Accepted Manuscript Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes Francisca C. Moreira, Rui A.R. Boaventura, Enric Brillas, Vítor J.P. Vilar PII:
S0043-1354(15)00102-5
DOI:
10.1016/j.watres.2015.02.029
Reference:
WR 11165
To appear in:
Water Research
Received Date: 18 November 2014 Revised Date:
26 January 2015
Accepted Date: 16 February 2015
Please cite this article as: Moreira, F.C., Boaventura, R.A.R., Brillas, E., Vilar, V.J.P., Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes, Water Research (2015), doi: 10.1016/j.watres.2015.02.029. 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.
ACCEPTED MANUSCRIPT BIODEGRADABLE FRACTION + RECALCITRANT FRACTION
EFFLUENT DISCHARGE INTO THE ENVIRONMENT OR FURTHER BIOLOGICAL OXIDATION
BIOLOGICAL OXIDATION SYSTEM
ELECTROLYTIC SYSTEM
IMMOBILIZED BIOMASS REACTOR
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CPCs STRUCTURE
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Remediation of a winery wastewater combining aerobic biological
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oxidation and electrochemical advanced oxidation processes
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Francisca C. Moreira a, Rui A.R. Boaventura a, Enric Brillas b, Vítor J.P. Vilar a,*
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a
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Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr.
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Roberto Frias, 4200-465 Porto (Portugal)
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b
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Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain)
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LSRE - Laboratory of Separation and Reaction Engineering - Associate Laboratory LSRE/LCM,
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Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física,
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Corresponding author. Tel.: +351 918257824; Fax: +351 225081674; E-mail address:
[email protected] (Vítor J.P. Vilar) 1
ACCEPTED MANUSCRIPT Abstract
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Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery
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wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as
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polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a
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biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical
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advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or
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transform them into simpler ones that can be further biodegraded. The biological oxidation led to
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above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-
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day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant
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fraction corresponding to 130 mg L-1 of DOC, 380 mg O2 L-1 of COD and 8.2 mg caffeic acid
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equivalent L-1 of total dissolved polyphenols. Various EAOPs such as anodic oxidation with
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electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar
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PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant
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containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a
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carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic
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collectors (CPCs). The influence of initial Fe2+ concentration and current density on the PEF
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process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2
EF > PEF > SPEF (see Fig. 5b), as predicted by the increasing rate
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of Fe3+ to Fe2+ regeneration of these EAOPs. During the SPEF process, the H2O2 concentration
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diminished to very low values, 4-9 mg L-1, when more pronounced DOC abatement was patent, 60-
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120 min, which confirms the operation at 25 mA cm-2 as a good option since a low j might not
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ensure the H2O2 occurrence during all the SPEF process.
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Fig. 5c outlines that the AO-H2O2 and EF processes were ineffective on the total dissolved
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polyphenols degradation. In contrast, the SPEF treatment was able to reduce these compounds to
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values as low as 0.4 mg caffeic acid equivalent L-1 after a short time of 120 min, whereas the PEF
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process reduced polyphenols concentration up to 2.6 mg caffeic acid equivalent L-1 at 180 min. The SPEF process under the best conditions considered in the current study reached DOC and
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COD removals of 86% and 68%, respectively, in relation to the biologically treated effluent after
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240 min of treatment, with energy consumptions of 45 kWh (kg DOC)-1 and 5.1 kWh m-3. Fig. 5d
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reveals that the COD decay was similar (for times below 90 min) or lower (for times above 90 min)
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than the DOC abatement, thereby suggesting a contribution of the particulate organic compounds to
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the COD value. A decrease of 54% in the total nitrogen content was observed during the SPEF
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process (see Table 1), which can be linked with the retention of some non-dissolved N-compounds
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into the precipitate during the EAOP since the total dissolved nitrogen remained unaffected. Table 1
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also shows that at 240 min of SPEF, COD and BOD5 complied with the Portuguese and the
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European legislation limits for discharge of WWTPs final effluents (Decree-Law no. 236/98 and
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Directive no. 91/271/CEE, respectively), in contrast with TSS, total nitrogen and total phosphorous
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parameters (total phosphorous only exceeded the European limit). Moreover, color, odor, NH4+,
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NO3- and SO42- parameters were in agreement with the Portuguese targets, but pH and total
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dissolved iron surpassed the limits. In this context, the final SPEF solution was neutralized to pH
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6.2 with subsequent sedimentation for 30 min with a resultant supernatant effluent displaying a total
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dissolved iron below the detection limit (0.13 mg L-1), a total phosphorous concentration of 0.35 mg
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L-1 and 55 mg TSS L-1 but without change on total nitrogen. Therefore, besides the application of a
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further step comprising the effluent neutralization and subsequent precipitation of the settleable
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compounds, the initial biological oxidation should be enhanced and include nitrifying and
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denitrifying
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bacteria
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neutralization/precipitation step led to the formation of 26 mL of sludge per L of treated winery
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wastewater that require further adequate treatment. Regarding the combination of the biological oxidation and SPEF processes, very high
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abatements on DOC, COD and BOD5 parameters of ca. 99% were attained, which is in agreement
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with the great COD removals of 95% and above 99% accomplished by Anastasiou et al. (2009) and
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Lucas et al. (2009b) for the combination of a biological oxidation and a further photo-Fenton or
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Fenton process, respectively.
