3. The pre-treatment of winery wastewater (influent COD = 1550 mg L-1) by coagulation, using a natural organic coagulant i.e. chitosan, was investigated by Rizzo et al. [28] as a feasible alternative to conventional coagulants based on metals, so as to produce a potentially reusable organic sludge. The efficiency of the coagulation was found to be high in terms of TSS (80%), turbidity (92%), and organic matter removal (73% in terms of COD). It should be noted that when coagulation reached the optimum condition (optimum dose = 20 mg L-1) in which the 8
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residual turbidity, COD, and TSS values were the lowest, no further improvements could be achieved by varying the pH (4 to 6.8). This result indicates that interparticle bridging rather than the neutralization charge and/or adsorption mechanism might be the main cause for the aggregation of particles.
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A similar and even higher efficiency on TSS (95.4%) and turbidity (92.6%) removal was also achieved by the application of
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coagulation/flocculation (experimental conditions: pH = 5 and 30 mL (5% w/v) coagulant dosage), using Ca(OH)2 and Al2(SO4)3 as a
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coagulant, respectively, as shown in the study by Braz et al. [27]. However, only a small part of COD (influent value = 31369-38391 mg L-1) was removed by this process; lower than 68%. Taking into account the inefficient removal of COD, the combination of long-term aerated
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storage (LTAS) followed by coagulation/flocculation with Ca(OH)2 was further investigated, enhancing the overall removal efficiency to
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approx. 85% for COD, 99% for TSS, and 97% for turbidity. An effective two-step sedimentation procedure with 0.1% organo-sepiolite and 0.1% sepiolite modified with crystal violet that changes the
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colloidal properties of winery effluents (influent COD = 2120-4940 mg L-1) was presented in the study of Rytwo et al. [26]. After the first step of the sedimentation procedure, the surface charge of the remaining dispersed particles was decreased by 50%, while after the second step by further 30%. In addition, almost complete TSS removal (98%) and a considerable turbidity reduction (44%) were achieved from the combined procedure, although the COD removal was low and ranged between 20-40%. According to the authors, the large differences between TSS and turbidity/COD reduction might indicate that very small dispersed particles largely made up the remaining turbidity, and the remaining COD presumably represented dissolved organic matter. 9
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Electrocoagulation (EC) was found to be an efficient process for the removal of COD (up to 42%; influent COD = 1500-17000 mg L-1) and total phosphorous (TP) (89%; influent TP = 13 mg L-1), while a moderate reduction of BOD (28%; influent BOD = 1500-2500 mg L-1) was also observed, as reported in the study of Kirzhner et al. [30]. The addition of 1 L min -1 O3 slightly enhanced the process efficiency (from 42
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to 48% COD removal), while in contrast, the addition of H2O2 had an adverse effect. In order to further enhance the removal efficiency, a
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two-stage process was applied, where in the first stage the effluent was treated by EC and its resulting flow was further purified in a second
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stage comprising by aquatic plants (i.e. salt marshes with rushes). At 1:1 dilution (with fresh water), 97.5 and 95.6% of the BOD were
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removed, after 23 days of treatment, with the floating H. umbellate and E. crassipes plants and aeration, respectively, while 98.2% of COD
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was also removed. The viability of an economic model was demonstrated for the case of 8000 m3 year-1 treatment facility (EC followed by aquatic plants) and the operating cost was calculated equal to 1.8 € m-3 of treated winery wastewater. The internal rate of return for this
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project was 29.5% and the payback time 4.0 years, suggesting thus the viability of the treatment process. In a recent study of Kara et al. [31] the treatment of winery effluents by EC using two different electrodes (Al and Fe) was investigated. The removal efficiency of the COD
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(influent COD = 25200-28640 mg L-1), color (influent value = 6500 Pt-Co) and turbidity (influent value = 2490 NTU) for Fe and Al electrodes were found to be dependent on initial pH, applied current density and operating time. When Fe electrodes were used, the removal efficiencies of COD, color, and turbidity were calculated as 46.6, 80.3, and 92.3%, respectively; while when Al electrodes were used, the removal efficiencies were found as 48.5% for COD, 97.2% for color, and 98.6% for turbidity. According to these results, the color and turbidity can be removed successfully by EC treatment from winery effluents, but the COD concentration remains too high for discharge (i.e. 10
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13810 and 15200 mg L-1 for Al and Fe electrodes, respectively) [31]. Therefore, EC process could be applied as pre- or post-treatment of other treatment technologies, such as a biological treatment that can achieve higher COD removal.
The most important parameters affecting the treatment efficiency of physicochemical processes are presented in Figure 2. Figure 3 (a)
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presents the COD removal efficiency of the abovementioned physicochemical processes. According to these studies, coagulation with
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chitosan was found to have the highest efficiency in the removal of COD (up to 73%) [28]. Based on the information presented herein, it is
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obvious that the use of alternative coagulants to chemical ones, like for examples biopolymers (e.g. chitosan) can be efficient towards the treatment of winery wastewater, while at the same time they have the advantage of being non-toxic, non-corrosive and safe to animals and
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4. Biological processes
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plants, without causing environmental pollution.
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Various biological processes for the treatment of winery wastewater have been applied including activated sludge, jet-loop reactor (JLR), sequential batch reactor (SBR), fixed bed biofilm reactor (FBBR) system, air micro-bubble bioreactor (AMBB), aerated submerged biofilters (ASBs), rotating biological contactor (RBC), aerated lagoons, biological sand filter (BSF), membrane bioreactor (MBR), anaerobic digestion, upflow anaerobic sludge blankets (UASB), anaerobic fluidized bed reactor (AFBR), upflow anaerobic filter (UAF), and anaerobic moving bed biofilm reactor (AMBBR), as presented in Table S1. Constructed wetlands (CW), with plants that can tolerate and detoxify wastewater, have also been considered as a means to treat this agro-industrial effluent. However, these fall out of the scope of this review 11
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paper as they combine physical, chemical and biological processes to remove the contaminants and do not belong clearly in one of the categories presented herein. As shown in the studies discussed below, COD, BOD, total nitrogen (TN) and TP are the most frequent parameters used for the determination of the efficiency of the biological processes for the treatment of winery wastewater.
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Biological treatment is considered environmentally friendly and, in most cases, cost-effective. Nevertheless, it is not able to remove
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adequately the organic matter present at high concentration levels in winery wastewater, and as a result some particularly toxic compounds
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may degrade so slowly as to be considered recalcitrant. In addition, in part due to the lack of an effective monitoring parameter for the living biomass and the intermittent load, the biological systems rarely are able to maximize their efficiency. Winery effluents are high in COD and
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color, generally acidic, and may contain phenolic species that can inhibit biological treatment systems [17]. Thus, care needs to be taken in
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the selection of the microorganisms employed and in their adaptation to treating these effluents. Moreover, it is well known that the control of biological processes is difficult, as bacterial growth is influenced by a great number of factors (Figure 2). The handling of volume and
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influent composition fluctuations by biological processes is not always successful, while allowing a series of start-up and shutdown activities is another main difficulty they face [21].
Aerobic microbiological treatment processes
Aerobic treatment systems are commonly used for the treatment of winery wastewater, as shown in Table S1, because of their high efficiency and ease of use. The biological treatment of winery wastewater started more than twenty years ago, with conventional activated 12
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sludge (CAS) providing a simple, flexible and economical treatment for the highly variable flow and characteristics of winery effluents, achieving removals even up to 98% for COD (influent value = 2000-9000 mg L-1) [32], 85% for P-PO4 [4], and 50% for BOD5 [33]. According to Fumi et al. [32], the CAS treatment plant can withstand large variations in the hydraulic and pollution load. Other important
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factors that favour an economical operation of the plant, according to this study, were the small amount of sludge produced (0.065 kg TSS
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kg-1 COD), the absence of use of pH correctors, settling agents and nutrients, the low level of manpower required to manage the process, and
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the vertical design, which reduces the footprint area occupied. In the study of Petruccioli et al. [4], the efficiency of the activated sludge
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process in removing the organic load from winery effluents was evaluated through the operation of (i) air bubble column bioreactor (ABB),
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(ii) fluidized-bed bioreactor (FBB) and (iii) packed-bed bioreactor (PBB). According to the results, the highest efficiency was obtained by ABB (92.2% COD removal; influent value = 800-11000 mg L-1). Moreover, as reported by Beck et al. [33], hydraulic optimization of the
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treatment line could be achieved by the installation of two CAS reactors instead of one (41% COD removal instead of 16%; influent value = 203-2120 mg L-1). The installation of a secondary clarifier between these two reactors improved further the treatment quality, reducing the
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BOD5 and COD by 50%.
A significantly high efficiency in the COD removal (90%) and the TN removal (60%) has been observed with the co-treatment of sewage and winery wastewater in a full-scale CAS treatment plant [20]. The WWTP considered in this work operated an extended-oxidation process during vintage (four months per year), and a pre-denitrification/oxidation process during the rest of the year. The observed yield coefficient for biomass growth (as kg MLVSS/kg COD removed) was nearly the same, varying from 0.24 to 0.28, despite the increase in the influent 13
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COD load during vintage (approximately twice higher from September to December than the rest of the year, 5480 kg d-1 vs. 2515 kg d-1). This could be explained considering that respiration rates during vintage were clearly higher compared to those observed during the ordinary period (January to April).
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The sequencing batch reactor (SBR) seems to be a very effective process for the treatment of winery wastewater (influent COD = 5200-
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17900 mg L-1), yielding a 95% COD elimination, 97.5% of BOD5, and a TN and TP removal of 50% and 88%, respectively [34]. These
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results, together with the low capital costs, and the moderate operating costs, showed that the process is appropriate to the depollution of
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wastewater from small wineries (i.e. 7300 hl yr-1). According to Petruccioli et al. [35] and Eusébio et al. [10], jet-loop activated sludge reactors (JLRs) were found able to achieve high yields
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of organic matter removal (80-90%; influent COD = 800-27200 mg L-1), while the TP and total phenolic compounds (TPh) removal efficiencies were more than 85% and up to 75%, respectively [35]. Possibly, the high TPh removal efficiency reported in this study was due
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to the combined effect of microorganisms able to degrade phenolic compounds (e.g. Pseudomonas), and to the favorable highly oxidizing conditions created by the strong turbulence, and aeration characteristic of the jet aeration system. In addition, although the aerobic treatment of winery wastewater using JLR was found to be technically feasible, sludge settleability required improvement, even though it was often within acceptable limits. In the study of Eusébio et al. [10], the operation of a JLR for more than 1 year induced the selection of acclimatized microorganisms, maintaining a high degree of conversion and productivity, and revealing good adaptation of the microbial inocula initially developed. The results of this study show that a specific microbial consortium was developed after a long operation time and strict bioreactor 14
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conditions, yielding a sufficient COD removal (>80%; influent value = 3100-27200 mg L-1). The predominant isolates were found to belong to the genera Bacillus and Pseudomonas. Later in the experiment, S. cerevisiae, a typical endogenous microorganism in the wastewater, was isolated, although its presence may be related to the development of biofilms. This was also in agreement with the study of Petruccioli et al.
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[35], where most isolates belong to the genus Pseudomonas and the yeast S. cerevisiae.
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In contrast, the rotating biological contactor (RBC) was found to be an ineffective biological system for the treatment of winery wastewater,
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since it slightly reduced the COD by 23-43% (influent value = 3828-8000 mg L-1) [5,36]. A significant finding is that yeasts play an important role in the biodegradation of winery effluents in RBC. More specifically, one of the yeast isolates, MEA5, was able to reduce the
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COD by 95% within 24 h under aerated conditions [5]. In this study, the most dominant yeast isolates in the microbial biofilms identified
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with the rDNA sequences, included S. cerevisiae, C. intermedia, H. uvarum and P. membranaefaciens. All these species are naturally associated with grapes (i.e. yeasts that exist on healthy and rotten grapes and yeasts that were added during the fermentation of wine), and with the exception of H. uvarum, they are able to form either simple or elaborate pseudohyphae. This is also in agreement with the study of
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Coetzee et al. [36], where the biofilms developed on glass slides in the winery wastewater consisted largely of yeasts with bacteria being less prominent. However, in the latter study only one of the yeast isolates (i.e. H. uvarum), showed mat formation, suggesting that this yeast can adhere to surfaces and may therefore be able to initiate biofilm formation. It should be mentioned that although the results presented in the abovementioned studies shed some light on the organisms associated with biofilms, more in-depth research is required to better understand the nature and dynamics of yeasts within microbial biofilms. In summary, considering the seasonal fluctuations in effluents discarded by 15
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wineries, the RBC could be only an effective primary treatment system to lower the COD to levels which facilitate further treatment by other biological or chemical processes.
The treatment of winery effluents in an air micro-bubble bioreactor (AMBB) in batch conditions showed a high COD and TPh removal
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efficiencies, up to 98.6% and 94%, respectively, after 15 days of treatment [37]. In a continuous flow process, the AMBB revealed a COD
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efficiency of 93% (influent COD = 1580-10170 mg L-1), which was found to be independent of the concentration of pollutants fed to the
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bioreactor. The obtained results are comparable and even better than those reported by Petruccioli et al., [35] and Eusébio et al., [38] (COD
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removal up to 90%), with the advantage of the low sludge production. A two-stage fixed bed biofilm reactor (FBBR) configuration used in the study of Andreottola et al. [39], achieved high efficiency even under
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higher fluctuations of flow and loads (91% COD removal on average; influent value = 7130 mg L-1), with good settleability of the sludge, without bulking problems. In this specific study, the difficulty in reaching further lower COD concentrations in the effluent was due to the
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non-biodegradable soluble fraction of COD (equal to 9.8% on average during the experimental period), as demonstrated from the results of respirometric tests. The 1st stage FBBR contributed for the most part to the oxidation of biodegradable COD, while the 2 nd stage was built only for the refining of 1st stage effluent in the case of presence of slowly biodegradable COD or in the case of flow rate peaks. Moreover, by carrying out two respirometric tests in parallel (the first with raw winery effluents and the second with 0.2 mm filtered wastewater) the same respirogram was obtained, indicating that the oxygen uptake rate (OUR) depends mainly on colloidal and soluble compounds.
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Two laboratory-scale aerated submerged biofilter (ASB) reactors were constructed to promote the treatment of two different fractions of winery effluents: (i) wastewater from the production area (ASB1; influent COD = 10649 mg L-1) and (ii) wastewater from the area where the washing of bottles and bottling of the wine were performed (ASB2; influent COD = 836 mg L-1) [40]. ASB1 removed on average 90% of
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COD although nitrogen was not removed. In contrast, the removal of COD in the ASB2 was 82% and the removal of nitrogen was 31%.
