Você está na página 1de 7

Desalination 306 (2012) 17

Contents lists available at SciVerse ScienceDirect

Desalination
journal homepage: www.elsevier.com/locate/desal

Winery wastewater treatment for water reuse purpose: Conventional activated


sludge versus membrane bioreactor (MBR)
A comparative case study
C. Valderrama a,, G. Ribera b, N. Bah b, M. Rovira a, b, T. Gimnez c, R. Nomen d, S. Lluch c,
M. Yuste d, X. Martinez-Llad b
a
Departament d'Enginyeria Qumica, Universitat Politcnica de Catalunya, Spain
b
Fundaci CTM Centre Tecnolgic, Avinguda Bases de Manresa 1, 08240 Manresa, Spain
c
HERA-AMASA, S.A. Grupo HERA, Area Tecnologas - Dep. Aguas, Paletes 6, Parque Tecnolgico del Valls, Cerdanyola 08290, Spain
d
Miguel Torres S.A., Miguel Torres 6, 08270 Vilafranca del Peneds, Spain

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.

1. Introduction typical specic production is reported in the range 14 m3/m3 of wine


produced, 6070% during the vintage period [6]. Winery wastewaters
Wine production processes generate organic and inorganic pollutions contain large amounts of biodegradable organics in addition to relatively
mostly associated with solid wastes and liquid efuents. The liquid efu- small concentrations of recalcitrant compounds: polyphenols, organic
ents usually referred as winery wastewater are mainly originated in acids and sugars and high chemical oxygen demand (COD) concentra-
washing operations during grape harvesting, pressing and rst fermenta- tions, up to 10 kg/m3 and relatively low presence of solids and nutrients
tion phases of wine processing [13]. As a consequence of the working pe- [7,8]. The disposal of winery efuents in streams, creeks, and rivers and
riod and the winemaking technologies, volumes and pollution loads on soils involves unacceptable environmental risks [1]. Therefore, the dis-
greatly vary over the year [4,5]. Consequently, the treatment system posal of winery wastewater is one of the main environmental problems
must be versatile to face both the loading regimen and stream uctuation; related to wine industries [5].
Several winery wastewater treatments are available, and among
them biological treatment methods have been recognized as a rea-
Corresponding author at: Departament d'Enginyeria Qumica, Universitat Politcnica
de Catalunya, Carrer Colom 1, Terrassa 08222, Barcelona, Spain. Tel.: +34 93 4011818;
sonable alternative way for a signicant degradation of wastewater
fax: +34 93 401 58 14. with high organic content, however, the presence of recalcitrant com-
E-mail address: cesar.alberto.valderrama@upc.edu (C. Valderrama). pounds for the microorganisms frequently makes impossible the