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3.3.5. Evolution of generated carboxylic acids and inorganic ions during EAOPs
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The ion-exclusion HPLC analysis on LMCA revealed the formation of oxalic (tr = 8.5 min) and
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malic (tr = 13.2 min) acids during the AO-H2O2, EF, PEF and SPEF treatments. These acids are
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expected to be formed from the oxidative cleavage of the benzenic ring of aromatic intermediates
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(Brillas et al., 2009). Malic acid can be subsequently transformed into oxalic acid, which is an
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ultimate acid that can be directly mineralized to CO2 (Vel Leitner and Doré, 1997; Oturan et al.,
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2008; Garcia-Segura and Brillas, 2011). Malic and oxalic acids may be primordially present in
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solution as Fe(III)-carboxylate complexes because the iron is mainly available as Fe3+ during the
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processes. Fig. 6a illustrates that in the AO-H2O2 process the LMCA were accumulated in very low
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amounts with a contribution never superior than 1.2% for DOC, suggesting inefficiency of this
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process to convert high-molecular aromatic compounds into the simple LMCA, in corroboration
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with the low mineralization attained. In contrast, in EF both acids were accumulated in larger extent
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with maximum concentrations of ca. 10 mg C L-1 for oxalic acid (see Fig. 6b) and ca. 5 mg C L-1 for
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malic acid (see Fig. 6c), corresponding to 24% of DOC due to LMCA at the end of the process (see
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Fig. 6a). In PEF and SPEF, both oxalic and malic acids were accumulated in low extent, below 3.0
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mg C L-1 (Figs. 6b and c), which might be related to a fast photolysis rate of Fe(III)-oxalate and
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Fe(III)-malate complexes.
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ACCEPTED MANUSCRIPT The mineralization of organic compounds is expected to be followed by the loss of their
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nitrogen and sulfur atoms in the form of inorganic ions such as NH4+, NO3-, NO2- and SO42-. In the
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SPEF process under the best conditions, NO2- was not found as expected due to their instability in
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strong oxidant media. NH4+, NO3- and total dissolved nitrogen concentrations remained almost
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unaffected, suggesting the inability of SPEF to degrade dissolved recalcitrant organic N-
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compounds. As aforementioned, total nitrogen decreased in an extent of 54%, pointing to the
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retention of non-dissolved N-compounds into the precipitate. On the other hand, SO42- was
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gradually released into the solution up to ca. 150 mg L-1 at 240 min, which can be mainly attributed
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to the dissolution of SO42- retained in the foam and also to a possible degradation of organic
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compounds containing sulfur in their structure.
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3.4. Biodegradability enhancement during SPEF process
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As abovementioned, alternatively to the application of a SPEF process to achieve organic loads
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in agreement with the discharge limits, the electrochemical process can be applied as a pre-
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treatment to transform recalcitrant compounds into simpler ones that can be subsequently
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biodegraded, thereby reducing the overall cost of the treatment. In this context, the biodegradability
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of the winery wastewater was assessed along the SPEF process by means of respirometry assays.