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Aerobic lagoons (fed-batch) can be reasonably effective for the removal of organic compounds from winery effluents, achieving 91% COD
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removal (influent value = 8700 mg L-1) after the 21st day of operation as demonstrated in pilot studies performed by Montalvo et al. [41]. This maximum average COD removal efficiency was maintained virtually constant until the end of the experiments (i.e. 54 days), indicating
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once again that a small fraction of the COD of this wastewater is not biodegradable or is resistant to the aerobic degradation (~790 ± 39 mg
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COD L-1), being in agreement with the study of Andreottola et al. [39]. During the first days of the experiments a predominance of yeast was observed, detecting also the presence of the protozoa Arcellas sp. When the pH achieved values close to 7 on the 13th day of operation, C. cucullulus was also detected, whereas when the system achieved a pseudo-equilibrium state at day 21, the protozoa Opercularia sp. was also
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present.
Finally, the effectiveness of membrane bioreactors (MBRs) for the treatment of winery effluents was found to be significantly high (>97% in terms of COD; influent value = 1000-13448 mg L-1) [8,42]. According to Artiga et al. [8] the accumulation of solids in terms of volatile suspended solids (VSS) in the reactor caused a decrease on the oxygen capacity of the system during the 50 days experimental period. It is important to mention that when the MBR was operated at higher biomass concentration, a decrease of the O2 concentration in the reactor 17
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was observed. Furthermore, a more frequent maintenance cleaning was required, while the increase of biomass did not enhance the effluent COD. In the study of Valderrama et al. [42], the average concentrations of microbial parameters, such as helmith eggs, were measured in the effluent stream of both a CAS and an MBR plant. These parameters were found to be lower than 1 egg 10 L-1 for MBR and equal to 386 eggs
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10 L-1 for CAS effluents, confirming thus that CAS process requires an additional treatment to achieve the microbial requirements for water
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reuse purpose (i.e. < 1 egg 10 L-1). Moreover, in this study operational cost estimation was performed for both technologies, based only on
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energy and chemical consumption, showing that CAS and MBR plants have very similar operational costs, equal to 0.38 and 0.40 € m-3 ,
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respectively. The influence of other operational inputs (i.e. the membrane replacement, or the cost of labor, etc.) was not considered in this
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study (were assumed equal for both plants). Even though the authors highlight that a fully automated MBR plant requires less labor than a CAS plant, a detailed economic analysis, which will consider both the capital, as well as the operational and maintenance costs of both
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biological processes was not provided.
The remediation capacities of biological sand filters (BSF) mesocosms for the treatment of winery wastewater (influent COD = 2304 mg L-1)
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was investigated in a study by Ramond et al. [43] in order to evaluate whether the sand filters can constitute an alternative and a valuable treatment process. The low pH and the high organic and salt contents, which characterize winery effluents, have all been shown to induce structural changes in environmental microbial communities. However, while the community structure changed over time, the remediation capacity remained high, with COD and TPh removal rates higher than 98% through-out the experimental period of 112 days. These results strongly suggested that there was a selection of functionally redundant microbial communities. 18
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The performance (expressed as % COD removal) of the abovementioned aerobic biological processes for the treatment of winery wastewater from either real or simulated effluents is illustrated in Figure 3 (b). As shown, the most efficient aerobic biological process was found to be the MBR [8,42], which is a relatively emerging technology providing very good commercial prospects, yielding the higher COD removal of
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97%, and almost complete removal of TSS (99%). As compared to conventional suspended-growth systems (e.g. CAS, SBR, etc.), MBR has
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the following advantages: (i) shorter HRT, (ii) fewer sludge production, (iii) more stable operation, (iv) reduced incidence of process upsets,
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and (v) simultaneous nitrification-denitrification. However, some of the disadvantages of the MBRs include (i) high capital costs for the
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membrane modules, (ii) limited data on membrane life, and thus a potential high recurring cost of periodic membrane replacement, (iii)
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higher energy costs due to membrane scouring as compared to conventional suspended-growth processes, (iv) potential membrane fouling that affects the ability to treat design flows, and (v) waste sludge from the membrane process may be more difficult to dewater. On the other
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hand, it should be mentioned that CAS and BSF, when are operating at optimum conditions, can also be considered as two of the most effective aerobic biological processes, which can remove high rates of organic load from real winery effluents, as high as 98% [32,43], and
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even up to 99% when the BSF was fed with simulated winery wastewater [44]. According to Ramond et al. [43] though, for the complete validation of BSF treatment process, long-term and replicate studies are still required. Since winery wastewater can be discharged in the environment mainly for irrigation purposes, it is important to comply with the local environmental limits of each country. Legislative policies, either on European or EU national level, do not exist regarding winery wastewater treatment and disposal. The enforcement of the qualitative limits included in the existing legislation for sewage wastewater disposal would 19
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be a responsible and urgent step in order to protect the environment and aquatic resources. The European Council Directive (91/271/EEC) [45] concerning urban wastewater treatment, sets maximum limits of 125 mg L-1 COD, 25 mg L-1 BOD5 and 35 mg L-1 TSS for treated urban effluents that can be used for irrigation and can be discharged in water dams and other water bodies. In line with this, it is obvious that a
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further pre- or post-treatment of winery effluents already treated by aerobic biological processes is required, before their disposal in the
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environment. This is due to the fact that the residual COD is generally higher than the limits stated in this Directive, as shown in Figure 3 (b)
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(i.e. ranges from 175 to 4200 mg L-1, with an exception of the MBR, CAS, air micro-bubble reactor and BSF where their average residual
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COD were approximately equal to 75 mg L-1 [8], 50 mg L-1 [46], 82 mg L-1 [37] and 46 mg L-1 [43], respectively).
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It is important to note that California and Australia have established relevant guidelines regarding the management and discharge of winery
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wastewater, as shown in Table 3. The California Regional Water Quality Control Board has established in 2002 the "General waste discharge requirements for discharges of winery waste to land" (ORDER No. R1-2002-0012) [47]. The BOD and TSS of the winery effluents for example should not be higher than 80 mg L-1 when the treated effluents are discharged to the land using spray irrigation, and
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not higher than 160 mg L-1 and
80 mg L-1 correspondingly, when drip irrigation is applied. In the case of Australia, the ANZECC
(Agriculture and Resource Management Council of Australia and New Zealand) and the ARMCANZ (Australian and New Zealand Environment and Conservation Council) have established in 1998 the "Effluent management guidelines for Australian wineries and distilleries" [48]. The Australian limits of winery effluents for discharge in aquatic bodies are 15 mg L-1 BOD5 and 50 mg L-1 TSS, while the
20
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limits for irrigation are 1500 kg BOD5 ha-1 month-1 and 704-2112 mg L-1 TDS [49]. Noteworthy is the fact that no COD limit values are specified in either the California or Australia guidelines.
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Anaerobic microbiological treatment processes
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Winery wastewater may also be treated using anaerobic biological treatment processes, as shown in Table S1. According to the results
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reported in the literature, anaerobic sequencing batch reactor (ASBR) can achieve a significant COD removal greater than 98% (influent
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COD = 8600 mg L-1), with HRT of 2.2 days, and a specific organic loading rate (OLR) of 0.96 g COD g-1 VSS d-1 [50]. In addition, the
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results of this study shown that (i) the acidification of the organic matter and the methanization of the volatile fatty acid (VFA) follow zeroorder reactions, while (ii) the effect on the gas production rate resulted in two level periods separated by a sharp break when the acidification
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stage was finished and only the breaking down of the VFA continued. The type of sludge (e.g. granular, sewage, etc.) seeded in an upflow anaerobic sludge blanket (UASB), plays an important role in reducing
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bioreactor start-up time and in increasing its efficiency, as well [51]. When using a granular sludge enriched with E. sakazakii, a microbial conditioning step was found to be necessary to aid the granules to acclimatize to the carbohydrate deficient winery effluent. This step reduced the start-up time of the UASB to just 17 days with a COD removal of higher than 90% (influent value = 2595 mg L-1), compared to the COD removal that was achieved, when the bioreactor was seeded only with conventional sludge ( O3/UV-C (21%) > O3 (12%) > UV-C 35
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( acetate > maleate > pyruvate > valerate > formate), corresponding to 17.6% of DOC.
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In order to achieve the highest COD removal (95%), using the combination of solar photo-Fenton and biological system (IBR), approximately 6 days (time necessary for the biological oxidation) were required, while 10 days were required when using the IBR only.
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According to the results of this study, the pre-oxidation step increases the biodegradability of the effluents and the microbial degradation rate, decreasing thus both the aeration demands and the retention time in the aeration tank. A summary of the overall COD removal efficiency of the various combined biological and AOPs that were used for the treatment of winery effluents, is presented in Figure 3 (d). The most efficient combined processes, using an AOP as pre-treatment, were found to be the heterogeneous solar Fenton oxidation followed by activated sludge [7] and the homogeneous solar photo-Fenton process followed by IBR 41
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[90], yielding the highest overall COD removal of 96 and 95%, respectively, while the less efficient in terms of COD removal was the ozonation followed by activated sludge [89] with only 65% removal. However, the initial COD value of the winery effluents used in the studies of Mosteo et al. [7] and Souza et al. [90] was approximately 3000 mg L-1, while those used in the study of Beltran et al. [89] was (21715 mg L-1), as shown in Table 6. Therefore, the large difference on the initial organic load of the effluents used
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almost sevenfold
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in the abovementioned studies, should be probably one of the main reasons justifying the lower efficiency of the combined ozonation -
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activated sludge process, and thus not a reliable comparison can be performed by considering the results of the above studies.
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AOPs as post-treatment
According to the literature [91,92], there are two types of wastewater, which should be treated by a biological process followed by AOPs: (i)
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wastewater containing biorecalcitrant compounds, and (ii) the highly biodegradable industrial wastewater. Winery effluents belong to the second type of wastewater, and as a consequence, several studies have been performed in which firstly the highly biodegradable part of the
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winery wastewater was eliminated biologically and then the recalcitrant contaminants were degraded by post-treatment via the application of an AOP, as shown in Table 6. The removal efficiency of the combined biological and Fenton oxidation treatment of wine-distillery effluents (influent COD = 18500 mg L1
) was investigated by de Heredia et al. [93]. The application of biological oxidation as a single process reduced the COD between 75 and
94% and the phenolic content in the range of 54 to 79%, depending on the initial organic content. Regarding the biomass, its evolution 42
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follows the typical growth-cycle phases for batch cultivation: acclimatization period → exponential growth phase → stationary phase → death phase of microorganisms. From an industrial point of view, the most interesting period in the growth cycle of a batch microbial cultivation is the exponential growth phase, when the population of biomass is perfectly acclimatized to the substrate. In this period, the rate
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of production of biomass has been described by a first-order kinetic equation as shown in the study by de Heredia et al. [93]. Moreover, the
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and TPh removals were higher than 90%.
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application of an advanced chemical post-treatment reduced the COD by 80%, with overall COD removal equal to 98%, while the aromatic
The efficiency of an SBR followed by homogeneous and heterogeneous photo-Fenton oxidation as a polishing step was investigated in the
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studies of Anastasiou et al. [94] and Ioannou et al. [95]. Biological oxidation resulted in about 50% COD and BOD5 reduction, and
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approximately 85% TSS reduction (influent COD = 16250 mg L-1; influent BOD5 = 3250 mg L-1) [94]. In this study, the effluent’s biodegradability was always low (about BOD5/COD= 0.2), regardless of the sampling point and the period of treatment. In general, organic matter degradation increases with increasing the treatment time by the homogenous Fenton’s reaction, reaching further COD and BOD5
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removal as high as 80% after 4 h of reaction. Finally, the combined SBR and homogeneous photo-Fenton oxidation resulted in the highest COD removal, even up to 95%. Additionally, according to Ioannou et al. [95], both the organic content (influent COD = 270 mg L-1), as well as the ecotoxicity of the effluents were reduced significantly during the homogeneous solar Fenton post-treatment, and reached additional values as high as 69%, 48%, 53% and 71% for COD, DOC, color and TPh, respectively. It is important to note that the biologically pretreated effluent was extremely toxic to D. magna (over 93% immobilization), while toxicity significantly decreases upon prolonged solar 43
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Fenton oxidation (e.g. at 27% after 240 min of treatment). Additionally, in this study, a comparison of the efficiency of the homogeneous and heterogeneous solar Fenton processes, concluded that the homogeneous system was the most efficient of the two. The authors reported that the efficiency of the heterogeneous process was limited by (i) light scattering effects caused by the high concentration of iron particles in
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the suspension, which inhibit the effective utilization of the photonic energy, and (ii) mass transfer limitations due to the heterogeneous
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matrix of the catalyst.
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The combined process of aerobic degradation in a long-term aerated storage followed by Fenton’s reagent oxidation was employed by Lucas et al. [96]. The results indicated that the aerobic biological degradation rates were between 76% and 96% for the COD removal at
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bench scale (4 L reactor), and between 64% and 96% at pilot scale (60 L reactor) (influent COD = 20000 mg L-1), for an HRT of 11 weeks
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and for an aeration time range from 2.4 h d-1 to 12 h d -1, respectively. The results of this study show that the degradation reached without aeration was very similar to the assays with aeration. However, harmful bad odors were produced, as result of the anaerobic biodegradation, and as a consequence, experiments with aeration were always preferable even with small aeration times. In contrast, the combined process
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(long-term aeration/Fenton reagent) led to a very high overall COD reduction that reached 99.5% when the mass ratio (R = H2O2/COD) used was equal to 2.5, maintaining constant the molar ratio H2O2/Fe2+ = 15. One of the main achievements of this combined process is the fact that the final winery effluents (COD residual = 100 mg L-1) met the Portuguese law for water reuse and discharge in water streams or on soil [96].