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

complete treatment of a winery wastewater [1]. In Europe, where 50%


of the wine is produced worldwide, wastewaters are pre-treated by
small wastewater treatment plants adopting the activated sludge
process and then are released in the sewerage system, which repre-
sents more than 70% of the produced wastewaters are treated by
means of the activated sludge process in large wineries [9]. However,
the intrinsic variability in ow and characteristics, and the necessity
to face high organic loading for relatively short periods during
harvesting and vintage generally determine problems for the opera-
tion of the activated sludge process. Recently, the use of membrane
bioreactors (MBR) has been considered as a suitable option for winery
wastewater treatment as they combine efciently the biochemical
oxygen demand (BOD), suspended solids, nitrogen and phosphorus re-
moval and microbial decontamination [1012]. The advantages of the
MBR system over conventional biological treatment processes include
maximum exibility of the biology according to the inuent loadings,
small footprint, the reduced sludge production and a compact system
with better solids removal, and disinfection [1315].
The increasing shortage of water resources in arid zones, zones
where grapes are usually grown, and the need to preserve the prima-
ry source for drinking purposes have increased interest in the reuse of
treated wastewater for irrigational, urban or industrial purposes [16].
Further, reuse of treated efuents provides a regular supply to users
and aids to assure the quality from a sanitary point of view as well
as environmentally [17]. In Spain, reclaimed water quality is regulat-
ed by the Royal Decree (1620/2007) [18] which is based on interna-
tional guidelines [17,1921] and aims to minimize the potentially
negative impact on public health. MBR systems are one of the best
available techniques for wastewater reclamation because treated
water quality easily meets the regulations' requirements.
The objective of this work is to compare the performance of a full
scale conventional activated sludge (CAS) process for winery and dis-
tillery wastewater treatment with a pilot scale MBR system in order
to evaluate the feasibility to, in the future, reclaim and reuse winery Fig. 1. Scheme of MBR system: 1. Aerobic reactor, 2. Fine bubble aeration system,
wastewater, which is not being done at the moment. For this purpose, 3. Membrane reactor, 4. Coarse bubble aeration system, 5. Recirculation and purge;
a pilot scale MBR system was installed parallel to the existing CAS and scheme of the CAS system: 1. Aerobic reactors, 2. Fine bubble aeration system,
3. Clariers, 4. Recirculation and purge.
winery wastewater treatment into the Miguel Torres S.A. facilities.
The treated efuents were evaluated in order to achieve the quality
criteria dened by the Spanish Royal Decree 1620/2007 for wastewa- NaOH, and (NH4)2HPO4 and NH4Cl are also added as nitrogen and
ter reuse [18]. phosphorous sources for the activated sludge process.
It is important to point out, that it is possible to work with only
2. Materials and methods one reactor if it is required, which represents a critical factor due to
the wide uctuation of winery wastewater. The two biological reac-
2.1. Existing productive process and wastewater treatment tors operate at high mass loading and in the activated sludge both
at total oxidation conditions. This continuous process is characterized
The productive process comprises several stages, including grape by an aeration phase by liquid oxygen (300 kg/h), automatically con-
reception, destemming, crushing, pressing, fermentation, aging, clar- trolled on the dissolved oxygen, oxidation reduction potential and
ication, stabilization, ltration, bottling, storage and expedition. pH. After the aerobic step, two secondary clariers (180 m 3) separate
Bottling is carried throughout the year. Both tap and groundwater the sludge and permeate by conventional settling.
are used and they are decalcied by ion exchange prior to entering
the productive process. Brine from ion exchange resin regeneration 2.2. MBR pilot plant description
is sent to the wastewater treatment plant.
The conventional wastewater treatment plant located at Miguel The MBR treatment plant (Fig. 1b) was designed, constructed and
Torres S.A. facilities receives, throughout the year, sanitary and indus- installed by Hera-Amasa. It was designed to perform the treatment in
trial wastewaters from the winemaking process. Both wastewaters two stages. In the rst zone, the bioreactor (aerobic conditions) in
get mixed at the plant header. which the organic matter is oxidized by means of an aeration system,
Distillery vinasses from the brandy making process enter the the reactor volume is variable, which suits to the temporality of the
treatment plant from October until May. They are neutralized with winery wastewater loading. This continuous process is characterized
NaOH and stored in open ponds before being mixed with wastewater. by an aeration phase which is guaranteed by a blower able to supply
The schematic diagram of both full scale CAS and pilot scale MBR air through a grid of ne bubble diffusers. This step is automatically
wastewater treatment plants is shown in Fig. 1. The CAS system com- controlled on the dissolved oxygen, oxidation reduction potential
prises aerobic biological degradation and secondary clarication and pH.
(Fig. 1a). The system consists of a pre-treatment unit (screening and The second zone is the ltration stage; here the efuent is ltered
grit removal units), a homogenizer tank (500 m 3) and then two bio- by means of at sheet (Kubota) membrane modules. The solid con-
logical reactors of 1050 m 3 each. Prior to entering the homogenizer centration was equilibrated between the bioreactor and the ltration
tank, inuent to the wastewater treatment plant is neutralized with zone throughout a recirculation system. The membrane module was
C. Valderrama et al. / Desalination 306 (2012) 17 3

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).

Parameter MBR (at sheet) Parameter Harvesting Harvesting Vinasse Process


and vinasse
Volume (m3) Bioreactor 1117
Membranes 3.5 pH 6.7 (2.5) 6.6 (2.1) 8.7 (1.4) N.D.
Membrane surface area (m2) 20 Conductivity (mS/cm) 5.6 (4.4) 3.6 (3.5) 4.1 (2.6) 4.5 (0.5)
Inow rate (m3/day) 6 Turbidity (NTU) 692 (407) 313 (100) 155 (20.5) 121 (21)
Outow rate (m3/day) 6 TSS (mg/L) 1230 (985) 662 (759) 271 (391) 178 (38)
Permeated ux (L/m2/h) 12.5 COD (mg/L) 13,448 (5055) 3887 (2106) 3400 (1682) 2323 (194)
Recirculation ow rate (%) 100 to 400 P-total (mg/L) 39.5 (14.8) 6.5 (0.6) 7.5 (0.4) 5.0 (0.8)
Operating conditions Permeation: 9 (min) N-total (mg/L) 34.0 N.D. 41.0 40.0
Relaxation: 1 (min)
ND: Not determined.
4 C. Valderrama et al. / Desalination 306 (2012) 17