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Fig. 7 reveals the bCOD/COD ratios attained throughout the treatment. Maximal bCOD/COD of 0.1
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were achieved for times of 40 and 90 min, corresponding to low biodegradable samples according
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to Ballesteros Martín et al. (2010). However, the short times employed in the respiration tests, ca.
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30 min, could be insufficient to degrade the total content of slowly biodegradable organic matter
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(Kümmerer et al., 2004), and, furthermore, the applied biomass was not adapted to degrade the
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organic matrix of the winery wastewater, probably reaching lower efficiencies than an adapted
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biomass test as Zahn-Wellens.
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4. Conclusions
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ACCEPTED MANUSCRIPT The raw winery wastewater exhibited a high biodegradability and, as a consequence, the
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biological oxidation treatment attained high DOC, COD and BOD5 removals above 97%. However,
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the biologically treated effluent was constituted of a bioresistant fraction comprising 130 mg L-1 of
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DOC, 380 mg O2 L-1 of COD and 8.2 mg caffeic acid equivalent L-1 of total dissolved polyphenols
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and a subsequent EAOP was then employed to mineralize the recalcitrant compounds or transform
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them into simpler ones. The degradation of the winery effluent by EAOPs could be efficiently
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carried out using 25 ºC and pH of 2.8 at a current density of 25 mA cm-2 and, for Fenton’s reaction
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based processes, an initial Fe2+ concentration of 35 mg L-1. The relative oxidative capability of
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EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF, with DOC removals on the
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biologically treated effluent of 36%, 54%, 84% and 86%, respectively, after 240 min of reaction.
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The poor DOC removal attained in AO-H2O2 revealed a small ability of BDD(•OH) generated at the
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anode surface to react with recalcitrant winery wastewater compounds. In EF, the production of
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•
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additional •OH production induced by UVA or solar radiation, respectively, along with the possible
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direct photolysis of complexes formed between Fe3+ and some organic intermediates, led to the
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fastest reaction rates. The SPEF process under the best conditions chosen in the present study
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attained removals of 86% for DOC and 68% for COD regarding the biologically treated effluent
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after 240 min of treatment, with energy consumptions of 45 kWh (kg DOC)-1 and 5.1 kWh m-3. At
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this time of SPEF, a total dissolved polyphenols content of 0.35 mg caffeic acid equivalent L-1 was
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found and color, odor, COD, BOD5, NH4+, NO3- and SO42- parameters complied with the European
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and/or Portuguese legislation limits for discharge of WWTPs final effluents. However, to achieve
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total nitrogen, total phosphorous, pH, total dissolved iron and TSS targets to discharge the winery
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wastewater into the environment, the biological oxidation treatment must be optimized to provide
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the removal of nitrogen and additional neutralization and precipitation steps should succeed the
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ACCEPTED MANUSCRIPT SPEF process. The respirometry assays revealed low biodegradability enhancement along the SPEF
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process.
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Acknowledgements
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Financial support was partially provided by (i) PEst-C/EQB/LA0020/2013 project, co-financed by
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FCT (Fundação para a Ciência e a Tecnologia) and FEDER (Fundo Europeu de Desenvolvimento
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Regional) under COMPETE program (Programa Operacional Fatores de Competitividade) of
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QREN (Quadro de Referência Estratégico Nacional); (ii) NORTE-07-0162-FEDER-000050
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project, co-financed by FEDER, QREN and ON2 program (Programa Operacional Regional do
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Norte); and (iii) funds of the Pluridisciplinar project SOLARVIN (PP-IJUP2011-46) from the
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University of Porto. F.C. Moreira acknowledges her Ph.D. fellowship SFRH/BD/80361/2011
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supported by FCT. V.J.P. Vilar acknowledges the FCT Investigator 2013 Programme
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(IF/01501/2013).
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Soares, P., Silva, T.C.V., Manenti, D., Souza, S.A.G.U., Boaventura, R.R., Vilar, V.P., 2014. Insights into real cotton-textile dyeing wastewater treatment using solar advanced oxidation processes. Environmental Science and Pollution Research 21(2), 932-945.