44
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Finally, solar photo-Fenton oxidation at bench scale was proved to be very efficient for the treatment of the winery effluents which were pretreated by a MBR, reaching an additional COD removal of approximately 70% (COD after MBR pre-treatment = 120 mg L-1), corresponding to a residual COD value of 33 mg L-1 [97]. The major part of COD was removed during first 30 min of chemical post-
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treatment (58%), while an additional 10% of COD was removed by increasing the treatment time to 90 min, after which a plateau was
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reached. The fast treatment realized during the first 30 min in which the major part of COD was removed from winery wastewater pretreated
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by MBR, is significant for a large-scale industrial application, since this can lead to a significant reduction in the operating costs as shorter
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reaction times are required, although MBR pretreatment cost must be accounted for. Solar photo-Fenton oxidation was also able to
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significantly remove the color (75±2.2%), as well as the toxicity towards D. magna (100%) and the phytotoxicity towards three plant species (L. sativum, S. alba and S. saccharatum) to values lower than 28% (in terms of plant growth inhibition). The application of the
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abovementioned combined process at pilot and industrial scale proved to be a very effective treatment of winery wastewater [22], lowering the concentration of organic pollutants in the effluent to values below that of the Cypriot discharge limits regarding urban wastewater (i.e.
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residual COD < 30 mg L-1 and residual TSS < 10 mg L-1). The overall cost (i.e. investment, operation and maintenance cost) to set up an integrated MBR with an additional solar Fenton system was estimated to be 4 € m-3 for a treatment capacity of 50 m3 d -1 and five-year operation.
Figure 3 (d) shows that the most efficient process combination (AOPs as pre- and post-treatment) is the long-term aerated storage followed by Fenton oxidation [96], which achieved almost complete removal of organic load, at 99.5% in terms of COD (residual COD = 100 mg L45
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1
). Furthermore, the combination of an advanced biological treatment, such as an MBR with solar Fenton oxidation, seems to be a very
promising process, both for the elimination of the winery wastewaters’ organic load (residual COD < 30 mg L-1), as well as its ecotoxicity, even at pilot/industrial scale [22,97]. The evaluation of the potential toxicity of the winery wastewater after each treatment process remains a
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knowledge gap in the literature, which requires further investigation.
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Summarizing, in Figure 4, the maximum organic load removal, as well as the influent and effluent organic load of the most efficient
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processes of each treatment subcategory (i.e. physicochemical, membrane filtration and separation processes, biological processes (aerobic and anaerobic), advanced oxidation processes and combined biological and advanced processes (AOPs as pre- and post-treatment)) are
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shown, in order to clearly present the most effective technologies applied for the treatment of winery wastewater.
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8. Conclusions and future perspective
The various wine processing systems applied at each winery, generate wastewater with specific properties, and therefore, establishing a
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general agreement on the most suitable and cost-effective process for their treatment is an arduous task. Numerous winery wastewater treatment processes are currently available, but the development of alternative process combinations is required, in order to increase the efficiency of removal of both the recalcitrant organic compounds, as well as ecotoxicity, with a simultaneous reduction of the investment and operational costs.
46
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The physicochemical processes (i.e. coagulation/flocculation, EC) have been found to be effective for the pre-treatment of winery wastewater, and more specifically, for lowering the TSS, the turbidity, as well as a part of the organic content to levels which can facilitate further treatment by other biological, membrane filtration and separation or advanced oxidation processes.
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Biological treatment is particularly appropriate to the treatment of winery wastewater, since the major part of its organic load is readily
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biodegradable. The newly developed MBR systems show high potential, although the small number of studies available does not provide
A
conclusive findings. Although biological processes have been found to be very effective for the treatment of winery wastewater, yielding
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high rates of organic load removal, the residual organic load of the effluents of aerobic/anaerobic biological treatment most often is higher
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than the limits stated in the European Directive 91/271/EEC regarding urban wastewater, therefore a further pre- or post-treatment before its
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safe disposal into the environment is required. Unfortunately, the data concerning the application of membrane filtration and separation processes for the treatment of winery wastewater are limited (i.e. only two published scientific studies till now), and as a consequence insufficient knowledge on their efficiency is so far
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available. The RO process seems to be a promising process. Nevertheless, it should be noted that the appropriate management of the concentrate produced and the fouling of the membranes, are the two major problems that need to be addressed. The literature suggests that advanced chemical oxidation processes hold good promises, with homogeneous solar Fenton oxidation, which appears to be a very effective process, while ozonation seems also to be a promising treatment process. However, the majority of the studies available refer to a bench or pilot scale and, therefore, further studies at pilot and full industrial scale are needed. 47
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The combination of AOPs and biological treatment (as pre- or post-treatment) can lead to a higher level of COD reduction than any singlestage treatment under the same operating conditions. More specifically, in the case of winery effluents, the use of AOPs as post-treatment of biological processes was found to be the most effective combination since it permits almost complete purification, compared to AOPs used
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as pre-treatment.
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An appraisal of the investment and operational costs of the processes considered for the treatment of winery wastewater is of major
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importance. In many studies, various aspects of the treatment cost are discussed, but very few studies specifically focus on it. Even in these
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cases, it is very difficult to compare the technologies among the various studies available, as the cost analyses are often based on different
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assumptions and, consequently, they can lead to very different treatment cost estimation. Hence, in spite of the intense scientific effort carried out by several research groups to study the technical feasibility of a wide variety of winery effluent treatment processes, the lack of
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information on cost makes difficult the determination of the Best Available Technology Not Entailing Excessive Cost (BATNEEC). As a consequence, careful economic analysis should be conducted to determine whether the most efficient combined processes are cost-effective,
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environmentally sensitive and technically reliable, allowing their full application at industrial scale. Finally, the set of physico-chemical and biological parameters used for the evaluation of the efficiency of the various processes, either standalone or combined ones, should be enlarged to include bioassays, like for example ecotoxicity and phytotoxicity tests.
48
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9. Acknowledgments
This study was performed, with the contribution of the LIFE financial instrument of the European Union, as part of the LIFE project “Advanced systems for the enhancement of the environmental performance of WINEries in Cyprus” WINEC LIFE08 ENV/CY/000455,
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aiming to support the development and implementation of policies and strategies especially focusing on the sustainable management and
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wastewater management of wineries. Nireas, International Water Research Center of the University of Cyprus (NEA
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Research Promotion Foundation.
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ΥΠΟΔΟΜΗ/ΣΤΡΑΤΗ/0308/09), is co-financed by the European Regional Development Fund and the Republic of Cyprus through the
49
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ED
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ED
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Figure Captions
Figure 1: Number of scientific studies published per year regarding the treatment of winery wastewater (from 1995 to 2014). Figure 2: Factors affecting the treatment efficiency of physicochemical, biological, membrane filtration and separation and advanced chemical
U
oxidation processes.
N
Figure 3: Organic load removal efficiency and residual organic load of (a) various physicochemical processes, (b) biological processes, (c) AOPs,
M
A
and (d) combined biological + AOPs processes used for winery wastewater treatment, according to the scientific literature. Figure 4: Maximum organic load removal of the most efficient processes of each treatment subcategory (i.e. physicochemical, membrane filtration
A CC
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ED
and separation processes, biological processes, advanced oxidation processes and combined processes) for winery wastewater.
69
ED
EP T
A CC
Figure 1
70
A
M
N
U
SC RI PT
ED
EP T
A CC
Figure 2
71
A
M
N
U
SC RI PT
SC RI PT M
A
N
U
(a)
CODresidual = 418 mg L-1
CODresidual = 13810 mg L -1 -1
ED
CODresidual = 15200 mg L
CODresidual=21625 mg L-1
EP T
CODresidual = 2118 mg L-1
A CC
CODresidual = 4790 mg L-1
The information from Figure 3(a) is taken from: [25-28,31]
72
SC RI PT o
-1
Residual COD (mg L ) 4560 680-3300 185 ~640 1233 175-577
A CC
Bar N 1 2 3 4 5 6
EP T
ED
M
A
N
U
(b)
o
Bar N 7 8 9 10 11 12
-1
Residual COD (mg L ) 82 46-314 50-4200 75-4120 2130 3900
o
Bar N 13 14 15 16 17 18
-1
Residual COD (mg L ) 4040 236-5415 8110 3200-5920 259-42900 582-750
o
Bar N 19 20 21
-1
Residual COD (mg L ) 132 160 170
The information from Figure 3(b) is taken from:[4,5,8,10,19,20,32-35,37-44,46,50-62,106,108-112,114,115,117-120,122]
73
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112 mg L-1 164 mg L 1850 mg L-1 1170-4725 mg L 1738 mg L-1
-1
-1
7000 mg L
311 mg L
1680 mg L
1042 mg L
U
-1
-1
-1
-1
2403 mg L
3337 mg L-1
M
A
N
1986 mg L
(c)
-1
451 mg L
-1
-1
A CC
EP T
ED
90400 mg L-1
The information from Figure 3(c) is taken from:[3, 71-80, 124, 125]
74
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132 mg L-1
147 mg L-1
812 mg L
-1
-1
100 mg L
(d)
-1
370 mg L
-1
A CC
EP T
ED
M
A
N
U
8686 mg L
The information from Figure 3(d) is taken from:[7, 88-90, 93, 94, 96]
* www: winery wastewater; ww: wastewater
Figure 3
75
SC RI PT U N A M ED EP T A CC Bar N 1 2 3 4 5 6 7
o
-1
Residual COD (mg L )
1550 5353 2500 5500 7587 8600 8000
418 140 75 110 75 172 160
Influent COD (mg L )
-1
Bar N 8 9 10 11 12 13 14
o
-1
-1
Influent COD (mg L )
Residual COD (mg L )
4400 2250 *(DOC) 970 3300 2958 20000 18500
132 112 *(DOC) 164 132 147 100 370
The information from Figure 4 is taken from:[7,8,28,32,42,44,50,57,62,67,74,76,90,93,96]
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Table 1: Reported qualitative characteristics of winery wastewater
Demand (COD)
L-1
Biochemical
mg -1
(BOD5)
Organic mg
ED
Total
Carbon (TOC)
Conductivity (EC)
cm-1
A CC
22418
6570
[4,6,10,30,32-34,56,71,90,94,98,99,102,103]
41
7363
1876
[3,8,73,77,80,90,98]
2.5
12.9
5.3
[3,5,7,10,14,26-28,30-32,36,39,41,42,51,61,64,71,73,77,7981,90,93,98-105]
mS
Total Solids (TS)
mg
1.1
5.6
3.46
[14,31,42,66,81,90,94,101,104]
748
18332
8660
[6,66,94,98,99]
661
12385
5625
[6,34,98,99]
66
8600
1700
[4,6,10,26-28,31-35,39,42,56,61,66,77,81,94,98-103]
-1
L
Volatile mg
Solids (TVS)
L-1
Suspended Solids mg (SS)
203
36,39,41,42,50,51,54,56,61,66,71,73,77,79,81,90,94,98-105]
L
Electrical
Total
11886 [3-8,10,27,28,30-
49105
-1
-
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pH
320
M
Oxygen Demand L
Mean References
U
Chemical Oxygen mg
Min Max
N
Unit
A
Parameter
-1
L
77
(TP)
L-1
Total
Nitrogen mg
(TN)
-1
2.1
280
53
[4,6,10,27,30,34-35,39,42,66,102,103]
10
415
118
[6,8,10,32,34,42,66,102,103]
205
[3,4,6,7,27,32,35,66,71,73,77,79,90,98,99,101,103]
L
phenolic mg L
A CC
EP T
ED
M
A
N
compounds (TPh)
0.51 1450
-1
U
Total
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Total Phosphorous mg
78
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Table 2: Physicochemical processes applied for the treatment of winery wastewater
TSS= 213-320 mg L-1
Measu re of treatm ent efficie ncy
Winery wastewater (Italy)
Chemical precipitation with chelating agents (trimercaptotria zine (TMT)) at pilot scale
COD, TSS, Cu, and Zn remova l and cost estimat ion
Operating conditions: capacity= 2.1 m3; TMT dose= 0.84 mL; pH= 8.5; reaction time= 15 min
COD, BOD and TP remova l
EC operating conditions: capacity= 1 L; I= 2 A; U= 10 V; treatment time= 10-40 min
1500-17000
BOD= 1500-2500 mg L-1
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TP= 13 mg L-1
Winery wastewater after pH adjustment to 6.0 (Israel)
Electrocoagulat ion (EC) followed by aquatic plants treatment technology (H. umbellate and E. crassipes)
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COD= mg L-1
ED
Zn= 0.14-1.47 mg L-1
pH= 3.8-4.0
Reference s
[25]
COD removal= 9%; TSS removal= 90%; Cu removal= 96%; Zn removal= 76%; cost= 14.6 € m -3
M
Cu= 0.68-1.63 mg L-1
Main findings/Removal efficiency
U
Technology characteristics
N
COD= 3090-7438 mg L-1
Matrix
A
Winery wastewater initial quality characteristics
[30]
COD removal= 28.2-41.9%; BOD removal= 16.427.9%; TP removal= 89.2% Further purification with aquatic plants treatment technology: COD removal= 98.2 %; BOD removal= 97.5%
47
VSS= 2820-6360 mg L-1 Turbidity= 319-782 NTU TPh= 1.06-1.35 mg L1
Winery wastewater (Italy)
COD= 1550 mg L-1
ED
TSS= 750 mg L-1
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Turbidity= 180 NTU
pH= 4.9-7.0
COD= 2120-4940 mg L-1
EC= 723-1472 mS cm-1
pH= 5.2 COD= 25200-28640 mg L-1 TSS= 1240 mg L-1
Combined LTAS process with coagulation (Ca(OH)2) operating conditions: volume= 60 L; flow rate= 125 L h-1; aeration period= 4 h d-1; HRT= 11 weeks
COD, TSS and turbidit y remova l
Operating conditions:capacity= 1 L; chitosan dose= 20-600 mg L-1; pH= 4-6.8; T= 20 oC; treatment time= 92 min
[28]
COD removal= 73%; turbidity removal= 92%; TSS removal= 80% No significant difference on the performance was observed with pH change
Two-step sedimentation reactor with the addition of organosepiolite and sepiolite particles as flocculants
COD, TSS and turbidit y remova l
Operating conditions: capacity= 100 mL; flocculants dose= 5 g L-1; treatment time= 11 min
Winery wastewater (Turkey)
Electrocoagulat ion (EC) using aluminum (Al) and iron (Fe)
COD, turbidit y and color remova