30000 7
a) Harvesting Harvesting
Harvesting and vinasse Harvesting-vinasse
25000 6
Vinasse
Vinasse
Process
COD (mg O2dm-3)

Log 10 (UFC100 ml-1)


20000 5 Process

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.

addition of nutrients in the wastewater treatment process. As can be


seen in Table 2, taking into account the total amount of COD in the ef- activated-sludge reactor [27]. This is due to the high biomass content
uent, there is a lack of nutrients, especially nitrogen, for the correct in the reactors of both processes.
operation of the aerobic biological oxidation process [27]. The biomass content (in terms of mixed liquor suspended solids or
The microbiological parameters of the wastewater treatment plant MLSS) is plotted in Fig. 6. The volatile suspended solids (VSS) content
efuent were also monitored by the annual stages of the wine produc- was also monitored. Although the MLSS concentrations of the CAS
tion process. The results obtained for total and faecal coliform and E. coli system are high compared with values found in urban wastewater
are shown in Fig. 4. The presence of this kind of contamination in the [27] and other winery wastewater treatment plants [28], the MBR
wastewater is related to the sanitary part of the treated wastewater. Re- system allows working with even higher MLSS concentrations than
sults obtained indicate that a signicant variability was observed for mi- CAS, which represents higher organic matter removal (Fig. 5) as a
crobiological parameters along the whole year and additionally conrm function of the reactor volumetric unit and under the same hydraulic
that CAS treatment requires a post-treatment process in order to reduce retention time (HRT). VSS was observed to be fairly stabilized, ac-
the microbial concentrations to the levels dened in Royal Decree 1620/ counting for around 75% of the total MLSS, which is within the
2007 [18]. reported limits of 7090% in biological treatment [15]. Despite the
high concentration of MLSS in the reactors of both systems, no prob-
lems of bulking in the CAS neither membrane fouling in the MBR,
3.2. MBR and CAS performance were reported.

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

EPS (mg gluc o albg SS-1)


60
25000
MLSS and VSS (mgL-1)

MLSS MBR EPS protein


VSS CAS 50
20000 VSS MBR
40
y = -18.05ln(x) + 136.4
15000
30 r2 = 0.7431

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.

considered, for instance, the membrane replacement, or the cost of


due to the exibility of the MBR conguration. Additionally, the MLSS labour, which was assumed equal for both plants; however, a fully
concentration inside the MBR reactor was rather stable during the exper- automated MBR plant requires less labour than a CAS plant. In this
imental period, with an average and maximum concentration of 16 and sense, a more detailed economical analysis is required, for instance,
22 g/L respectively. a life cycle costing study which considers the capital investment,
In order to determine the fouling potential of membranes, the ex- actual rates for nancial parameters of credits and energy prices.
tracellular polymeric substances (EPS) and soluble microbial products
(SMP) were monitored during the experiment. Deposition/accumulation
of SMP or EPS has been reported to have large fouling ability due to their 3.4. Quality criteria for wastewater reuse
interaction with membrane material [29]. Typically, the EPS and the SMP
solution are characterized according to its relative content of protein (p) During winery wastewater treatment with both CAS and MBR
and carbohydrate (c). The EPS and SMP were correlated to different pro- plants, the quality of efuents for both systems was monitored and
cess parameters, such as: TMP, permeate ux and permeability calculat- evaluated according to the limits determined by the Spanish Royal
ed according to Judd [14]. A fairly good correlation was obtained Decree 1620/2007 for wastewater reuse. The evolutions of efuent
between EPS and permeability as can be seen in Fig. 8. TSS for both processes are shown in Fig. 9. Furthermore, the values
This correlation indicates that permeability decreases when the EPS of 10 and 20 mg/L (for wastewater efuents) determined by the
content increases and vice versa. In this case the EPSp reported higher Spanish Royal Decree for residential and urban use, respectively are
correlation coefcient than EPSc. It can be explained since EPSp generally also shown in Fig. 9. It can be observed that MBR efuent was lower
has hydrophobic tendencies while EPSc is more hydrophilic [30] and than the limits dened for urban, agricultural and recreational use.
may therefore interact more strongly with the membrane [14]. On the Furthermore, the average efuent TSS concentration reported was
other hand the SMP showed poor correlation to the process parameters 2 mg/L, and an average removal of 99% was achieved conrming a
(data not shown). Finally the EPS and SMP contents were also monitored higher TSS efciency removal for the MBR process. The quality criteria
in the CAS system and compared to the MBR conguration. The signi- dened for the international guidelines varied from 5 to 30 mg/L for
cant differences observed were the variability and the higher values some states in the USA [20] to 20 mg/L in certain government regula-
obtained in the MBR plant due to the higher SS and SSv concentrations. tions [19]. Thus, the values obtained in this study are under the Span-
From the point of view of economical analysis, an operational cost ish Royal Decree and other international guidelines and regulations
estimation of both CAS and MBR plants was performed based on en- for water reuse.
ergy and chemical consumption, considering these as the main com- On the other side, the most commonly used indicators of sewage
ponents on the total operational cost [31]. The results showed that treatment effectiveness are thermotolerant (or faecal) coliforms. E. coli,
total operational costs were 0.38 and 0.40 /m 3 for CAS and MBR which is the thermotolerant coliform species most commonly found
plants, respectively. The inuence of other operation inputs was not in human waste, is generally accepted as being a suitable indicator of