705 706 707
Souza, B.S., Moreira, F.C., Dezotti, M.W.C., Vilar, V.J.P., Boaventura, R.A.R., 2013. Application of biological oxidation and solar driven advanced oxidation processes to remediation of winery wastewater. Catalysis Today 209, 201-208.
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Sun, Y., Pignatello, J.J., 1993. Photochemical reactions involved in the total mineralization of 2,4-D by Fe3+/H2O2/UV. Environmental Science & Technology 27(2), 304-310.
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ACCEPTED MANUSCRIPT Vel Leitner, N.K., Doré, M., 1997. Mecanisme d'action des radicaux OH⋅ sur les acides glycolique, glyoxylique, acetique et oxalique en solution aqueuse: Incidence sur la consammation de peroxyde d'hydrogene dans les systemes H2O2/UV et O3/H2O2. Water Research 31(6), 1383-1397.
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Wang, C.-T., Chou, W.-L., Chung, M.-H., Kuo, Y.-M., 2010. COD removal from real dyeing wastewater by electro-Fenton technology using an activated carbon fiber cathode. Desalination 253(1–3), 129-134.
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Wang, L.K., Shammas, N.K., Hung, Y.-T.E., 2009. Advanced biological treatment processes, Handbook of enviromental engineering, Vol. 9, Humana Press, New York.
718 719 720
Zhu, X., Tian, J., Liu, R., Chen, L., 2011. Optimization of Fenton and electro-Fenton oxidation of biologically treated coking wastewater using response surface methodology. Separation and Purification Technology 81(3), 444-450.
721 722 723
Zuo, Y., Hoigne, J., 1992. Formation of hydrogen peroxide and depletion of oxalic acid in atmospheric water by photolysis of iron(III)-oxalato complexes. Environmental Science & Technology 26(5), 1014-1022.
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ACCEPTED MANUSCRIPT Figure captions
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Fig. 1. Research articles on winery wastewater remediation per year arranged by treatment process
726
(source: http://www.scopus.com/, December 2013, search for “winery wastewater treatment” with
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further manual refinement to exclude misclassified articles and distribute them by treatment
728
process).
729
Fig. 2. Assessment of the biological oxidation efficiency in the treatment of the raw winery
730
wastewater in terms of () DOC removal, () total dissolved polyphenols and () pH.
731
Fig. 3. Influence of initial Fe2+ concentration on (a) normalized DOC removal and (b) total
732
dissolved iron concentration as a function of time in PEF degradations of the winery wastewater
733
after biological oxidation using a BDD anode, 25 ºC, j = 100 mA cm-2 and pH = 2.8. [Fe2+]0: ()
734
20, () 35 and () 70 mg L-1.
735
Fig. 4. Effect of current density (j) on (a) normalized DOC removal, (b) energy consumption per
736
unit DOC mass, (c) H2O2 concentration and (d) total dissolved polyphenols as a function of time in
737
PEF degradations of the winery wastewater after biological oxidation using a BDD anode, 25 ºC,
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[Fe2+]0 = 35 mg L-1 and pH = 2.8. j: () 10, () 25 and () 100 mA cm-2.
739
Fig. 5. Evolution of (a) normalized DOC removal, (b) H2O2 concentration and (c) total dissolved
740
polyphenols as a function of time in the degradation of the winery wastewater after biological
741
oxidation under different EAOPs using a BDD anode, 25 ºC, j = 25 mA cm-2, pH = 2.8 and [Fe2+]0
742
= 35 mg L-1 in EF, PEF and SPEF. EAOP: () AO-H2O2, () EF, () PEF and () SPEF. The
743
inset panel of Fig. 5a depicts the normalized DOC removal in PEF and SPEF systems as a function
744
of accumulated UV energy per L of solution. (d) SPEF process assessment in terms of ()
745
normalized DOC removal and () normalized COD removal.
746
Fig. 6. Time course of (a) percentage of [LMCA]/DOC ratio and (b) oxalic and (c) malic acids
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during the () AO-H2O2, () EF, () PEF and () SPEF processes of Fig. 5.