Operating conditions for Fe electrode: capacity= 1.5 L; pH= 7; current density= 300 A m-2; T= 25 oC; operating time= 90 min
130.3-
[27]
COD removal= 31.5-37.9%; turbidity removal= 92.6%; TSS removal= 95.4%
Winery wastewater before and after neutralization of pH (Israel)
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TSS= 1400-1600 mg L-1
Turbidity= 163.3 NTU
Coagulation using a natural organic coagulant (chitosan)
Coagulation operating conditions: capacity= 500 mL; pH= 5.0; coagulant dose= 30 mL; treatment time= 47 min
COD removal= 84.5%; turbidiy removal= 96.6%; TSS removal= 99.1%; VSS removal= 98.7%
M
pH= 6.8
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TSS= 3490-7660 mg L-1
COD, TSS, VSS and turbidit y remova l
U
COD= 31369-38391 mg L-1
Coagulation / flocculation process using four different coagulants (FeSO4, Al2(SO 4)3, FeCl3 and Ca(OH)2) combined with long-term aerated storage (LTAS)
N
Winery wastewater (Portugal)
A
pH= 4.25-4.56
[26]
COD removal= 20-40%; turbidity removal= 44%; TSS removal= 98%
[31]
COD removal= 46.6%; turbidity removal= 92.3%;
48
electrodes
l
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EC= 3.5 mS cm-1
color removal= 80.3%
Color= 6500 Pt-Co
Operating conditions for Al electrode: capacity= 1.5 L; pH= 5.2; current density= 300 A m -2; T= 25 oC; operating time= 120 min
Turbidity= 2490 NTU
COD removal= 48.5%; turbidity removal= 98.6%; color removal= 97.2% Operating conditions: capacity= 1000 mL; coagulants’ dose= 16-490 mg polymer mg clay-1; treatment time= 10 min
[29]
U
Light intensit y and cost estimat ion
N
Coagulation / flocculation based on the use of claypolymer nanocomposite s ((i) polyDADMAC (PD)-sepiolite; (ii) chitosansepiolite and (iii) PDVolclay bentonite)
PD-sepiolite: Light intensity= 70%
A
Winery wastewater (Israel)
Chitosan-sepiolite: Light intensity= 78% PD-bentonite: Light intensity= 68% Cost= 1.1-1.4 € m -3 treated wastewater
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ED
M
Data not given
49
Table 3:Guidelines and limits ofwinery effluentsdischarge in aquatic ecosystems and landin Australia and California
Discharge limits Country
Australia* Winery wastewater Discharge limits for irrigation
-
-
Spray irrigation orfrost protection
Dripirrigati on
6.5-9
5-8.5
-
-
-
-
-
-
80
160 -
pH COD (mg L-1) -1
-
15
1500 (kg BOD5ha 1 month-1)
TN (mg L-1)
0.5
5 (< 500 Kg N ha-1year1 )
-
TP (mg L-1)
0.05
0.05
-
TSS (mg L-1)
50
Gross solids should be removed
80
TDS (mg L-1)
90%; aromatic compounds removal> 90%
COD= 20000 mg L
BOD5= 11000 mg L-1
Winery wastewater (Portugal)
TSS= 8600 mg L-1
COD removal
-1
COD= 264-270 mg L
A
DOC= 100-110 mg L-1
BOD5= 111-113 mg L1
TSS= 225-245 mg L-1
Winery wastewater (Cyprus)
Operating conditions: biological system capacity= 4 and 60 L; HRT= 11 weeks; aeration times= 2.412 h d-1; oxidation system capacity= 500 mL; H2O2/Fe2+= 15; pH= 3.5; T= 30 oC
[96]
Pilot-scale long-term biological aerated storage: capacity= 60L; COD removal= 64-96% for aeration time 2.4-12 h d-1
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pH= 8.3
Combined process: COD removal= 95%
Bench-scale long-term biological aerated storage: capacity= 4L; COD removal= 88-96% for aeration time= 2.4-12 h d-1
TE
TPh= 680 mg L-1
Combined long-term aerated storage (at bench and pilot scale) and Fenton oxidation
M
-1
D
pH= 3.9
A
Photo-Fenton process: COD removal= 80%
Combined process:overall COD removal= 99.5% Combined Sequential Batch Reactor (SBR) and homogeneous or heterogeneous solar photo-
COD, DOC, color, TPh removal and ecotoxicity (D. magna)
Operating conditions of post-treatments: oxidation system capacity= 300 mL; Fe2+= 5-20 mg L-1; H2O2= 50-1000 mg L-1; FeSBA-15= 100 mg L-1; T = 25±0.1 °C Homogenous solar Fenton: COD removal= 69%; DOC removal= 48%; TPh removal= 71%; toxicity (D. magna)= 27% (immobilization)
57
[95]
Fenton oxidation
COD= 120 mg L
DOC= 30 mg L-1 BOD5< 5 mg L-1 TSS= 8 mg L-1 TN= 4 mg L-1
pH= 7.8-8.5 -1
COD= 150-210 mg L DOC= 30-60 mg L-1
Winery wastewater (Cyprus)
BOD5< 5 mg L-1 TSS= 7-11 mg L-1
COD, DOC and color removal, toxicity (D. magna) and phytotoxicit y (S. alba, L. sativum, S. saccharatu m)
Operating conditions of post-treatment: oxidation system capacity= 300 mL; pH= 3; Fe2+= 1-10 mg L-1; H2O2= 25-500 mg L-1; T= 25±0.1 oC
Combined Membrane Bioreactor (MBR) and solar Fenton oxidation at pilot and industrial scale
COD, DOC and color removal, toxicity (D. magna) and phytotoxicit y (S. alba, L. sativum, S. saccharatu m)
Operating conditions of post-treatment:oxidation system capacity= 60L; pH= 3; Fe2+= 1-5 mg L-1; H2O2= 100-750 mg L-1
[97]
COD removal= 70±3.3%; DOC removal= 53±3.7%; color removal= 75±2.2%; elimination of toxicity towards D. magna; plant growth inhibition< 28%
COD removal= 85%; DOC removal= 62-68%; color removal= 80%; elimination of toxicity towards D. magna; plant growth inhibition< 5.2%; Overall investment and operational cost of MBR + solar Fenton= 4 € m-3 for the treatment of 50 m3 d-1
A
CC
EP
TE
D
M
A
N
U
TN= 1-1.6 mg L-1
Combined Membrane Bioreactor (MBR) and solar photoFenton oxidation at bench scale
PT
Winery wastewater (Cyprus)
-1
RI
pH= 8.2
Heterogeneous solar Fenton process: COD removal= 20%; DOC removal= 20%
SC
TPh= 3.8-4.7 mg L-1
58
[22]
S0304-3894(14)01027-9 http://dx.doi.org/doi:10.1016/j.jhazmat.2014.12.043 HAZMAT 16478
To appear in:
Journal of Hazardous Materials
Received date: Revised date: Accepted date:
29-10-2014 18-12-2014 22-12-2014
Please cite this article as: L.A.Ioannou, G.Li Puma, D.Fatta-Kassinos, Treatment of winery wastewater by physicochemical, biological and advanced processes: A review, Journal of Hazardous Materials http://dx.doi.org/10.1016/j.jhazmat.2014.12.043 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Treatment of winery wastewater by physicochemical, biological and advanced processes: A review L.A. Ioannoua, G. Li Pumab, D. Fatta-Kassinosa*
a
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Department of Civil Engineering and Environmental Engineering and Nireas-International Water Research Centre, School of Engineering,
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University of Cyprus, P.O. Box 20537, 1678 Nicosia, Cyprus b
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Environmental Nanocatalysis and Photoreaction Engineering, Department of Chemical Engineering, Loughborough University,
ED
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Loughborough LE11 3TU, United Kingdom
Abstract
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Corresponding author: *Despo Fatta-Kassinos: [email protected]
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Winery wastewater is a major waste stream resulting from numerous cleaning operations that occur during the production stages of wine. The resulting effluent contains various organic and inorganic contaminants and its environmental impact is notable, mainly due to its high organic/inorganic load, the large volumes produced and its seasonal variability. Several processes for the treatment of winery wastewater are currently available, but the development of alternative treatment methods is necessary, in order to (i) maximize the efficiency and flexibility of the treatment process to meet the discharge requirements for winery effluents, and (ii) decrease both the environmental footprint, as well 1
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as the investment/operational costs of the process. This review, presents the state-of-the-art of the processes currently applied and/or tested for the treatment of winery wastewater, which were divided into five categories: i.e. physicochemical, biological, membrane filtration and separation, advanced oxidation processes, and combined biological and advanced oxidation processes. The advantages and disadvantages,
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as well as the main parameters/factors affecting the efficiency of winery wastewater treatment are discussed. Both bench- and
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pilot/industrial-scale processes have been considered for this review.
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Keywords: winery wastewater; biological processes; physicochemical processes; membranes; advanced oxidation processes
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1. Why winery wastewater requires sustainable management
Wine production, traditionally and among the population, is perceived to be an environmentally friendly process and it is widely practiced in
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many agricultural and rural regions opening onto the Mediterranean and the Atlantic seas including France, Italy, Spain, Portugal, Greece and Turkey, Central and East Europe including Germany, Hungary, Romania and Bulgaria, the New World regions including Australia, New
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Zealand, South Africa, USA, Chile and Argentina and finally China in which the production of wine is predicted to soar. However, wine production requires a considerable amount of resources such as water, energy, fertilizers and organic supplements, and produces large volumes of waste streams [1,2]. These waste streams include solid organic waste (e.g. grape marc, skins, pips, etc.), wastewater, greenhouse gases (e.g. CO2, volatile organic compounds, etc.), and packaging waste [3].
2
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Winery wastewater, is a major waste stream resulting from a number of activities that includes cleaning of tanks, washing of floors and equipment, rinsing of transfer lines, barrel cleaning, off wine and product losses, bottling facilities, filtration units and rainwater diverted into, or captured in the wastewater management system. The effluent produced contains various contaminants, such as ethanol, sugars,
N
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organic acids, phenolic compounds, etc. [4-7].
A
Both the volumes and the pollution load of winery effluents vary greatly in relation to the working period (i.e. vintage, racking, bottling),
M
and the kind of the wine produced (e.g. red, white, sparkling, etc.) [8,9]. It is estimated that a winery produces between 1.3 and 1.5 kg of residues per liter of wine produced, 75% of which is winery wastewater [3]. Due to the seasonal operation of wine industries unique
ED
problems arise for the treatment processes in terms of wastewater volume and composition [10]. As a result, treatment plants must be
[11].
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flexible to changes in the loading regime and must quickly adapt to sequences of start-ups and closedowns, and also intervals of inactivity
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The environmental impact of wastewater from the wine industry is notable (i.e. pollution of water, degradation of soil and damage to vegetation arising from wastewater disposal practices, odors and air emissions resulting from the management of wastewater) mainly due to the high organic load and the large volumes produced [12]. Each winery is unique with regard to the volume of wastewater generated (highly variable, 0.5-14 L per litre of wine produced) and the disposal practices applied [13]. Winery wastewater can cause eutrophication (nutrient enrichment) of water resources (i.e. natural streams, rivers, dams and wetlands). If high levels of biological oxygen demand (BOD) in 3
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untreated winery wastewater are allowed to flow into streams, rivers and lakes, the dissolved oxygen (DO) in the waterways may be quickly consumed, leading to the suffocation of aquatic and amphibious life [14]. In addition, application of winery effluent to soil without an appropriate monitoring programme, can alter the physicochemical properties of groundwater by affecting color, pH and electrical
U
conductivity from the leaching of organic and inorganic ions [15]. The high acidity of winery wastewater can affect plant vigor by reducing
N
the availability of plant nutrients (particularly phosphorous and calcium) and decreasing populations of useful microbes [16]. In addition, the
A
high percentage of organic compounds and salts contained in winery effluents can cause significant inhibitory effects on plant growth, while
M
the high electrical conductivity causes retardation of germination, since it makes the water uptake by seeds difficult [11]. In addition,
ED
numerous phenolic compounds are present in wines and winery wastewater, as a result of their extraction from the skin, the flesh and seeds of grapes. Although, phenolic compounds form a relatively small portion of the organic load of winery effluents, they can cause significant
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environmental damage if released untreated in the environment [17] since some of these compounds are toxic to human, animals and many
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microorganisms, even at relatively low concentrations [18], and they are also particularly resistant to degradation [11].
Winery effluents are in general biodegradable and the period during which the ratio BOD5/COD is higher is during the vintage period, because of the presence of molecules, such as sugars and ethanol [19]. Part of the organic load contained in the winery effluents is however, biorecalcitrant and potentially toxic to various microorganisms and plant species. The COD concentration of winery effluents ranges from 320 to 49105 mg L-1 (mean value: 11886 mg L-1), while the BOD5 ranges from 203 to 22418 mg L-1 (mean value: 6570 mg L-1). A summary of the qualitative characteristics of the effluents from a number of wineries, according to the literature, is presented in Table 1. 4
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2. Processes currently applied for the treatment of winery wastewater
Even though the main qualitative characteristics of winery wastewater are well known, it is quite difficult to establish a criterion to define in advance the pollution load, since it depends on the winemaking mode and the technologies adopted [20]. There are several options for their
N
U
treatment, aiming to achieve not only a high degree of organic/inorganic load reduction, but also a significant reduction of suspended solids
A
[21].
M
The processes that are used currently for the treatment of winery wastewater are for the purpose of this review divided into five categories:
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physicochemical, biological, membrane filtration and separation, advanced oxidation processes (AOPs), and combined biological + advanced chemical processes. For each category the main findings are discussed along with the parameters used for assessing their treatment
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efficiency. The physicochemical and biological processes are already applied at industrial scale, while the advanced processes are mostly applied at smaller scales (i.e. bench and pilot scale) and detailed knowledge for their upscaling is still missing. To the authors’ knowledge
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only one industrial-scale application of an advanced chemical process for the treatment of winery effluents is currently available in the literature [22].
Figure 1 presents the number of journal publications regarding the winery wastewater treatment during the period 1995-2014. According to the literature, the treatment of winery effluents started timidly more than forty years ago, with the study of Haynes et al. [23], where a longterm activated sludge system followed by tertiary sand filter was constructed and operated at a winery in New York. As shown in Figure 1, 5
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winery wastewater treatment showed a modest increase by the middle of 2000s, followed by a much more robust upward trend since ca. 2009. It is apparent that the evolution of the number of studies related to the different treatment technologies abovementioned, is constantly increasing, with the aim to bridge the various knowledge gaps associated with (i) the increase of the treatment efficiency of each process (i.e.
U
evaluation of the efficiency of the new developed and/or combined processes, upscaling of the various advanced processes, etc.), and (ii) the
A
N
safe disposal of this effluent into the environment (i.e. assessment of the treated effluents’ toxicity and phytotoxicity, etc.).