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)

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
for winery wastewater treatment, Water Sci. Technol. 62 (2010) 27542759.
recreational reuse. Finally, the operational cost of MBR is higher than [10] P. Artiga, M. Carballa, J.M. Garrido, R. Mendez, Treatment of winery wastewaters
CAS plant, however it can be considered competitive when compared in a membrane submerged bioreactor, Water Sci. Technol. 56 (2007) 6369.
with other technologies [1,32]. [11] G. Guglielmi, G. Andreottola, P. Foladori, G. Ziglio, Membrane bioreactors for winery
wastewater treatment: case-studies at full scale, Water Sci. Technol. 60 (2009)
12011207.
4. Conclusions [12] P. Artiga, E. Ficara, F. Malpei, J.M. Garrido, R. Mndez, Treatment of two industrial
wastewaters in a submerged membrane bioreactor, Desalination 179 (2005)
161169.
This study evaluates the treatment of winery wastewater by a CAS [13] D. Jeison, J.B. van Lier, Thermophilic treatment of acidied and partially acidied
system and MBR pilot plant installed in the Miguel Torres facilities. wastewater using an anaerobic submerged MBR: factors affecting long-term
The winery wastewater characterization showed a wide variability in operational ux, Water Res. 41 (2007) 38683879.
[14] S. Judd, The MBR Book: Principles and Applications of Membrane Bioreactors for
terms of COD due to the different annual stages in the wine making pro-
Water and Wastewater Treatment, Second Edition Elsevier, 2011.
cess. The MBR pilot plant built and operated by Hera-Amasa showed [15] P.K. Tewari, R.K. Singh, V.S. Batra, M. Balakrishnan, Membrane bioreactor (MBR)
signicant exibility to reduce the COD concentration with removal for wastewater treatment: ltration performance evaluation of low cost polymeric
efciency over close 100% biodegradable fraction of the COD. Further- and ceramic membranes, Sep. Purif. Techol. 71 (2010) 200204.
[16] F. Zanetti, G. De Luca, R. Sacchetti, Performance of a full-scale membrane bioreac-
more, the MBR performance showed a fairly stable operation in terms tor system in treating municipal wastewater for reuse purposes, Bioresour.
of TMP and permeability despite the high variability of the wastewater Technol. 101 (2010) 37683771.
treated. From the point of view of the fouling potential a direct correla- [17] R. Iglesias, E. Ortega, G. Batanero, L. Quintas, Water reuse in Spain: data overview
and costs estimation of suitable treatment trains, Desalination 263 (2010) 110.
tion within EPSp and permeability was obtained. It can be explained by [18] Ministerio Espaol de la Presidencia, Real Decreto 1620/2007, por el que se
the hydrophobic character of this fraction and its potential interaction establece el rgimen jurdico de la reutilizacin de las aguas depuradas, Bol. Of.
with the membrane. The results indicate that MBR pilot plant can Estado 294 (2007) 5063950661.
[19] Queensland Government, Queensland Water Recycling Guidelines, Environmen-
achieve high removal efciencies in winery wastewater treatment and tal Protection Agency, The State of Queensland (Australia), 2005. http://www.
that MBR permeate is suitable for urban, agricultural and recreational derm.qld.gov.au/water/regulation/recycling/pdf/recycle_guidelines.pdf.
reuse according to the quality criteria dened by the Spanish Royal [20] US EPA, Guidelines for Water Reuse EPA/624/R-04/108, Environmental Protection
Agency, Washington DC, USA, 2004.