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conditions of Fig. 5 assessed by respirometry. The inset panel depicts the biodegradable character of
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a sample according to its bCOD/COD ratio. A.B.O.: Winery wastewater after biological oxidation.
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ACCEPTED MANUSCRIPT Table 1. Physicochemical characterization of the winery wastewater samples (raw, after 10 days of biological oxidation and after 240 min of SPEF process using a BDD anode, [Fe2+]0 = 35 mg L-1, j = 25 mA cm-2, pH = 2.8 and 25 ºC) and discharge limits for WWTPs final effluents according to
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Portuguese legislation (Decree-Law no. 236/98) and European Directive no. 91/271/CEE. Winery wastewater Raw
Color
Dark violet
Light brown
d
e
n.d. Weak n.d.e 8.3 20 2998 1561 30 480 350 130 (97%) 380 (97%) 150 (98%) 0.4 -g
S0043-1354(15)00102-5
DOI:
10.1016/j.watres.2015.02.029
Reference:
WR 11165
To appear in:
Water Research
Received Date: 18 November 2014 Revised Date:
26 January 2015
Accepted Date: 16 February 2015
Please cite this article as: Moreira, F.C., Boaventura, R.A.R., Brillas, E., Vilar, V.J.P., Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes, Water Research (2015), doi: 10.1016/j.watres.2015.02.029. 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.
ACCEPTED MANUSCRIPT BIODEGRADABLE FRACTION + RECALCITRANT FRACTION
EFFLUENT DISCHARGE INTO THE ENVIRONMENT OR FURTHER BIOLOGICAL OXIDATION
BIOLOGICAL OXIDATION SYSTEM
ELECTROLYTIC SYSTEM
IMMOBILIZED BIOMASS REACTOR
CONDITIONER TANK
ELECTROCHEMICAL CELL
H2SO4 NaOH AIR
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RECALCITRANT FRACTION
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BORONDOPED DIAMOND (BDD) ANODE
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CPCs STRUCTURE
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Remediation of a winery wastewater combining aerobic biological
2
oxidation and electrochemical advanced oxidation processes
3
Francisca C. Moreira a, Rui A.R. Boaventura a, Enric Brillas b, Vítor J.P. Vilar a,*
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a
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Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr.
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Roberto Frias, 4200-465 Porto (Portugal)
7
b
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Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona (Spain)
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*
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LSRE - Laboratory of Separation and Reaction Engineering - Associate Laboratory LSRE/LCM,
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Laboratori d’Electroquímica dels Materials i del Medi Ambient, Departament de Química Física,
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Corresponding author. Tel.: +351 918257824; Fax: +351 225081674; E-mail address:
[email protected] (Vítor J.P. Vilar) 1
ACCEPTED MANUSCRIPT Abstract
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Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery
13
wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as
14
polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a
15
biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical
16
advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or
17
transform them into simpler ones that can be further biodegraded. The biological oxidation led to
18
above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-
19
day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant
20
fraction corresponding to 130 mg L-1 of DOC, 380 mg O2 L-1 of COD and 8.2 mg caffeic acid
21
equivalent L-1 of total dissolved polyphenols. Various EAOPs such as anodic oxidation with
22
electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar
23
PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant
24
containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a
25
carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic
26
collectors (CPCs). The influence of initial Fe2+ concentration and current density on the PEF
27
process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2
EF > PEF > SPEF (see Fig. 5b), as predicted by the increasing rate
447
of Fe3+ to Fe2+ regeneration of these EAOPs. During the SPEF process, the H2O2 concentration
448
diminished to very low values, 4-9 mg L-1, when more pronounced DOC abatement was patent, 60-
449
120 min, which confirms the operation at 25 mA cm-2 as a good option since a low j might not
450
ensure the H2O2 occurrence during all the SPEF process.