M
Various review papers are available in the scientific literature addressing selected issues regarding the production and management of winery wastewater. The review of Melamane et al. [11] summarizes the efficiency of various processes applied for the treatment of wine-distillery
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wastewater, with emphasis on anaerobic biological processes, as well as membrane bioreactors (MBRs). In this review, the use of winery
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effluents for irrigation, direct discharge on soil or in groundwater, evaporation and discharge to urban wastewater treatment plants (WWTPs) are discussed. Strong and Burgess [17] review the treatment of phenolic compound-rich wastewaters by physicochemical, aerobic biological
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systems and hybrid treatment methods and the valuable products (lignolytic enzymes such as laccase) derived from fungal treatment of winery and distillery wastewater. Andreottola et al. [24] provide an overview on the existing status and advances in the biological treatment of winery wastewater, considering both bench-, pilot- and full-scale studies. Also, the advantages and disadvantages, as well as the removal efficiency of biological processes applied for the treatment of these effluents are presented. Moreover, the review of Mosse et al. [21] describes the processes that are available for the treatment of these effluents in Australia, discussing also advantages and disadvantages of
6
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their use. Also, the disposal options that are mainly applied (i.e. land disposal and irrigation), as well as impacts induced to the soil by this practice (e.g. increased soil fertility, salinity, changes to the soil microbial community, etc.) are discussed.
The aim of the present paper is to provide a review on the efficiency of different processes for the treatment of winery wastewater, namely
N
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physicochemical, biological, membrane filtration and separation, advanced oxidation processes, and various integrated processes and
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critically discuss their main findings, regarding (i) the efficiency for the removal of both organic and inorganic loads, (ii) the economic and
M
operational feasibility, (iii) effluents’ quality and potential toxicity to various microorganisms and plant species, and (iv) the possible need for further pre- or post-treatment, ensuring thus the safe disposal of the treated wastewater in the environment or for water reuse. According
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to the authors’ knowledge this is the first review paper, where an effort to include all the studies available in the literature, regarding winery
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wastewater treatment, is made.
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3. Physicochemical processes
There are various physicochemical processes that have been successfully applied for the treatment of real winery effluent, such as chemical precipitation with chelating agents [25], sedimentation with the addition of flocculants [26], coagulation/flocculation [27-29] and electrocogualation (EC) [30,31], as shown in Table 2.
7
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When comparing the efficiencies of the various processes, attention must be paid due to the fact that the qualitative characteristics of the initial effluents used in each study differ substantially (as shown in Tables 2, 4-6 and Table S1). From the studies discussed below, it is obvious, that the most common parameters measured in order to evaluate the efficiency of the various physicochemical processes are the
N
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total suspended solids (TSS), turbidity and COD removal.
A
The effectiveness of a pre-treatment process based on chemical precipitation with chelating agents (i.e. trimercaptotriazine (TMT)) at a pilot
M
scale, for the reduction of turbidity, as well as heavy metals (i.e. Cu and Zn) from real winery wastewater (influent COD = 3090-7438 mg L1
) was investigated by Andreotolla et al. [25]. In this study, high removals of TSS, Cu and Zn were achieved, equal to 90%, 96% and 76%,
ED
respectively, although the COD removal was only 9% of COD. The low COD removal occurred since 92% of winery wastewater was in
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soluble form, for which chemical precipitation is not effective. The treatment cost of the winery wastewater, taking into account the plant management, chemical doses, periodically effluent quality controls, electricity, sludge disposal and taxes for the discharge into the public
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sewerage, was estimated to be 14.6 € m-3. The pre-treatment of winery wastewater (influent COD = 1550 mg L-1) by coagulation, using a natural organic coagulant i.e. chitosan, was investigated by Rizzo et al. [28] as a feasible alternative to conventional coagulants based on metals, so as to produce a potentially reusable organic sludge. The efficiency of the coagulation was found to be high in terms of TSS (80%), turbidity (92%), and organic matter removal (73% in terms of COD). It should be noted that when coagulation reached the optimum condition (optimum dose = 20 mg L-1) in which the 8
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residual turbidity, COD, and TSS values were the lowest, no further improvements could be achieved by varying the pH (4 to 6.8). This result indicates that interparticle bridging rather than the neutralization charge and/or adsorption mechanism might be the main cause for the aggregation of particles.
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A similar and even higher efficiency on TSS (95.4%) and turbidity (92.6%) removal was also achieved by the application of
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coagulation/flocculation (experimental conditions: pH = 5 and 30 mL (5% w/v) coagulant dosage), using Ca(OH)2 and Al2(SO4)3 as a
M
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coagulant, respectively, as shown in the study by Braz et al. [27]. However, only a small part of COD (influent value = 31369-38391 mg L-1) was removed by this process; lower than 68%. Taking into account the inefficient removal of COD, the combination of long-term aerated
ED
storage (LTAS) followed by coagulation/flocculation with Ca(OH)2 was further investigated, enhancing the overall removal efficiency to
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approx. 85% for COD, 99% for TSS, and 97% for turbidity. An effective two-step sedimentation procedure with 0.1% organo-sepiolite and 0.1% sepiolite modified with crystal violet that changes the
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colloidal properties of winery effluents (influent COD = 2120-4940 mg L-1) was presented in the study of Rytwo et al. [26]. After the first step of the sedimentation procedure, the surface charge of the remaining dispersed particles was decreased by 50%, while after the second step by further 30%. In addition, almost complete TSS removal (98%) and a considerable turbidity reduction (44%) were achieved from the combined procedure, although the COD removal was low and ranged between 20-40%. According to the authors, the large differences between TSS and turbidity/COD reduction might indicate that very small dispersed particles largely made up the remaining turbidity, and the remaining COD presumably represented dissolved organic matter. 9
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Electrocoagulation (EC) was found to be an efficient process for the removal of COD (up to 42%; influent COD = 1500-17000 mg L-1) and total phosphorous (TP) (89%; influent TP = 13 mg L-1), while a moderate reduction of BOD (28%; influent BOD = 1500-2500 mg L-1) was also observed, as reported in the study of Kirzhner et al. [30]. The addition of 1 L min -1 O3 slightly enhanced the process efficiency (from 42
U
to 48% COD removal), while in contrast, the addition of H2O2 had an adverse effect. In order to further enhance the removal efficiency, a
N
two-stage process was applied, where in the first stage the effluent was treated by EC and its resulting flow was further purified in a second
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stage comprising by aquatic plants (i.e. salt marshes with rushes). At 1:1 dilution (with fresh water), 97.5 and 95.6% of the BOD were
M
removed, after 23 days of treatment, with the floating H. umbellate and E. crassipes plants and aeration, respectively, while 98.2% of COD
ED
was also removed. The viability of an economic model was demonstrated for the case of 8000 m3 year-1 treatment facility (EC followed by aquatic plants) and the operating cost was calculated equal to 1.8 € m-3 of treated winery wastewater. The internal rate of return for this
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project was 29.5% and the payback time 4.0 years, suggesting thus the viability of the treatment process. In a recent study of Kara et al. [31] the treatment of winery effluents by EC using two different electrodes (Al and Fe) was investigated. The removal efficiency of the COD
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(influent COD = 25200-28640 mg L-1), color (influent value = 6500 Pt-Co) and turbidity (influent value = 2490 NTU) for Fe and Al electrodes were found to be dependent on initial pH, applied current density and operating time. When Fe electrodes were used, the removal efficiencies of COD, color, and turbidity were calculated as 46.6, 80.3, and 92.3%, respectively; while when Al electrodes were used, the removal efficiencies were found as 48.5% for COD, 97.2% for color, and 98.6% for turbidity. According to these results, the color and turbidity can be removed successfully by EC treatment from winery effluents, but the COD concentration remains too high for discharge (i.e. 10
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13810 and 15200 mg L-1 for Al and Fe electrodes, respectively) [31]. Therefore, EC process could be applied as pre- or post-treatment of other treatment technologies, such as a biological treatment that can achieve higher COD removal.
The most important parameters affecting the treatment efficiency of physicochemical processes are presented in Figure 2. Figure 3 (a)
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presents the COD removal efficiency of the abovementioned physicochemical processes. According to these studies, coagulation with
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chitosan was found to have the highest efficiency in the removal of COD (up to 73%) [28]. Based on the information presented herein, it is
M
obvious that the use of alternative coagulants to chemical ones, like for examples biopolymers (e.g. chitosan) can be efficient towards the treatment of winery wastewater, while at the same time they have the advantage of being non-toxic, non-corrosive and safe to animals and
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4. Biological processes
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plants, without causing environmental pollution.
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Various biological processes for the treatment of winery wastewater have been applied including activated sludge, jet-loop reactor (JLR), sequential batch reactor (SBR), fixed bed biofilm reactor (FBBR) system, air micro-bubble bioreactor (AMBB), aerated submerged biofilters (ASBs), rotating biological contactor (RBC), aerated lagoons, biological sand filter (BSF), membrane bioreactor (MBR), anaerobic digestion, upflow anaerobic sludge blankets (UASB), anaerobic fluidized bed reactor (AFBR), upflow anaerobic filter (UAF), and anaerobic moving bed biofilm reactor (AMBBR), as presented in Table S1. Constructed wetlands (CW), with plants that can tolerate and detoxify wastewater, have also been considered as a means to treat this agro-industrial effluent. However, these fall out of the scope of this review 11
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paper as they combine physical, chemical and biological processes to remove the contaminants and do not belong clearly in one of the categories presented herein. As shown in the studies discussed below, COD, BOD, total nitrogen (TN) and TP are the most frequent parameters used for the determination of the efficiency of the biological processes for the treatment of winery wastewater.
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Biological treatment is considered environmentally friendly and, in most cases, cost-effective. Nevertheless, it is not able to remove
A
adequately the organic matter present at high concentration levels in winery wastewater, and as a result some particularly toxic compounds
M
may degrade so slowly as to be considered recalcitrant. In addition, in part due to the lack of an effective monitoring parameter for the living biomass and the intermittent load, the biological systems rarely are able to maximize their efficiency. Winery effluents are high in COD and
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color, generally acidic, and may contain phenolic species that can inhibit biological treatment systems [17]. Thus, care needs to be taken in
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the selection of the microorganisms employed and in their adaptation to treating these effluents. Moreover, it is well known that the control of biological processes is difficult, as bacterial growth is influenced by a great number of factors (Figure 2). The handling of volume and
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influent composition fluctuations by biological processes is not always successful, while allowing a series of start-up and shutdown activities is another main difficulty they face [21].
Aerobic microbiological treatment processes
Aerobic treatment systems are commonly used for the treatment of winery wastewater, as shown in Table S1, because of their high efficiency and ease of use. The biological treatment of winery wastewater started more than twenty years ago, with conventional activated 12
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sludge (CAS) providing a simple, flexible and economical treatment for the highly variable flow and characteristics of winery effluents, achieving removals even up to 98% for COD (influent value = 2000-9000 mg L-1) [32], 85% for P-PO4 [4], and 50% for BOD5 [33]. According to Fumi et al. [32], the CAS treatment plant can withstand large variations in the hydraulic and pollution load. Other important
U
factors that favour an economical operation of the plant, according to this study, were the small amount of sludge produced (0.065 kg TSS
N
kg-1 COD), the absence of use of pH correctors, settling agents and nutrients, the low level of manpower required to manage the process, and
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the vertical design, which reduces the footprint area occupied. In the study of Petruccioli et al. [4], the efficiency of the activated sludge
M
process in removing the organic load from winery effluents was evaluated through the operation of (i) air bubble column bioreactor (ABB),
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(ii) fluidized-bed bioreactor (FBB) and (iii) packed-bed bioreactor (PBB). According to the results, the highest efficiency was obtained by ABB (92.2% COD removal; influent value = 800-11000 mg L-1). Moreover, as reported by Beck et al. [33], hydraulic optimization of the
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treatment line could be achieved by the installation of two CAS reactors instead of one (41% COD removal instead of 16%; influent value = 203-2120 mg L-1). The installation of a secondary clarifier between these two reactors improved further the treatment quality, reducing the
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BOD5 and COD by 50%.
A significantly high efficiency in the COD removal (90%) and the TN removal (60%) has been observed with the co-treatment of sewage and winery wastewater in a full-scale CAS treatment plant [20]. The WWTP considered in this work operated an extended-oxidation process during vintage (four months per year), and a pre-denitrification/oxidation process during the rest of the year. The observed yield coefficient for biomass growth (as kg MLVSS/kg COD removed) was nearly the same, varying from 0.24 to 0.28, despite the increase in the influent 13
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COD load during vintage (approximately twice higher from September to December than the rest of the year, 5480 kg d-1 vs. 2515 kg d-1). This could be explained considering that respiration rates during vintage were clearly higher compared to those observed during the ordinary period (January to April).
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The sequencing batch reactor (SBR) seems to be a very effective process for the treatment of winery wastewater (influent COD = 5200-
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17900 mg L-1), yielding a 95% COD elimination, 97.5% of BOD5, and a TN and TP removal of 50% and 88%, respectively [34]. These
M
results, together with the low capital costs, and the moderate operating costs, showed that the process is appropriate to the depollution of
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wastewater from small wineries (i.e. 7300 hl yr-1). According to Petruccioli et al. [35] and Eusébio et al. [10], jet-loop activated sludge reactors (JLRs) were found able to achieve high yields
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of organic matter removal (80-90%; influent COD = 800-27200 mg L-1), while the TP and total phenolic compounds (TPh) removal efficiencies were more than 85% and up to 75%, respectively [35]. Possibly, the high TPh removal efficiency reported in this study was due
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to the combined effect of microorganisms able to degrade phenolic compounds (e.g. Pseudomonas), and to the favorable highly oxidizing conditions created by the strong turbulence, and aeration characteristic of the jet aeration system. In addition, although the aerobic treatment of winery wastewater using JLR was found to be technically feasible, sludge settleability required improvement, even though it was often within acceptable limits. In the study of Eusébio et al. [10], the operation of a JLR for more than 1 year induced the selection of acclimatized microorganisms, maintaining a high degree of conversion and productivity, and revealing good adaptation of the microbial inocula initially developed. The results of this study show that a specific microbial consortium was developed after a long operation time and strict bioreactor 14
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conditions, yielding a sufficient COD removal (>80%; influent value = 3100-27200 mg L-1). The predominant isolates were found to belong to the genera Bacillus and Pseudomonas. Later in the experiment, S. cerevisiae, a typical endogenous microorganism in the wastewater, was isolated, although its presence may be related to the development of biofilms. This was also in agreement with the study of Petruccioli et al.
