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H I G H L I G H T S
Winery wastewater from Miguel Torres S.A. facilities showed very high temporal variability.
COD removal was 95% and 97% for the CAS and MBR systems respectively.
MBR produced a very high quality treated wastewater in terms of COD, suspended solids and microbiological contamination.
MBR treated wastewater meets the requirements for reuse in agricultural practices.
Water permeability in the MBR system was correlated to the presence of EPS.
a r t i c l e i n f o a b s t r a c t
Article history: A comparative study was carried out in order to evaluate the winery wastewater treatment by a MBR pilot plant
Received 13 June 2012 and compare it to a full-scale conventional activated sludge system. The MBR pilot plant was constructed and
Received in revised form 8 August 2012 operated by Hera-Amasa and continuously fed with real winery wastewater generated in wine-making process
Accepted 10 August 2012
in Bodegas Torres facilities (Catalonia, Spain). The inuent and efuents were monitored and controlled in order
Available online 6 September 2012
to reach the quality determined by the Spanish legislation as well as the international guidelines and regulations
Keywords:
for wastewater reuse and reclamation. After 6 months of continuous operations the physico-chemical and
Winery wastewater microbial parameters of the MBR plant achieved the specications dened for urban service, agricultural and rec-
Membrane bioreactor reational uses. The MBR plant showed a quite stable and exible operation during the experiment. A signicant
Flat sheet correlation between EPSc and permeability conrmed the inuence of the hydrophilic fraction on the membrane
Wastewater regeneration fouling potential.
Water reuse 2012 Elsevier B.V. All rights reserved.
0011-9164/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.desal.2012.08.016
2 C. Valderrama et al. / Desalination 306 (2012) 17
physically cleaned by 1 min membrane relaxation every 9 min of according to Mamais et al. [23]. Total anions and cations were analysed
operation. During membrane cleaning, water ltration is stopped by ion chromatography (Dionex ICS-2100).
and membrane fouling is removed through air scouring. Although
air ows lower than 0.5 Nm 3m 2h 1 are usually used at full 3. Results and discussion
scale plants, 0.9 Nm 3m 2h 1 was used in this study due to pilot
scale considerations. In Table 1 the most important design parameters 3.1. Wastewater characterization
for MBR pilot plant are summarized. Finally the data collection and con-
trol process were performed by means of programmable logic control- In order to evaluate the variability of the wastewater generated in
ler (PLC). It should be noticed that, due to the inherent conguration the wine making process, a characterization of the wastewater generat-
of both systems, it would be difcult that a malfunction would limit ed was performed from October 2008 to June 2009. Sampling periods
the production in the CAS system while in the MBR, in case of inactivity, were divided in four different annual stages according to the wine pro-
there would not be permeation of water through the membrane. duction process: harvesting (September to October), harvesting and
vinasse generation (November to January), vinasse generation (January
2.3. Experimental procedure to May) and process (May to August).
Harvesting is the time of the year with the highest production and
Winery wastewater treatment experiments started on October of when the highest amount of wastewater is generated. Grape process-
2009 for the MBR pilot plant. Both CAS and MBR plants were continu- ing and bottling are carried through this period but also sanitary
ously fed with winery wastewater from the wine production process. wastewaters are entering the wastewater treatment plant. During
This water was pre-treated by a screening unit (1 mm) and then the harvesting and vinasse generation period the nal harvesting pro-
pumped into the buffer tank of 500 m 3 from which both CAS and cesses take place no more grapefruits are entering the process but
MBR plants were fed. Both treatment plants were simultaneously oper- sanitary wastewaters are still generated. Vinasses start to arrive at
ated for a period of 5 months controlling physico-chemical and biolog- the wastewater treatment plant.
ical parameters in inuent (buffer tank) and the efuents from both Vinasse period is characterized by high vinasse generation, sani-
plants. tary wastewater and other process wastewaters including bottling.