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Fig. 5c outlines that the AO-H2O2 and EF processes were ineffective on the total dissolved
452
polyphenols degradation. In contrast, the SPEF treatment was able to reduce these compounds to
453
values as low as 0.4 mg caffeic acid equivalent L-1 after a short time of 120 min, whereas the PEF
454
process reduced polyphenols concentration up to 2.6 mg caffeic acid equivalent L-1 at 180 min. The SPEF process under the best conditions considered in the current study reached DOC and
456
COD removals of 86% and 68%, respectively, in relation to the biologically treated effluent after
457
240 min of treatment, with energy consumptions of 45 kWh (kg DOC)-1 and 5.1 kWh m-3. Fig. 5d
458
reveals that the COD decay was similar (for times below 90 min) or lower (for times above 90 min)
459
than the DOC abatement, thereby suggesting a contribution of the particulate organic compounds to
460
the COD value. A decrease of 54% in the total nitrogen content was observed during the SPEF
461
process (see Table 1), which can be linked with the retention of some non-dissolved N-compounds
462
into the precipitate during the EAOP since the total dissolved nitrogen remained unaffected. Table 1
463
also shows that at 240 min of SPEF, COD and BOD5 complied with the Portuguese and the
464
European legislation limits for discharge of WWTPs final effluents (Decree-Law no. 236/98 and
465
Directive no. 91/271/CEE, respectively), in contrast with TSS, total nitrogen and total phosphorous
466
parameters (total phosphorous only exceeded the European limit). Moreover, color, odor, NH4+,
467
NO3- and SO42- parameters were in agreement with the Portuguese targets, but pH and total
468
dissolved iron surpassed the limits. In this context, the final SPEF solution was neutralized to pH
469
6.2 with subsequent sedimentation for 30 min with a resultant supernatant effluent displaying a total
470
dissolved iron below the detection limit (0.13 mg L-1), a total phosphorous concentration of 0.35 mg
471
L-1 and 55 mg TSS L-1 but without change on total nitrogen. Therefore, besides the application of a
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further step comprising the effluent neutralization and subsequent precipitation of the settleable
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compounds, the initial biological oxidation should be enhanced and include nitrifying and
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denitrifying
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bacteria
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as
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neutralization/precipitation step led to the formation of 26 mL of sludge per L of treated winery
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wastewater that require further adequate treatment. Regarding the combination of the biological oxidation and SPEF processes, very high
478
abatements on DOC, COD and BOD5 parameters of ca. 99% were attained, which is in agreement
479
with the great COD removals of 95% and above 99% accomplished by Anastasiou et al. (2009) and
480
Lucas et al. (2009b) for the combination of a biological oxidation and a further photo-Fenton or
481
Fenton process, respectively.
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3.3.5. Evolution of generated carboxylic acids and inorganic ions during EAOPs
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The ion-exclusion HPLC analysis on LMCA revealed the formation of oxalic (tr = 8.5 min) and
484
malic (tr = 13.2 min) acids during the AO-H2O2, EF, PEF and SPEF treatments. These acids are
485
expected to be formed from the oxidative cleavage of the benzenic ring of aromatic intermediates
486
(Brillas et al., 2009). Malic acid can be subsequently transformed into oxalic acid, which is an
487
ultimate acid that can be directly mineralized to CO2 (Vel Leitner and Doré, 1997; Oturan et al.,
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2008; Garcia-Segura and Brillas, 2011). Malic and oxalic acids may be primordially present in
489
solution as Fe(III)-carboxylate complexes because the iron is mainly available as Fe3+ during the
490
processes. Fig. 6a illustrates that in the AO-H2O2 process the LMCA were accumulated in very low
491
amounts with a contribution never superior than 1.2% for DOC, suggesting inefficiency of this
492
process to convert high-molecular aromatic compounds into the simple LMCA, in corroboration
493
with the low mineralization attained. In contrast, in EF both acids were accumulated in larger extent
494
with maximum concentrations of ca. 10 mg C L-1 for oxalic acid (see Fig. 6b) and ca. 5 mg C L-1 for
495
malic acid (see Fig. 6c), corresponding to 24% of DOC due to LMCA at the end of the process (see
496
Fig. 6a). In PEF and SPEF, both oxalic and malic acids were accumulated in low extent, below 3.0
497
mg C L-1 (Figs. 6b and c), which might be related to a fast photolysis rate of Fe(III)-oxalate and
498
Fe(III)-malate complexes.