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[35], where most isolates belong to the genus Pseudomonas and the yeast S. cerevisiae.
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In contrast, the rotating biological contactor (RBC) was found to be an ineffective biological system for the treatment of winery wastewater,
M
A
since it slightly reduced the COD by 23-43% (influent value = 3828-8000 mg L-1) [5,36]. A significant finding is that yeasts play an important role in the biodegradation of winery effluents in RBC. More specifically, one of the yeast isolates, MEA5, was able to reduce the
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COD by 95% within 24 h under aerated conditions [5]. In this study, the most dominant yeast isolates in the microbial biofilms identified
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with the rDNA sequences, included S. cerevisiae, C. intermedia, H. uvarum and P. membranaefaciens. All these species are naturally associated with grapes (i.e. yeasts that exist on healthy and rotten grapes and yeasts that were added during the fermentation of wine), and with the exception of H. uvarum, they are able to form either simple or elaborate pseudohyphae. This is also in agreement with the study of
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Coetzee et al. [36], where the biofilms developed on glass slides in the winery wastewater consisted largely of yeasts with bacteria being less prominent. However, in the latter study only one of the yeast isolates (i.e. H. uvarum), showed mat formation, suggesting that this yeast can adhere to surfaces and may therefore be able to initiate biofilm formation. It should be mentioned that although the results presented in the abovementioned studies shed some light on the organisms associated with biofilms, more in-depth research is required to better understand the nature and dynamics of yeasts within microbial biofilms. In summary, considering the seasonal fluctuations in effluents discarded by 15
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wineries, the RBC could be only an effective primary treatment system to lower the COD to levels which facilitate further treatment by other biological or chemical processes.
The treatment of winery effluents in an air micro-bubble bioreactor (AMBB) in batch conditions showed a high COD and TPh removal
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efficiencies, up to 98.6% and 94%, respectively, after 15 days of treatment [37]. In a continuous flow process, the AMBB revealed a COD
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efficiency of 93% (influent COD = 1580-10170 mg L-1), which was found to be independent of the concentration of pollutants fed to the
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bioreactor. The obtained results are comparable and even better than those reported by Petruccioli et al., [35] and Eusébio et al., [38] (COD
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removal up to 90%), with the advantage of the low sludge production. A two-stage fixed bed biofilm reactor (FBBR) configuration used in the study of Andreottola et al. [39], achieved high efficiency even under
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higher fluctuations of flow and loads (91% COD removal on average; influent value = 7130 mg L-1), with good settleability of the sludge, without bulking problems. In this specific study, the difficulty in reaching further lower COD concentrations in the effluent was due to the
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non-biodegradable soluble fraction of COD (equal to 9.8% on average during the experimental period), as demonstrated from the results of respirometric tests. The 1st stage FBBR contributed for the most part to the oxidation of biodegradable COD, while the 2 nd stage was built only for the refining of 1st stage effluent in the case of presence of slowly biodegradable COD or in the case of flow rate peaks. Moreover, by carrying out two respirometric tests in parallel (the first with raw winery effluents and the second with 0.2 mm filtered wastewater) the same respirogram was obtained, indicating that the oxygen uptake rate (OUR) depends mainly on colloidal and soluble compounds.
16
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Two laboratory-scale aerated submerged biofilter (ASB) reactors were constructed to promote the treatment of two different fractions of winery effluents: (i) wastewater from the production area (ASB1; influent COD = 10649 mg L-1) and (ii) wastewater from the area where the washing of bottles and bottling of the wine were performed (ASB2; influent COD = 836 mg L-1) [40]. ASB1 removed on average 90% of
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COD although nitrogen was not removed. In contrast, the removal of COD in the ASB2 was 82% and the removal of nitrogen was 31%.
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Aerobic lagoons (fed-batch) can be reasonably effective for the removal of organic compounds from winery effluents, achieving 91% COD
M
A
removal (influent value = 8700 mg L-1) after the 21st day of operation as demonstrated in pilot studies performed by Montalvo et al. [41]. This maximum average COD removal efficiency was maintained virtually constant until the end of the experiments (i.e. 54 days), indicating
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once again that a small fraction of the COD of this wastewater is not biodegradable or is resistant to the aerobic degradation (~790 ± 39 mg
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COD L-1), being in agreement with the study of Andreottola et al. [39]. During the first days of the experiments a predominance of yeast was observed, detecting also the presence of the protozoa Arcellas sp. When the pH achieved values close to 7 on the 13th day of operation, C. cucullulus was also detected, whereas when the system achieved a pseudo-equilibrium state at day 21, the protozoa Opercularia sp. was also
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present.
Finally, the effectiveness of membrane bioreactors (MBRs) for the treatment of winery effluents was found to be significantly high (>97% in terms of COD; influent value = 1000-13448 mg L-1) [8,42]. According to Artiga et al. [8] the accumulation of solids in terms of volatile suspended solids (VSS) in the reactor caused a decrease on the oxygen capacity of the system during the 50 days experimental period. It is important to mention that when the MBR was operated at higher biomass concentration, a decrease of the O2 concentration in the reactor 17
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was observed. Furthermore, a more frequent maintenance cleaning was required, while the increase of biomass did not enhance the effluent COD. In the study of Valderrama et al. [42], the average concentrations of microbial parameters, such as helmith eggs, were measured in the effluent stream of both a CAS and an MBR plant. These parameters were found to be lower than 1 egg 10 L-1 for MBR and equal to 386 eggs
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10 L-1 for CAS effluents, confirming thus that CAS process requires an additional treatment to achieve the microbial requirements for water
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reuse purpose (i.e. < 1 egg 10 L-1). Moreover, in this study operational cost estimation was performed for both technologies, based only on
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energy and chemical consumption, showing that CAS and MBR plants have very similar operational costs, equal to 0.38 and 0.40 € m-3 ,
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respectively. The influence of other operational inputs (i.e. the membrane replacement, or the cost of labor, etc.) was not considered in this
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study (were assumed equal for both plants). Even though the authors highlight that a fully automated MBR plant requires less labor than a CAS plant, a detailed economic analysis, which will consider both the capital, as well as the operational and maintenance costs of both
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biological processes was not provided.
The remediation capacities of biological sand filters (BSF) mesocosms for the treatment of winery wastewater (influent COD = 2304 mg L-1)
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was investigated in a study by Ramond et al. [43] in order to evaluate whether the sand filters can constitute an alternative and a valuable treatment process. The low pH and the high organic and salt contents, which characterize winery effluents, have all been shown to induce structural changes in environmental microbial communities. However, while the community structure changed over time, the remediation capacity remained high, with COD and TPh removal rates higher than 98% through-out the experimental period of 112 days. These results strongly suggested that there was a selection of functionally redundant microbial communities. 18
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The performance (expressed as % COD removal) of the abovementioned aerobic biological processes for the treatment of winery wastewater from either real or simulated effluents is illustrated in Figure 3 (b). As shown, the most efficient aerobic biological process was found to be the MBR [8,42], which is a relatively emerging technology providing very good commercial prospects, yielding the higher COD removal of
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97%, and almost complete removal of TSS (99%). As compared to conventional suspended-growth systems (e.g. CAS, SBR, etc.), MBR has
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the following advantages: (i) shorter HRT, (ii) fewer sludge production, (iii) more stable operation, (iv) reduced incidence of process upsets,
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and (v) simultaneous nitrification-denitrification. However, some of the disadvantages of the MBRs include (i) high capital costs for the
M
membrane modules, (ii) limited data on membrane life, and thus a potential high recurring cost of periodic membrane replacement, (iii)
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higher energy costs due to membrane scouring as compared to conventional suspended-growth processes, (iv) potential membrane fouling that affects the ability to treat design flows, and (v) waste sludge from the membrane process may be more difficult to dewater. On the other
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hand, it should be mentioned that CAS and BSF, when are operating at optimum conditions, can also be considered as two of the most effective aerobic biological processes, which can remove high rates of organic load from real winery effluents, as high as 98% [32,43], and
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even up to 99% when the BSF was fed with simulated winery wastewater [44]. According to Ramond et al. [43] though, for the complete validation of BSF treatment process, long-term and replicate studies are still required. Since winery wastewater can be discharged in the environment mainly for irrigation purposes, it is important to comply with the local environmental limits of each country. Legislative policies, either on European or EU national level, do not exist regarding winery wastewater treatment and disposal. The enforcement of the qualitative limits included in the existing legislation for sewage wastewater disposal would 19
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be a responsible and urgent step in order to protect the environment and aquatic resources. The European Council Directive (91/271/EEC) [45] concerning urban wastewater treatment, sets maximum limits of 125 mg L-1 COD, 25 mg L-1 BOD5 and 35 mg L-1 TSS for treated urban effluents that can be used for irrigation and can be discharged in water dams and other water bodies. In line with this, it is obvious that a
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further pre- or post-treatment of winery effluents already treated by aerobic biological processes is required, before their disposal in the
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environment. This is due to the fact that the residual COD is generally higher than the limits stated in this Directive, as shown in Figure 3 (b)
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(i.e. ranges from 175 to 4200 mg L-1, with an exception of the MBR, CAS, air micro-bubble reactor and BSF where their average residual
M
COD were approximately equal to 75 mg L-1 [8], 50 mg L-1 [46], 82 mg L-1 [37] and 46 mg L-1 [43], respectively).
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It is important to note that California and Australia have established relevant guidelines regarding the management and discharge of winery
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wastewater, as shown in Table 3. The California Regional Water Quality Control Board has established in 2002 the "General waste discharge requirements for discharges of winery waste to land" (ORDER No. R1-2002-0012) [47]. The BOD and TSS of the winery effluents for example should not be higher than 80 mg L-1 when the treated effluents are discharged to the land using spray irrigation, and
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not higher than 160 mg L-1 and
80 mg L-1 correspondingly, when drip irrigation is applied. In the case of Australia, the ANZECC
(Agriculture and Resource Management Council of Australia and New Zealand) and the ARMCANZ (Australian and New Zealand Environment and Conservation Council) have established in 1998 the "Effluent management guidelines for Australian wineries and distilleries" [48]. The Australian limits of winery effluents for discharge in aquatic bodies are 15 mg L-1 BOD5 and 50 mg L-1 TSS, while the
20
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limits for irrigation are 1500 kg BOD5 ha-1 month-1 and 704-2112 mg L-1 TDS [49]. Noteworthy is the fact that no COD limit values are specified in either the California or Australia guidelines.
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Anaerobic microbiological treatment processes
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Winery wastewater may also be treated using anaerobic biological treatment processes, as shown in Table S1. According to the results
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reported in the literature, anaerobic sequencing batch reactor (ASBR) can achieve a significant COD removal greater than 98% (influent
M
COD = 8600 mg L-1), with HRT of 2.2 days, and a specific organic loading rate (OLR) of 0.96 g COD g-1 VSS d-1 [50]. In addition, the
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results of this study shown that (i) the acidification of the organic matter and the methanization of the volatile fatty acid (VFA) follow zeroorder reactions, while (ii) the effect on the gas production rate resulted in two level periods separated by a sharp break when the acidification
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stage was finished and only the breaking down of the VFA continued. The type of sludge (e.g. granular, sewage, etc.) seeded in an upflow anaerobic sludge blanket (UASB), plays an important role in reducing
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bioreactor start-up time and in increasing its efficiency, as well [51]. When using a granular sludge enriched with E. sakazakii, a microbial conditioning step was found to be necessary to aid the granules to acclimatize to the carbohydrate deficient winery effluent. This step reduced the start-up time of the UASB to just 17 days with a COD removal of higher than 90% (influent value = 2595 mg L-1), compared to the COD removal that was achieved, when the bioreactor was seeded only with conventional sludge ( O3/UV-C (21%) > O3 (12%) > UV-C 35
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( acetate > maleate > pyruvate > valerate > formate), corresponding to 17.6% of DOC.
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In order to achieve the highest COD removal (95%), using the combination of solar photo-Fenton and biological system (IBR), approximately 6 days (time necessary for the biological oxidation) were required, while 10 days were required when using the IBR only.
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According to the results of this study, the pre-oxidation step increases the biodegradability of the effluents and the microbial degradation rate, decreasing thus both the aeration demands and the retention time in the aeration tank. A summary of the overall COD removal efficiency of the various combined biological and AOPs that were used for the treatment of winery effluents, is presented in Figure 3 (d). The most efficient combined processes, using an AOP as pre-treatment, were found to be the heterogeneous solar Fenton oxidation followed by activated sludge [7] and the homogeneous solar photo-Fenton process followed by IBR 41
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[90], yielding the highest overall COD removal of 96 and 95%, respectively, while the less efficient in terms of COD removal was the ozonation followed by activated sludge [89] with only 65% removal. However, the initial COD value of the winery effluents used in the studies of Mosteo et al. [7] and Souza et al. [90] was approximately 3000 mg L-1, while those used in the study of Beltran et al. [89] was (21715 mg L-1), as shown in Table 6. Therefore, the large difference on the initial organic load of the effluents used
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almost sevenfold
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in the abovementioned studies, should be probably one of the main reasons justifying the lower efficiency of the combined ozonation -
M
A
activated sludge process, and thus not a reliable comparison can be performed by considering the results of the above studies.
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AOPs as post-treatment
According to the literature [91,92], there are two types of wastewater, which should be treated by a biological process followed by AOPs: (i)
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wastewater containing biorecalcitrant compounds, and (ii) the highly biodegradable industrial wastewater. Winery effluents belong to the second type of wastewater, and as a consequence, several studies have been performed in which firstly the highly biodegradable part of the
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winery wastewater was eliminated biologically and then the recalcitrant contaminants were degraded by post-treatment via the application of an AOP, as shown in Table 6. The removal efficiency of the combined biological and Fenton oxidation treatment of wine-distillery effluents (influent COD = 18500 mg L1
) was investigated by de Heredia et al. [93]. The application of biological oxidation as a single process reduced the COD between 75 and
94% and the phenolic content in the range of 54 to 79%, depending on the initial organic content. Regarding the biomass, its evolution 42
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follows the typical growth-cycle phases for batch cultivation: acclimatization period → exponential growth phase → stationary phase → death phase of microorganisms. From an industrial point of view, the most interesting period in the growth cycle of a batch microbial cultivation is the exponential growth phase, when the population of biomass is perfectly acclimatized to the substrate. In this period, the rate
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of production of biomass has been described by a first-order kinetic equation as shown in the study by de Heredia et al. [93]. Moreover, the
A
M
and TPh removals were higher than 90%.