Finally, during the process period, cleaning, bottling and sanitary
2.4. Sampling, analysis and control wastewaters comprise the highest part of the generated wastewater.
Hourly samples of the inuent wastewater were collected during
During the initial wastewater characterization, samples were col- each period by means of an automatic sampler and mixed to generate
lected hourly using a fraction collector system (ISCO 6712) equipped daily average wastewater. Results from wastewater characterization
with 24 bottles (1 L). COD, pH, and conductivity were analysed in are summarized in Table 2. A signicant COD variability was observed
hourly samples. Turbidity, TSS, P-total and N-total were analysed in for each production stage with exception of the process wastewater
daily samples obtained by composition of hourly samples. which reported typical values of urban wastewater, as can be seen
In order to monitor MBR and CAS performance, inlet wastewater in Fig. 2. Previous studies also report the concentrations observed
samples were collected from the homogenizer tank that fed both sys- and the elevated variability during the harvesting and the process
tems. Outlet samples from the MBR system were collected after the seasons [24,25]. These variations in COD content of the wastewater
membrane separation, while efuent samples from the CAS system produced in wineries should be taken into account when designing
were collected after the secondary clariers. All samples were preserved their treatment [10]. Similar values of COD concentration were ob-
according to [22] and stored in a refrigerator (4 C) until analysis. served in the inuent wastewater during the pilot plant operation
COD, turbidity, BOD5, total and volatile suspended solids (TSS and (data not shown).
VSS) were analysed following methods 5220D, 2130D, 5210B, and The COD fraction characterization was performed to two consecu-
2540G dened in the Standard Methods for the Examination of Water tive daily samples for the vinasse and process stage (Fig. 3). The results
and Wastewater [22], respectively. Total nitrogen was analysed by a indicate that the readily biodegradable soluble complex fraction is
total nitrogen analyser (Analytik-Jena 3100 N/C). Total phosphorus higher for both stages, however an increase in nonbiodegradable frac-
was analysed following method UNE-EN ISO 6878. Microbiological tion is observed in process water. In fact, the ratio between the readily
characterization was also performed following standard methods biodegradable COD and the total COD varies from 0.2 to 0.6 during the
9222B, 9222D and UNE-EN ISO 93081 for total coliform, faecal coli- sanitary period to 0.9 during the vinasse period. These results are in
form, and Escherichia coli. Extracellular polymeric substances (EPS) agreement with the results shown in previous studies and reveal that,
and soluble microbial products (SMP) were analysed following the despite the high organic pollution generated, most of the winery waste-
method proposed by Judd [14]. COD fractionation was determined com- water is readily biodegradable [8,26].
bining COD and respirometric analysis to quantify biodegradable frac- The conductivity values observed are higher than those previously
tions (Respirometer SURCIS BMT). Briey, soluble fractions were reported in the literature [26]. This is probably due to the discharge
determined by ltering through 0.45 m acetate lters, while colloidal of brine from the ion exchange process and the neutralization and
fractions were determined by occulation with zinc sulphate 1 M
Table 2
Table 1 Physico-chemical characterization of the inuent winery wastewater during the differ-
Design parameters of MBR pilot treatment plant. ent annual stages of the wine production process. Mean values (standard deviation).
30000 7
a) Harvesting Harvesting
Harvesting and vinasse Harvesting-vinasse
25000 6
Vinasse
Vinasse
Process
COD (mg O2dm-3)
4
15000
3
10000
2
5000
1
0
0 10 20 30 40
0
t (h) Total coliform Faecal coliform Escherichia Coli
Fig. 2. Winery wastewater characterization, COD variability in hourly samples during Fig. 4. Microbial characterization of winery CAS efuent by different stages of wine
the different annual stages of the wine production process. production process, performed following standard methods 9222B, 9222D and UNE
EN ISO 93081.
The MBR pilot plant started to operate at the end of the harvesting 3.3. Membrane performance
period in 2009. Inuent COD during the experimental period uctuated
from 100 mg/L to more than 8000 mg/L. The COD removal efciency as The variation of permeate ux and the trans-membrane pressure
a function of food-to-microorganism (F/M) ratio is presented in (TMP) is shown in Fig. 7. As can be seen, the maximum ux (15 L/m2h)
Fig. 5. No signicant variability was observed for the MBR treatment, was reached after 51 days and resulted in a clear increase of the TMP
obtaining removals over 90%. Despite the high pollution loads of the (>160 mbar). The TMP was reduced by reducing the permeate ux,
inuent wastewater the average COD removal was 97 and 95% for however after 56 days and accidental purge of the solids in reactor the
MBR and CAS respectively. Food-to-microorganism (F/M) ratios ob- TMP (Fig. 7) and the permeability were affected. In this case, the ow
served were slightly lower than the typical values for a complete mix rate was reduced and the recirculation rate was modied in order to
achieve higher solid concentration into the membrane reactor. It is
5000 important to point out that this kind of incident can be easily solved
Particulate non-biodegradable
Soluble non-biodegradable 100
4000 Particulate biodegradable
Colloidal biodegradable
98
COD (mg O2dm-3)
Soluble biodegradable
y = 1.12ln(x) + 99.917
COD removal (%)
3000
r2 = 0.5333
96
2000
94
y = 2.37ln(x) + 103.9
r2 = 0.9245 MBR
92
1000
CAS
90
0.00 0.05 0.10 0.15 0.20 0.25 0.30
0
Vinasse 1 Vinasse 2 Process 1 Process 2 F/M (kg COD/MLTSS/day)
Fig. 3. COD fraction characterization in daily average samples from winery wastewater Fig. 5. COD removal efciency as a function of food-to-microorganism (F/M) ratio for
vinasse and process stage. winery treatment by MBR and CAS process.