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ACCEPTED MANUSCRIPT The mineralization of organic compounds is expected to be followed by the loss of their
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nitrogen and sulfur atoms in the form of inorganic ions such as NH4+, NO3-, NO2- and SO42-. In the
501
SPEF process under the best conditions, NO2- was not found as expected due to their instability in
502
strong oxidant media. NH4+, NO3- and total dissolved nitrogen concentrations remained almost
503
unaffected, suggesting the inability of SPEF to degrade dissolved recalcitrant organic N-
504
compounds. As aforementioned, total nitrogen decreased in an extent of 54%, pointing to the
505
retention of non-dissolved N-compounds into the precipitate. On the other hand, SO42- was
506
gradually released into the solution up to ca. 150 mg L-1 at 240 min, which can be mainly attributed
507
to the dissolution of SO42- retained in the foam and also to a possible degradation of organic
508
compounds containing sulfur in their structure.
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3.4. Biodegradability enhancement during SPEF process
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As abovementioned, alternatively to the application of a SPEF process to achieve organic loads
511
in agreement with the discharge limits, the electrochemical process can be applied as a pre-
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treatment to transform recalcitrant compounds into simpler ones that can be subsequently
513
biodegraded, thereby reducing the overall cost of the treatment. In this context, the biodegradability
514
of the winery wastewater was assessed along the SPEF process by means of respirometry assays.
515
Fig. 7 reveals the bCOD/COD ratios attained throughout the treatment. Maximal bCOD/COD of 0.1
516
were achieved for times of 40 and 90 min, corresponding to low biodegradable samples according
517
to Ballesteros Martín et al. (2010). However, the short times employed in the respiration tests, ca.
518
30 min, could be insufficient to degrade the total content of slowly biodegradable organic matter
519
(Kümmerer et al., 2004), and, furthermore, the applied biomass was not adapted to degrade the
520
organic matrix of the winery wastewater, probably reaching lower efficiencies than an adapted
521
biomass test as Zahn-Wellens.
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4. Conclusions
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biological oxidation treatment attained high DOC, COD and BOD5 removals above 97%. However,
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the biologically treated effluent was constituted of a bioresistant fraction comprising 130 mg L-1 of
526
DOC, 380 mg O2 L-1 of COD and 8.2 mg caffeic acid equivalent L-1 of total dissolved polyphenols
527
and a subsequent EAOP was then employed to mineralize the recalcitrant compounds or transform
528
them into simpler ones. The degradation of the winery effluent by EAOPs could be efficiently
529
carried out using 25 ºC and pH of 2.8 at a current density of 25 mA cm-2 and, for Fenton’s reaction
530
based processes, an initial Fe2+ concentration of 35 mg L-1. The relative oxidative capability of
531
EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF, with DOC removals on the
532
biologically treated effluent of 36%, 54%, 84% and 86%, respectively, after 240 min of reaction.
533
The poor DOC removal attained in AO-H2O2 revealed a small ability of BDD(•OH) generated at the
534
anode surface to react with recalcitrant winery wastewater compounds. In EF, the production of
535
•
536
additional •OH production induced by UVA or solar radiation, respectively, along with the possible
537
direct photolysis of complexes formed between Fe3+ and some organic intermediates, led to the
538
fastest reaction rates. The SPEF process under the best conditions chosen in the present study
539
attained removals of 86% for DOC and 68% for COD regarding the biologically treated effluent
540
after 240 min of treatment, with energy consumptions of 45 kWh (kg DOC)-1 and 5.1 kWh m-3. At
541
this time of SPEF, a total dissolved polyphenols content of 0.35 mg caffeic acid equivalent L-1 was
542
found and color, odor, COD, BOD5, NH4+, NO3- and SO42- parameters complied with the European
543
and/or Portuguese legislation limits for discharge of WWTPs final effluents. However, to achieve
544
total nitrogen, total phosphorous, pH, total dissolved iron and TSS targets to discharge the winery
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wastewater into the environment, the biological oxidation treatment must be optimized to provide
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the removal of nitrogen and additional neutralization and precipitation steps should succeed the
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ACCEPTED MANUSCRIPT SPEF process. The respirometry assays revealed low biodegradability enhancement along the SPEF
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process.