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application of an advanced chemical post-treatment reduced the COD by 80%, with overall COD removal equal to 98%, while the aromatic
The efficiency of an SBR followed by homogeneous and heterogeneous photo-Fenton oxidation as a polishing step was investigated in the
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studies of Anastasiou et al. [94] and Ioannou et al. [95]. Biological oxidation resulted in about 50% COD and BOD5 reduction, and
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approximately 85% TSS reduction (influent COD = 16250 mg L-1; influent BOD5 = 3250 mg L-1) [94]. In this study, the effluent’s biodegradability was always low (about BOD5/COD= 0.2), regardless of the sampling point and the period of treatment. In general, organic matter degradation increases with increasing the treatment time by the homogenous Fenton’s reaction, reaching further COD and BOD5
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removal as high as 80% after 4 h of reaction. Finally, the combined SBR and homogeneous photo-Fenton oxidation resulted in the highest COD removal, even up to 95%. Additionally, according to Ioannou et al. [95], both the organic content (influent COD = 270 mg L-1), as well as the ecotoxicity of the effluents were reduced significantly during the homogeneous solar Fenton post-treatment, and reached additional values as high as 69%, 48%, 53% and 71% for COD, DOC, color and TPh, respectively. It is important to note that the biologically pretreated effluent was extremely toxic to D. magna (over 93% immobilization), while toxicity significantly decreases upon prolonged solar 43
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Fenton oxidation (e.g. at 27% after 240 min of treatment). Additionally, in this study, a comparison of the efficiency of the homogeneous and heterogeneous solar Fenton processes, concluded that the homogeneous system was the most efficient of the two. The authors reported that the efficiency of the heterogeneous process was limited by (i) light scattering effects caused by the high concentration of iron particles in
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the suspension, which inhibit the effective utilization of the photonic energy, and (ii) mass transfer limitations due to the heterogeneous
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N
matrix of the catalyst.
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The combined process of aerobic degradation in a long-term aerated storage followed by Fenton’s reagent oxidation was employed by Lucas et al. [96]. The results indicated that the aerobic biological degradation rates were between 76% and 96% for the COD removal at
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bench scale (4 L reactor), and between 64% and 96% at pilot scale (60 L reactor) (influent COD = 20000 mg L-1), for an HRT of 11 weeks
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and for an aeration time range from 2.4 h d-1 to 12 h d -1, respectively. The results of this study show that the degradation reached without aeration was very similar to the assays with aeration. However, harmful bad odors were produced, as result of the anaerobic biodegradation, and as a consequence, experiments with aeration were always preferable even with small aeration times. In contrast, the combined process
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(long-term aeration/Fenton reagent) led to a very high overall COD reduction that reached 99.5% when the mass ratio (R = H2O2/COD) used was equal to 2.5, maintaining constant the molar ratio H2O2/Fe2+ = 15. One of the main achievements of this combined process is the fact that the final winery effluents (COD residual = 100 mg L-1) met the Portuguese law for water reuse and discharge in water streams or on soil [96].
44
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Finally, solar photo-Fenton oxidation at bench scale was proved to be very efficient for the treatment of the winery effluents which were pretreated by a MBR, reaching an additional COD removal of approximately 70% (COD after MBR pre-treatment = 120 mg L-1), corresponding to a residual COD value of 33 mg L-1 [97]. The major part of COD was removed during first 30 min of chemical post-
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treatment (58%), while an additional 10% of COD was removed by increasing the treatment time to 90 min, after which a plateau was
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reached. The fast treatment realized during the first 30 min in which the major part of COD was removed from winery wastewater pretreated
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by MBR, is significant for a large-scale industrial application, since this can lead to a significant reduction in the operating costs as shorter
M
reaction times are required, although MBR pretreatment cost must be accounted for. Solar photo-Fenton oxidation was also able to
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significantly remove the color (75±2.2%), as well as the toxicity towards D. magna (100%) and the phytotoxicity towards three plant species (L. sativum, S. alba and S. saccharatum) to values lower than 28% (in terms of plant growth inhibition). The application of the
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abovementioned combined process at pilot and industrial scale proved to be a very effective treatment of winery wastewater [22], lowering the concentration of organic pollutants in the effluent to values below that of the Cypriot discharge limits regarding urban wastewater (i.e.
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residual COD < 30 mg L-1 and residual TSS < 10 mg L-1). The overall cost (i.e. investment, operation and maintenance cost) to set up an integrated MBR with an additional solar Fenton system was estimated to be 4 € m-3 for a treatment capacity of 50 m3 d -1 and five-year operation.
Figure 3 (d) shows that the most efficient process combination (AOPs as pre- and post-treatment) is the long-term aerated storage followed by Fenton oxidation [96], which achieved almost complete removal of organic load, at 99.5% in terms of COD (residual COD = 100 mg L45
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1
). Furthermore, the combination of an advanced biological treatment, such as an MBR with solar Fenton oxidation, seems to be a very
promising process, both for the elimination of the winery wastewaters’ organic load (residual COD < 30 mg L-1), as well as its ecotoxicity, even at pilot/industrial scale [22,97]. The evaluation of the potential toxicity of the winery wastewater after each treatment process remains a
U
knowledge gap in the literature, which requires further investigation.
A
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Summarizing, in Figure 4, the maximum organic load removal, as well as the influent and effluent organic load of the most efficient
M
processes of each treatment subcategory (i.e. physicochemical, membrane filtration and separation processes, biological processes (aerobic and anaerobic), advanced oxidation processes and combined biological and advanced processes (AOPs as pre- and post-treatment)) are
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shown, in order to clearly present the most effective technologies applied for the treatment of winery wastewater.
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8. Conclusions and future perspective
The various wine processing systems applied at each winery, generate wastewater with specific properties, and therefore, establishing a
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general agreement on the most suitable and cost-effective process for their treatment is an arduous task. Numerous winery wastewater treatment processes are currently available, but the development of alternative process combinations is required, in order to increase the efficiency of removal of both the recalcitrant organic compounds, as well as ecotoxicity, with a simultaneous reduction of the investment and operational costs.
46
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The physicochemical processes (i.e. coagulation/flocculation, EC) have been found to be effective for the pre-treatment of winery wastewater, and more specifically, for lowering the TSS, the turbidity, as well as a part of the organic content to levels which can facilitate further treatment by other biological, membrane filtration and separation or advanced oxidation processes.
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Biological treatment is particularly appropriate to the treatment of winery wastewater, since the major part of its organic load is readily
N
biodegradable. The newly developed MBR systems show high potential, although the small number of studies available does not provide
A
conclusive findings. Although biological processes have been found to be very effective for the treatment of winery wastewater, yielding
M
high rates of organic load removal, the residual organic load of the effluents of aerobic/anaerobic biological treatment most often is higher
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than the limits stated in the European Directive 91/271/EEC regarding urban wastewater, therefore a further pre- or post-treatment before its
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safe disposal into the environment is required. Unfortunately, the data concerning the application of membrane filtration and separation processes for the treatment of winery wastewater are limited (i.e. only two published scientific studies till now), and as a consequence insufficient knowledge on their efficiency is so far
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available. The RO process seems to be a promising process. Nevertheless, it should be noted that the appropriate management of the concentrate produced and the fouling of the membranes, are the two major problems that need to be addressed. The literature suggests that advanced chemical oxidation processes hold good promises, with homogeneous solar Fenton oxidation, which appears to be a very effective process, while ozonation seems also to be a promising treatment process. However, the majority of the studies available refer to a bench or pilot scale and, therefore, further studies at pilot and full industrial scale are needed. 47
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The combination of AOPs and biological treatment (as pre- or post-treatment) can lead to a higher level of COD reduction than any singlestage treatment under the same operating conditions. More specifically, in the case of winery effluents, the use of AOPs as post-treatment of biological processes was found to be the most effective combination since it permits almost complete purification, compared to AOPs used
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as pre-treatment.
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An appraisal of the investment and operational costs of the processes considered for the treatment of winery wastewater is of major
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importance. In many studies, various aspects of the treatment cost are discussed, but very few studies specifically focus on it. Even in these
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cases, it is very difficult to compare the technologies among the various studies available, as the cost analyses are often based on different
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assumptions and, consequently, they can lead to very different treatment cost estimation. Hence, in spite of the intense scientific effort carried out by several research groups to study the technical feasibility of a wide variety of winery effluent treatment processes, the lack of
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information on cost makes difficult the determination of the Best Available Technology Not Entailing Excessive Cost (BATNEEC). As a consequence, careful economic analysis should be conducted to determine whether the most efficient combined processes are cost-effective,
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environmentally sensitive and technically reliable, allowing their full application at industrial scale. Finally, the set of physico-chemical and biological parameters used for the evaluation of the efficiency of the various processes, either standalone or combined ones, should be enlarged to include bioassays, like for example ecotoxicity and phytotoxicity tests.
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9. Acknowledgments
This study was performed, with the contribution of the LIFE financial instrument of the European Union, as part of the LIFE project “Advanced systems for the enhancement of the environmental performance of WINEries in Cyprus” WINEC LIFE08 ENV/CY/000455,
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aiming to support the development and implementation of policies and strategies especially focusing on the sustainable management and
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wastewater management of wineries. Nireas, International Water Research Center of the University of Cyprus (NEA
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Research Promotion Foundation.
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ΥΠΟΔΟΜΗ/ΣΤΡΑΤΗ/0308/09), is co-financed by the European Regional Development Fund and the Republic of Cyprus through the
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[106] D. Bolzonella, M. Zanette, P. Battistoni, F. Cecchi, Treatment of winery wastewater in a conventional municipal activated sludge
A CC
process: five years of experience. Water Sci. Technol. 56 (2) (2007) 79-87.
[107] P.J. Strong, Fungal remediation and subsequent methanogenic digestion of sixteen winery wastewaters. S. Afr. J. Enol. Vitic. 29 (2) (2008) 85-93.
[108] A. Eusebi, P. Nardelli, G. Gatti, P. Battistoni, F. Cecchi, From conventional activated sludge to alternate oxic/anoxic process: the optimisation of winery wastewater treatment. Water Sci. Technol. 60 (4) (2009) 1041-1048. 65
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[109] G. Guglielmi, G. Andreottola, P. Foladori, G. Ziglio, Membrane bioreactors for winery wastewater treatment: case-studies at full scale. Water Sci. Technol. 60 (5) (2009) 1201-1207.
[110] S. López-Palau, J. Dosta, J. Mata-Alvarez, Start-up of an aerobic granular sequencing batch reactor for the treatment of winery
N
U
wastewater. Water Sci. Technol. 60 (4) (2009) 1049-1054.
M
Technol. 62 (12) (2010) 2754-2759.
A
[111] D. Bolzonella, F. Fatone, P. Pavan, F. Cecchi, Application of a membrane bioreactor for winery wastewater treatment. Water Sci.
ED
[112] S. López-Palau, A. Pinto, N. Basset, J. Dosta, J. Mata-Álvarez, ORP slope and feast-famine strategy as the basis of the control of a
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granular sequencing batch reactor treating winery wastewater. Biochem. Eng. J. 68 (2012) 190-198.
[113] A. Massot, K. Esteve, P. Noilet, C. Meoule, C. Poupot, M. Mietton-Peuchot, Biodegradation of phytosanitary products in biological
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wastewater treatment. Water Res. 46 (2012) 1785-1792.
[114] P.J. Welz, J-B. Ramond, D.A. Cowan, S.G. Burton, Phenolic removal processes in biological sand filters, sand columns and microcosms. Bioresource Technol. 119 (2012) 262-269.
66
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[115] P.J. Welz, Z. Palmer, S. Isaacs, B. Kirby, M. le Roes-Hill, Analysis of substrate degradation, metabolite formation and microbial community responses in sand bioreactors treating winery wastewater: A comparative study. J. Environ. Manage. 145 (2014) 147-156.
[116] B. Fernández, I. Seijo, G. Ruiz-Filippi, E. Roca, L. Tarenzi, J. Lema, Characterization, management and treatment of wastewater from
N
U
white wine production. Water Sci. Technol. 56 (2) (2007) 121-128.
A
[117] Th. Arnaud, Treatment of winery wastewater with an anaerobic rotating biological contactor. Water Sci. Technol. 60 (2) (2009) 371-
M
379.
ED
[118] R. Rajinikanth, R. Ganesh, R. Escudie, I. Mehrotra, P. Kumar, J.V. Thanikal, M. Torrijos, High rate anaerobic filter with floating
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supports for the treatment of effluents from small-scale agro-food industries. Desal. Water Treat. 4 (1-3) (2009) 183-190.
[119] C. García-Diéguez, F. Molina, E. Fernández, E. Roca, Control of Re-startup of Anaerobic USBF Reactors after Short Stops. Ind. Eng.
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Chem. Res. 49 (10) (2010) 4748-4755.
[120] A. Vlyssides, E. Barampouti, S. Mai, A. Stamatoglou, E. Tsimas, Alternative biological systems for the treatment of vinasse from wine. Water Sci. Technol. 62 (12) (2010) 2899-2904.
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[121] C. García-Diéguez, F. Molina, E. Roca, Multi-objective cascade controller for an anaerobic digester. Process Biochem. 46 (4) (2011) 900-909.
[122] R. Camarillo, J. Rincón, Effect of inhibitory compounds on the two-phase anaerobic digestion performance of diluted wastewaters
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U
from the alimentary industry. Chem. Eng. J. 193 (2012) 68-76.
A
[123] E. Rodríguez, G. Márquez, J.C. Carpintero, F.J. Beltrán, P. Álvarez, Sequential use of bentonites and solar photocatalysis to treat
M
winery wastewater. J. Agric. Food Chem. 56 (24) (2008) 11956-11961.
ED
[124] M.A. Martın Santos, J.L. Fernandez Bocanegra, A. Martın Martın, I. Garcıa Garcıa. Ozonation of vinasse in acid and alkaline media. J.
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Chem. Technol. Biotechnol. 78 (2003) 1121-1127.
[125] M. Hadavifar, A.A. Zinatizadeh, H. Younesi, M. Galehdar. Fenton and photo-Fenton treatment of distillery effluent and optimization
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of treatment conditions with response surface methodology. Asia-Pac. J. Chem. Eng. 5 (2010) 454-464.
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Figure Captions
Figure 1: Number of scientific studies published per year regarding the treatment of winery wastewater (from 1995 to 2014). Figure 2: Factors affecting the treatment efficiency of physicochemical, biological, membrane filtration and separation and advanced chemical
U
oxidation processes.