Decree for water reuse. Furthermore, the efuent reached most of the [21] World Health Organization, Guidelines for the Safe Use of Wastewaters, Excreta
quality specications dened by international guidelines and regula- and Greywater, World Health Organization, Geneva, Switzerland, 2006.
tions for water reuse and reclamation. [22] L. Clesceri, A. Greenberg, A. Eaton, Standard Methods for the Examination of
Water and Wastewater, 20th Edition United Book Press, Baltimore, 1998.
[23] D. Mamais, D. Jenkins, P. Prrr, A rapid physicalchemical method for the determi-
Acknowledgments nation of readily biodegradable soluble COD in municipal wastewater, Water Res.
27 (1993) 195197.
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.
Tecnolgico Industria (CDTI) in the framework of the CENIT project [25] M.A. Bustamante, C. Paredes, R. Moral, J. Moreno-Caselles, A. Perez-Espinosa, M.D.
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)
145151.
[26] C. Beck, G. Prades, A.G. Sadowski, Activated sludge wastewater treatment plants
References optimisation to face pollution overloads during grape harvest periods, Water
Sci. Technol. 51 (2005) 8188.
[1] M.S. Lucas, J.A. Peres, G.L. Puma, Treatment of winery wastewater by ozone-based [27] G. Tchobanoglous, F. Burton, H.D. Stensel, Wastewater Engineering. Treatment
advanced oxidation processes (O3, O3/UV and O3/UV/H2O2) in a pilot-scale bubble and Reuse, McGraw-Hill, New York, 2003.
column reactor and process economics, Sep. Purif. Technol. 72 (2010) 235241. [28] M.D. Fumi, G. Parodi, E. Parodi, A. Silva, R. Marchetti, Optimisation of long-term
[2] R. Mosteo, M.P. Ormad, J.L. Ovelleiro, Photo-Fenton processes assisted by solar light activated-sludge treatment of winery wastewater, Bioresour. Technol. 52 (1995)
used as preliminary step to biological treatment applied to winery wastewaters, 4551.
Water Sci. Technol. 56 (2007) 8994. [29] A.R. Pendashteh, A. Fakhrl-Razi, S.S. Madaeni, L.C. Abdullah, Z.Z. Abidin, D.R.A.
[3] A.R. Mulidzi, Winery and distillery wastewater treatment by constructed wetland Biak, Membrane foulants characterization in a membrane bioreactor (MBR)
with shorter retention time, Water Sci. Technol. 61 (2010) 26112615. treating hypersaline oily wastewater, Chem. Eng. J. 168 (2011) 140150.
[4] M. Petruccioli, J.C. Duarte, A. Eusebio, F. Federici, Aerobic treatment of winery waste- [30] Y. Liu, H.H.P. Fang, Inuences of extracellular polymeric substances (EPS) on oc-
water using a jet-loop activated sludge reactor, Process Biochem. 37 (2002) 821829. culation, settling, and dewatering of activated sludge, Crit. Rev. Env. Sci. Technol.
[5] T.E. Agustina, H.M. Ang, V.K. Pareek, Treatment of winery wastewater using a 33 (2003) 237273.
photocatalytic/photolytic reactor, Chem. Eng. J. 135 (2008) 151156. [31] P. Cot, M. Masini, D. Mourato, Comparison of membrane options for water reuse
[6] G. Andreottola, P. Foladori, G. Ziglio, Biological treatment of winery wastewater: and reclamation, Desalination 167 (2004) 111.
an overview, Water Sci. Technol. 60 (2009) 11171125. [32] F. Kirzhner, Y. Zimmels, Y. Shraiber, Combined treatment of highly contaminated
[7] L. Serrano, D. de la Varga, I. Ruiz, M. Soto, Winery wastewater treatment in a hybrid winery wastewater, Sep. Purif. Technol. 63 (2008) 3844.
constructed wetland, Ecol. Eng. 37 (2011) 744753.
[8] R. Braz, A. Pirra, M.S. Lucas, J.A. Peres, Combination of long term aerated storage and
chemical coagulation/occulation to winery wastewater treatment, Desalination
263 (2010) 226232.