C. Valderrama et al. / Desalination 306 (2012) 17 5
30000 70
EPS glucose
MLSS CAS
10000 20
y = -4.859ln(x) + 35.801
10 r2 = 0.7284
5000
0
0 0 200 400 600 800 1000
10/2009
11/2009
11/2009
12/2009
01/2010
01/2010
02/2010
03/2010
03/2010
04/2010
05/2010
Permeability (Lm-2h-1bar-1)
Fig. 8. EPS and permeability correlation for MBR pilot plant in winery wastewater
Fig. 6. MLSS and VSS evolution in CAS and MBR treatment process for winery wastewa- treatment.
ter, following methods 5220D, 2130D, 5210B, and 2540G dened in the Standard
Methods for the Examination Of Water and Wastewater.
100 100
180
TSS effluent
TMP 25
160
140 Flux Removal
20 80 80
Flux (Lm-2h-1)
TMP (-mbar)
120
Spanish Royal decree
100 15
(Urban use)
Removal (%)
TSS (mg L-1)
80 60 60
Spanish Royal decree
10
60 (Residential use)
40
5
20 40 40
0 0
09-12-09
14-12-09
19-12-09
24-12-09
29-12-09
03-01-10
08-01-10
13-01-10
18-01-10
23-01-10
28-01-10
02-02-10
07-02-10
12-02-10
17-02-10
22-02-10
27-02-10
04-03-10
09-03-10
20 20
0 10 20 30 40 50 60 70 80 90
Dates /Experimental days 0 0
CAS MBR
Fig. 7. Transmembrane pressure (TMP) and temperature corrected ux (20 C) varia-
tions during the experiment for MBR pilot plant in winery wastewater treatment. Fig. 9. Average TSS removal in MBR and CAS efuents.
6 C. Valderrama et al. / Desalination 306 (2012) 17
10 Table 3
9 Efluent MBR Physico-chemical characterization of CAS and MBR efuents during experimental
8 Efluent CAS period.
Spanish Royal Decree (Agricultural Use)
log 10 (CFU/100)
7 CAS MBR
6
Parameter Average Standard Average Standard
5 deviation deviation
4
pH 7.3 0.4 7.3 0.3
3 Conductivity (mS/cm) 3.3 0.9 3.4 0.9
2 Turbidity (NTU) 38.2 40.4 4.0 3.4
1 BOD5 (mg/L) 7 9 9 22
TSS (mg/L) 26 8.1 2.0 9.0
0
COD (mg/L) 222.8 321.2 113.7 150.4
Total coliform Faecal coliform E. Coli
P-total (mg/L) 5.3 3.3 4.9 2.3
N-total (mg/L) 1.7 5.1 5.7 7.1
Fig. 10. Microbial evaluation for the MBR and CAS efuents and quality criteria for
Cl (mg/L) 423.4 92.4 459.2 97.9
reuse purpose, performed following standard methods 9222B, 9222D and UNE EN
PO43 (mg/L) 11.4 5.9 11.0 6.6
ISO 93081.
SO42 (mg/L) 194.5 68.4 171.1 69.3
NO3 (mg/L) 3.7 10.8 24.6 8.1
reduction of bacterial pathogens in recycled water before storage [19]. Ca2+ (mg/L) 152.8 56.1 125.9 46.4
For this purpose the microbial parameters were also monitored in Mg2+ (mg/L) 40.3 35.9 39.6 37.4
order to dene if the efuent from MBR pilot plant was under the limits K+ (mg/L) 199.8 95.1 198.0 85.9
Na+ (mg/L) 438.4 115.5 444.6 140.0
dened for wastewater reuse. The evolution of the inuent and efuent NH4+ (mg/L) 1.8 2.2 4.3 6.1
concentration of E. coli, total and faecal coliform (log10 CFU/100 mL) as SARa 8.1 2.9 8.8 3.7
well as the limit dened by the Spanish Royal Decree for this parameter Hardness (mg/L) 547 288 477 269
for wastewater reuse are shown in Fig. 10. It can be observed that MBR Intestinal nematode 386 103.6 1 0
(eggs/10 L)
efuent was more than 10 times lower than the limit dened for agricul-
Escherichia coli 5.14 5.46 0.47 0.34
tural use, which is, apart from the residential, the most restrictive use. Log 10 (CFU/100 mL)
Most of the days E. coli was not detected in the efuent, which is the Total coliform 5.81 6.12 0.60 0.30
limit of wastewater treated for residential use. Considering the results log10 (CFU/100 mL)
of E. coli removal, which is the indicator used in all regulations, MBR Faecal coliform 5.66 6.00 0.61 0.26
log10 (CFU/100 mL)
treatment for winery wastewater will provide water suitable for
a
urban, agricultural and recreational uses, according to present regula- Sodium adsorption ratio (SAR).