N
Figure 3: Organic load removal efficiency and residual organic load of (a) various physicochemical processes, (b) biological processes, (c) AOPs,
M
A
and (d) combined biological + AOPs processes used for winery wastewater treatment, according to the scientific literature. Figure 4: Maximum organic load removal of the most efficient processes of each treatment subcategory (i.e. physicochemical, membrane filtration
A CC
EP T
ED
and separation processes, biological processes, advanced oxidation processes and combined processes) for winery wastewater.
69
ED
EP T
A CC
Figure 1
70
A
M
N
U
SC RI PT
ED
EP T
A CC
Figure 2
71
A
M
N
U
SC RI PT
SC RI PT M
A
N
U
(a)
CODresidual = 418 mg L-1
CODresidual = 13810 mg L -1 -1
ED
CODresidual = 15200 mg L
CODresidual=21625 mg L-1
EP T
CODresidual = 2118 mg L-1
A CC
CODresidual = 4790 mg L-1
The information from Figure 3(a) is taken from: [25-28,31]
72
SC RI PT o
-1
Residual COD (mg L ) 4560 680-3300 185 ~640 1233 175-577
A CC
Bar N 1 2 3 4 5 6
EP T
ED
M
A
N
U
(b)
o
Bar N 7 8 9 10 11 12
-1
Residual COD (mg L ) 82 46-314 50-4200 75-4120 2130 3900
o
Bar N 13 14 15 16 17 18
-1
Residual COD (mg L ) 4040 236-5415 8110 3200-5920 259-42900 582-750
o
Bar N 19 20 21
-1
Residual COD (mg L ) 132 160 170
The information from Figure 3(b) is taken from:[4,5,8,10,19,20,32-35,37-44,46,50-62,106,108-112,114,115,117-120,122]
73
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112 mg L-1 164 mg L 1850 mg L-1 1170-4725 mg L 1738 mg L-1
-1
-1
7000 mg L
311 mg L
1680 mg L
1042 mg L
U
-1
-1
-1
-1
2403 mg L
3337 mg L-1
M
A
N
1986 mg L
(c)
-1
451 mg L
-1
-1
A CC
EP T
ED
90400 mg L-1
The information from Figure 3(c) is taken from:[3, 71-80, 124, 125]
74
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132 mg L-1
147 mg L-1
812 mg L
-1
-1
100 mg L
(d)
-1
370 mg L
-1
A CC
EP T
ED
M
A
N
U
8686 mg L
The information from Figure 3(d) is taken from:[7, 88-90, 93, 94, 96]
* www: winery wastewater; ww: wastewater
Figure 3
75
SC RI PT U N A M ED EP T A CC Bar N 1 2 3 4 5 6 7
o
-1
Residual COD (mg L )
1550 5353 2500 5500 7587 8600 8000
418 140 75 110 75 172 160
Influent COD (mg L )
-1
Bar N 8 9 10 11 12 13 14
o
-1
-1
Influent COD (mg L )
Residual COD (mg L )
4400 2250 *(DOC) 970 3300 2958 20000 18500
132 112 *(DOC) 164 132 147 100 370
The information from Figure 4 is taken from:[7,8,28,32,42,44,50,57,62,67,74,76,90,93,96]
76
SC RI PT Figure 4
Table 1: Reported qualitative characteristics of winery wastewater
Demand (COD)
L-1
Biochemical
mg -1
(BOD5)
Organic mg
ED
Total
Carbon (TOC)
Conductivity (EC)
cm-1
A CC
22418
6570
[4,6,10,30,32-34,56,71,90,94,98,99,102,103]
41
7363
1876
[3,8,73,77,80,90,98]
2.5
12.9
5.3
[3,5,7,10,14,26-28,30-32,36,39,41,42,51,61,64,71,73,77,7981,90,93,98-105]
mS
Total Solids (TS)
mg
1.1
5.6
3.46
[14,31,42,66,81,90,94,101,104]
748
18332
8660
[6,66,94,98,99]
661
12385
5625
[6,34,98,99]
66
8600
1700
[4,6,10,26-28,31-35,39,42,56,61,66,77,81,94,98-103]
-1
L
Volatile mg
Solids (TVS)
L-1
Suspended Solids mg (SS)
203
36,39,41,42,50,51,54,56,61,66,71,73,77,79,81,90,94,98-105]
L
Electrical
Total
11886 [3-8,10,27,28,30-
49105
-1
-
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pH
320
M
Oxygen Demand L
Mean References
U
Chemical Oxygen mg
Min Max
N
Unit
A
Parameter
-1
L
77
(TP)
L-1
Total
Nitrogen mg
(TN)
-1
2.1
280
53
[4,6,10,27,30,34-35,39,42,66,102,103]
10
415
118
[6,8,10,32,34,42,66,102,103]
205
[3,4,6,7,27,32,35,66,71,73,77,79,90,98,99,101,103]
L
phenolic mg L
A CC
EP T
ED
M
A
N
compounds (TPh)
0.51 1450
-1
U
Total
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Total Phosphorous mg
78
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Table 2: Physicochemical processes applied for the treatment of winery wastewater
TSS= 213-320 mg L-1
Measu re of treatm ent efficie ncy
Winery wastewater (Italy)
Chemical precipitation with chelating agents (trimercaptotria zine (TMT)) at pilot scale
COD, TSS, Cu, and Zn remova l and cost estimat ion
Operating conditions: capacity= 2.1 m3; TMT dose= 0.84 mL; pH= 8.5; reaction time= 15 min
COD, BOD and TP remova l
EC operating conditions: capacity= 1 L; I= 2 A; U= 10 V; treatment time= 10-40 min
1500-17000
BOD= 1500-2500 mg L-1
A CC
TP= 13 mg L-1
Winery wastewater after pH adjustment to 6.0 (Israel)
Electrocoagulat ion (EC) followed by aquatic plants treatment technology (H. umbellate and E. crassipes)
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COD= mg L-1
ED
Zn= 0.14-1.47 mg L-1
pH= 3.8-4.0
Reference s
[25]
COD removal= 9%; TSS removal= 90%; Cu removal= 96%; Zn removal= 76%; cost= 14.6 € m -3
M
Cu= 0.68-1.63 mg L-1
Main findings/Removal efficiency
U
Technology characteristics
N
COD= 3090-7438 mg L-1
Matrix
A
Winery wastewater initial quality characteristics
[30]
COD removal= 28.2-41.9%; BOD removal= 16.427.9%; TP removal= 89.2% Further purification with aquatic plants treatment technology: COD removal= 98.2 %; BOD removal= 97.5%
47
VSS= 2820-6360 mg L-1 Turbidity= 319-782 NTU TPh= 1.06-1.35 mg L1
Winery wastewater (Italy)
COD= 1550 mg L-1
ED
TSS= 750 mg L-1
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Turbidity= 180 NTU
pH= 4.9-7.0
COD= 2120-4940 mg L-1
EC= 723-1472 mS cm-1
pH= 5.2 COD= 25200-28640 mg L-1 TSS= 1240 mg L-1
Combined LTAS process with coagulation (Ca(OH)2) operating conditions: volume= 60 L; flow rate= 125 L h-1; aeration period= 4 h d-1; HRT= 11 weeks
COD, TSS and turbidit y remova l
Operating conditions:capacity= 1 L; chitosan dose= 20-600 mg L-1; pH= 4-6.8; T= 20 oC; treatment time= 92 min
[28]
COD removal= 73%; turbidity removal= 92%; TSS removal= 80% No significant difference on the performance was observed with pH change
Two-step sedimentation reactor with the addition of organosepiolite and sepiolite particles as flocculants
COD, TSS and turbidit y remova l
Operating conditions: capacity= 100 mL; flocculants dose= 5 g L-1; treatment time= 11 min
Winery wastewater (Turkey)
Electrocoagulat ion (EC) using aluminum (Al) and iron (Fe)
COD, turbidit y and color remova
Operating conditions for Fe electrode: capacity= 1.5 L; pH= 7; current density= 300 A m-2; T= 25 oC; operating time= 90 min
130.3-
[27]
COD removal= 31.5-37.9%; turbidity removal= 92.6%; TSS removal= 95.4%
Winery wastewater before and after neutralization of pH (Israel)
A CC
TSS= 1400-1600 mg L-1
Turbidity= 163.3 NTU
Coagulation using a natural organic coagulant (chitosan)
Coagulation operating conditions: capacity= 500 mL; pH= 5.0; coagulant dose= 30 mL; treatment time= 47 min
COD removal= 84.5%; turbidiy removal= 96.6%; TSS removal= 99.1%; VSS removal= 98.7%
M
pH= 6.8
SC RI PT
TSS= 3490-7660 mg L-1
COD, TSS, VSS and turbidit y remova l
U
COD= 31369-38391 mg L-1
Coagulation / flocculation process using four different coagulants (FeSO4, Al2(SO 4)3, FeCl3 and Ca(OH)2) combined with long-term aerated storage (LTAS)
N
Winery wastewater (Portugal)
A
pH= 4.25-4.56
[26]
COD removal= 20-40%; turbidity removal= 44%; TSS removal= 98%
[31]
COD removal= 46.6%; turbidity removal= 92.3%;
48
electrodes
l
SC RI PT
EC= 3.5 mS cm-1
color removal= 80.3%
Color= 6500 Pt-Co
Operating conditions for Al electrode: capacity= 1.5 L; pH= 5.2; current density= 300 A m -2; T= 25 oC; operating time= 120 min
Turbidity= 2490 NTU
COD removal= 48.5%; turbidity removal= 98.6%; color removal= 97.2% Operating conditions: capacity= 1000 mL; coagulants’ dose= 16-490 mg polymer mg clay-1; treatment time= 10 min
[29]
U
Light intensit y and cost estimat ion
N
Coagulation / flocculation based on the use of claypolymer nanocomposite s ((i) polyDADMAC (PD)-sepiolite; (ii) chitosansepiolite and (iii) PDVolclay bentonite)
PD-sepiolite: Light intensity= 70%
A
Winery wastewater (Israel)
Chitosan-sepiolite: Light intensity= 78% PD-bentonite: Light intensity= 68% Cost= 1.1-1.4 € m -3 treated wastewater
A CC
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ED
M
Data not given
49
Table 3:Guidelines and limits ofwinery effluentsdischarge in aquatic ecosystems and landin Australia and California
Discharge limits Country
Australia* Winery wastewater Discharge limits for irrigation
-
-
Spray irrigation orfrost protection
Dripirrigati on
6.5-9
5-8.5
-
-
-
-
-
-
80
160 -
pH COD (mg L-1) -1
-
15
1500 (kg BOD5ha 1 month-1)
TN (mg L-1)
0.5
5 (< 500 Kg N ha-1year1 )
-
TP (mg L-1)
0.05
0.05
-
TSS (mg L-1)
50
Gross solids should be removed
80
TDS (mg L-1)
90%; aromatic compounds removal> 90%
COD= 20000 mg L
BOD5= 11000 mg L-1
Winery wastewater (Portugal)
TSS= 8600 mg L-1
COD removal
-1
COD= 264-270 mg L
A
DOC= 100-110 mg L-1
BOD5= 111-113 mg L1
TSS= 225-245 mg L-1
Winery wastewater (Cyprus)
Operating conditions: biological system capacity= 4 and 60 L; HRT= 11 weeks; aeration times= 2.412 h d-1; oxidation system capacity= 500 mL; H2O2/Fe2+= 15; pH= 3.5; T= 30 oC
[96]
Pilot-scale long-term biological aerated storage: capacity= 60L; COD removal= 64-96% for aeration time 2.4-12 h d-1
EP CC
pH= 8.3
Combined process: COD removal= 95%
Bench-scale long-term biological aerated storage: capacity= 4L; COD removal= 88-96% for aeration time= 2.4-12 h d-1
TE
TPh= 680 mg L-1
Combined long-term aerated storage (at bench and pilot scale) and Fenton oxidation
M
-1
D
pH= 3.9
A
Photo-Fenton process: COD removal= 80%
Combined process:overall COD removal= 99.5% Combined Sequential Batch Reactor (SBR) and homogeneous or heterogeneous solar photo-
COD, DOC, color, TPh removal and ecotoxicity (D. magna)
Operating conditions of post-treatments: oxidation system capacity= 300 mL; Fe2+= 5-20 mg L-1; H2O2= 50-1000 mg L-1; FeSBA-15= 100 mg L-1; T = 25±0.1 °C Homogenous solar Fenton: COD removal= 69%; DOC removal= 48%; TPh removal= 71%; toxicity (D. magna)= 27% (immobilization)
57
[95]
Fenton oxidation
COD= 120 mg L
DOC= 30 mg L-1 BOD5< 5 mg L-1 TSS= 8 mg L-1 TN= 4 mg L-1
pH= 7.8-8.5 -1
COD= 150-210 mg L DOC= 30-60 mg L-1
Winery wastewater (Cyprus)
BOD5< 5 mg L-1 TSS= 7-11 mg L-1
COD, DOC and color removal, toxicity (D. magna) and phytotoxicit y (S. alba, L. sativum, S. saccharatu m)
Operating conditions of post-treatment: oxidation system capacity= 300 mL; pH= 3; Fe2+= 1-10 mg L-1; H2O2= 25-500 mg L-1; T= 25±0.1 oC
Combined Membrane Bioreactor (MBR) and solar Fenton oxidation at pilot and industrial scale
COD, DOC and color removal, toxicity (D. magna) and phytotoxicit y (S. alba, L. sativum, S. saccharatu m)
Operating conditions of post-treatment:oxidation system capacity= 60L; pH= 3; Fe2+= 1-5 mg L-1; H2O2= 100-750 mg L-1
[97]
COD removal= 70±3.3%; DOC removal= 53±3.7%; color removal= 75±2.2%; elimination of toxicity towards D. magna; plant growth inhibition< 28%
COD removal= 85%; DOC removal= 62-68%; color removal= 80%; elimination of toxicity towards D. magna; plant growth inhibition< 5.2%; Overall investment and operational cost of MBR + solar Fenton= 4 € m-3 for the treatment of 50 m3 d-1
A
CC
EP
TE
D
M
A
N
U
TN= 1-1.6 mg L-1
Combined Membrane Bioreactor (MBR) and solar photoFenton oxidation at bench scale
PT
Winery wastewater (Cyprus)
-1
RI
pH= 8.2
Heterogeneous solar Fenton process: COD removal= 20%; DOC removal= 20%
SC
TPh= 3.8-4.7 mg L-1
58
[22]