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Acknowledgements
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Financial support was partially provided by (i) PEst-C/EQB/LA0020/2013 project, co-financed by
551
FCT (Fundação para a Ciência e a Tecnologia) and FEDER (Fundo Europeu de Desenvolvimento
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Regional) under COMPETE program (Programa Operacional Fatores de Competitividade) of
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QREN (Quadro de Referência Estratégico Nacional); (ii) NORTE-07-0162-FEDER-000050
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project, co-financed by FEDER, QREN and ON2 program (Programa Operacional Regional do
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Norte); and (iii) funds of the Pluridisciplinar project SOLARVIN (PP-IJUP2011-46) from the
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University of Porto. F.C. Moreira acknowledges her Ph.D. fellowship SFRH/BD/80361/2011
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supported by FCT. V.J.P. Vilar acknowledges the FCT Investigator 2013 Programme
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(IF/01501/2013).
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ACCEPTED MANUSCRIPT Figure captions
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Fig. 1. Research articles on winery wastewater remediation per year arranged by treatment process
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(source: http://www.scopus.com/, December 2013, search for “winery wastewater treatment” with
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further manual refinement to exclude misclassified articles and distribute them by treatment
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process).
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Fig. 2. Assessment of the biological oxidation efficiency in the treatment of the raw winery
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wastewater in terms of () DOC removal, () total dissolved polyphenols and () pH.
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Fig. 3. Influence of initial Fe2+ concentration on (a) normalized DOC removal and (b) total
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dissolved iron concentration as a function of time in PEF degradations of the winery wastewater
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after biological oxidation using a BDD anode, 25 ºC, j = 100 mA cm-2 and pH = 2.8. [Fe2+]0: ()
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20, () 35 and () 70 mg L-1.
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Fig. 4. Effect of current density (j) on (a) normalized DOC removal, (b) energy consumption per
736
unit DOC mass, (c) H2O2 concentration and (d) total dissolved polyphenols as a function of time in
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PEF degradations of the winery wastewater after biological oxidation using a BDD anode, 25 ºC,
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[Fe2+]0 = 35 mg L-1 and pH = 2.8. j: () 10, () 25 and () 100 mA cm-2.
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Fig. 5. Evolution of (a) normalized DOC removal, (b) H2O2 concentration and (c) total dissolved
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polyphenols as a function of time in the degradation of the winery wastewater after biological
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oxidation under different EAOPs using a BDD anode, 25 ºC, j = 25 mA cm-2, pH = 2.8 and [Fe2+]0
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= 35 mg L-1 in EF, PEF and SPEF. EAOP: () AO-H2O2, () EF, () PEF and () SPEF. The
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inset panel of Fig. 5a depicts the normalized DOC removal in PEF and SPEF systems as a function
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of accumulated UV energy per L of solution. (d) SPEF process assessment in terms of ()
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normalized DOC removal and () normalized COD removal.
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Fig. 6. Time course of (a) percentage of [LMCA]/DOC ratio and (b) oxalic and (c) malic acids
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during the () AO-H2O2, () EF, () PEF and () SPEF processes of Fig. 5.
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ACCEPTED MANUSCRIPT Fig. 7. Biodegradability of samples collected at different times of a SPEF treatment under the
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conditions of Fig. 5 assessed by respirometry. The inset panel depicts the biodegradable character of
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a sample according to its bCOD/COD ratio. A.B.O.: Winery wastewater after biological oxidation.
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ACCEPTED MANUSCRIPT Table 1. Physicochemical characterization of the winery wastewater samples (raw, after 10 days of biological oxidation and after 240 min of SPEF process using a BDD anode, [Fe2+]0 = 35 mg L-1, j = 25 mA cm-2, pH = 2.8 and 25 ºC) and discharge limits for WWTPs final effluents according to
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Portuguese legislation (Decree-Law no. 236/98) and European Directive no. 91/271/CEE. Winery wastewater Raw
Color
Dark violet
Light brown
d
e
n.d. Weak n.d.e 8.3 20 2998 1561 30 480 350 130 (97%) 380 (97%) 150 (98%) 0.4 -g