tions and guidelines [1821]. However, it should be pointed out that
most of these guidelines and regulations dene other microbial param- related to the nutrient addition and inuent neutralization with
eters which are necessarily required to determine the quality classica- NaOH and NH4Cl. Also the discharge of decalcication brine could
tion for water reuse. be responsible to the values observed. Microltration membranes
The total and faecal coliforms, which are generally used as indica- used in the MBR system only rejected suspended solids larger than
tors to determine the degree of disinfection [20] were also monitored 0.2 m. In both systems, CAS and MBR, in case that dissolved salts
during the experiment (also shown in Fig. 10), and it can be observed should be removed prior to water reuse, an additional desalination
that inuent concentration was around 6 log10 CFU/100 mL, while stage (reverse osmosis, nanoltration, electrodialysis reversal, ion ex-
MBR efuent was lower than 10 CFU/100 mL. Other microbial param- change) must be considered. A physico-chemical characterization of
eter measured was the helminth eggs, which must be in a concentra- MBR efuent is summarized in Table 3.
tion lower than 1 egg/10 L in the water to be reclaimed. In this case, The results obtained in this study can be compared to other winery
the average concentrations were b 1 and 386 eggs/10 L for MBR and wastewater strategies, and in this sense, literature review indicates that
CAS efuents, respectively, thus conrming that CAS process requires different technologies are considered for this purpose; however few of
an additional treatment to achieve the microbial requirements for them are focused on water reuse. In most of the studies, the COD remov-
water reuse purpose. al efciency is the key parameter to assess the technical feasibility of the
Finally, major cations and anions were also monitored in efuents winery wastewater treatment. In this sense the COD removal rates
as can be seen in Fig. 11. No signicant differences were observed be- obtained by MBR plant are higher than those reported when using a
tween the inuents and both efuents with the exception of ammoni- jet-loop activated sludge reactor [4], long term aerated storage and
um, nitrates and nitrites (related to the biological activity). The high chemical coagulation/occulation [8], a hybrid constructed wetland
values of chloride and sodium concentration observed could be [7], and a photocatalytic/photolytic reactor [5]. Furthermore, the MBR
a) b)
1.E+03 1.E+03
Total concentration (mgL-1)
Infuent Efluent CAS Efluent MBR Infuent Efluent CAS Efluent MBR
1.E+02 1.E+02
1.E+01 1.E+01
1.E+00 1.E+00
1.E-01 1.E-01
chloride phospates sulphates nitrates nitrites bromide ammonia calcium magnesium potassium sodium
Fig. 11. a) Anions and b) cations evaluation in the inuent and MBR and CAS efuents, determined by ion chromatography.
C. Valderrama et al. / Desalination 306 (2012) 17 7
efuent achieved the quality criteria dened for urban, agricultural and [9] D. Bolzonella, F. Fatone, P. Pavan, F. Cecchi, Application of a membrane bioreactor
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system and MBR pilot plant installed in the Miguel Torres facilities. wastewater using an anaerobic submerged MBR: factors affecting long-term
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[14] S. Judd, The MBR Book: Principles and Applications of Membrane Bioreactors for
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Agency, Washington DC, USA, 2004.
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This research was nancially supported by the Centro de Desarrollo [24] G. Andreottola, P. Foladori, P. Nardelli, A. Denicolo, Treatment of winery wastewa-
ter in a full-scale xed bed biolm reactor, Water Sci. Technol. 51 (2005) 7179.
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DEMETER. The authors are also grateful to the anonymous reviewers Perez-Murcia, Uses of winery and distillery efuents in agriculture: characterisa-
for their constructive criticism of the original paper. tion of nutrient and hazardous components, Water Sci. Technol. 51 (2005)
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[26] C. Beck, G. Prades, A.G. Sadowski, Activated sludge wastewater treatment plants
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