Combining UASB technology and advanced oxidation

Water Science and Technology Vol 45 No 10 pp 329334 IWA Publishing 2002

processes (AOPs) to treat food processing wastewaters
G.O. Sigge, * T.J. Britz,* P.C. Fourie,** C.A. Barnardt,*** and R. Strydom***
* Department of Food Science, University of Stellenbosch, Private Bag X1, Matieland 7602, South Africa
** ARC-INFRUITEC, Private Bag X5013, Stellenbosch 7599, South Africa
*** Oz Purification, P.O. Box 154, Ifafi 0260, South Africa

Abstract UASB treatment of fruit cannery and winery effluents was shown to be feasible. However, the
treated effluents still have residual COD levels well above the legal limit of 75 mg.l1 for direct discharge to a
water system and a form of post-treatment is necessary to reduce the COD further. Ozone and
ozone/hydrogen peroxide were used in combination with a granular activated carbon contacting column to
assess the effectiveness as a post-treatment option for the UASB treated fruit cannery and winery effluent.
Colour reduction in the effluents ranged from 66 to 90% and COD reductions of 2755% were achieved.
The combination of ozone and hydrogen peroxide gave better results than ozonation alone. Significant
progress was thus made in achieving the legal limit of 75 mg.l1.
Keywords Cannery effluent; granular activated carbon; hydrogen peroxide; ozone; post-treatment; UASB;
winery effluent

Introduction
Due to the nature of the fruit and vegetable canning process, large volumes of water are
used in product transportation, washing and rinsing, blanching, retorting and cooling
operations (Water Research Commission, 1987a; Wayman, 1996). The wine industry is no
different, producing large volumes of wastewater throughout the year. Most of the water
originates from cellar cooling and floor and equipment washdown (Ronquest, 1999). These
industries are thus faced with firstly, maintaining a profitable level of production while
reducing the intake of fresh, potable water, and secondly, disposing of the large volumes of
effluent in an environmentally responsible manner.
Treatment of these effluents (seasonal fruit cannery and winery) by upflow anaerobic
sludge blanket (UASB) reactors has recently been shown to be a feasible option. COD
reductions of up to 93% at organic loading rates (OLR) of 10.95 kgCOD.m3.d1 and
hydraulic retention times (HRT) of <12 h (Trnovec and Britz, 1998) were achieved
treating a fruit canning wastewater. Similarly, COD reductions of 93% at an OLR of 11.05
kgCOD.m3.d1 and a HRT of 14 h were achieved treating a winery wastewater (Ronquest,
1999). In many instances the COD level of the final effluent is still well above the South
African legal limit permitted for wastewaters (75 mg.l1) to be discharged to a water system
(Water Research Commission, 1987b) and a further post-treatment is thus necessary.
The use of advanced advanced oxidation processes (AOPs) in the treatment of waste-
waters has recently become popular (Hunt and Marias, 1997; Camel and Bermond, 1998).
AOPs have been defined as processes which involve the generation of hydroxyl radicals in
sufficient quantity to effect water purification. The most common processes are O3/H2O2,
O3/UV and H2O2/UV. The use of these AOPs is thus an attempt to produce the maximum
amount of these hydroxyl radicals (Gottschalk et al., 2000). The hydroxyl radical has a high
oxidation potential (2.8 eV) and attacks organic molecules by either abstracting a hydrogen
atom or by adding to double bonds. Organic molecules are thus mineralized to non-toxic
forms such as carbon dioxide or water (Mourand et al., 1995; Gulyas et al., 1995; Beltrn et 329
 al., 1999). Some organic compounds react rapidly with ozone leading to destruction, while
others are only partially oxidized. Partially oxidized molecules become more polar, pro-
ducing more complexed insoluble materials which are then easily removed/absorbed by
activated carbon filters (Gulyas et al., 1995). Granular activated carbon (GAC) is thus
used effectively in removing taste and odour compounds, colour, organics, excess chlorine,
pesticides and toxic and mutagenic substances, due to the large adsorption area
(500600 m2.g1) available (Bitton, 1994).
G.O. Sigge et al.

The COD contents of several food processing wastewaters have been successfully
degraded using ozone, H2O2 and/or UV, including fruit cannery, distillery, poultry and
tomato processing wastewaters (Chang and Sheldon, 1989; Beltrn et al., 1997; Sigge et
al., 2001). Lowering of the polyphenol contents of table olive debittering wastewaters
(Beltrn et al., 1999) and decolorization of yeast-production industry wastewaters has also
been achieved (Filipovc-Kovacevic and Sipos, 1995).
The aim of this study was to investigate the possibilities of using combinations of UASB
technology, ozonation, granular activated carbon and hydrogen peroxide to treat cannery
and winery wastewaters.

Materials and methods

Effluents
A fruit cannery effluent with an average COD of 7,500 mg.l1 and pH of ca. 5.0 was collect-
ed from a nearby fruit cannery during the apricot canning season. After sedimentation, to
separate the excess solid material, the pH of the effluent was adjusted to 7.5 before use as
substrate for anaerobic treatment.
A winery effluent with an average COD of 3,700 mg.l1 and pH of ca. 4.8 was collected
from a local winery. Solid material was removed by sedimentation and the pH of the efflu-
ent was then adjusted to 7.5 before use as substrate for anaerobic treatment.

Anaerobic treatment
A 2.3 l laboratory-scale upflow anaerobic sludge blanket (UASB) bioreactor was used
(Trnovec and Britz, 1998) and operated at 35C (Meyer et al., 1985). The volume of the
biogas was determined using a manometric unit equipped with an electronically controlled
counter and a gas-tight valve and the volumes corrected to standard temperature and pres-
sure. The substrate was fed semi-continuously to the bioreactor by means of a peristaltic
pump (Watson-Marlow 302S) controlled by an electronic timer. The bioreactor was run at a
HRT of 24 h. The pH, COD, alkalinity, orthophosphate phosphorous, total solids of the
bioreactor effluent were monitored (Standard Methods, 1992).

Oxidation
Ozonation of the UASB treated fruit cannery and winery effluent was done in a continuous
mode, bubble/GAC contacting setup. This consisted of a glass bubbling column connected
to a GAC column. Ozone was bubbled upwards through the glass column, while the efflu-
ent was re-circulated from the bubbling column through a GAC contacting column. The
bubbling column (l = 90 cm;  = 6 cm) had a sintered glass disc at one end for bubble gen-
eration. The GAC contacting column consisted of a closed stainless steel cartridge (l = 20
cm;  = 6.5 cm) filled with granular activated carbon. An ozone generator (Oz Purification,
Ifafi) producing 9.0 g .h1 O3 at a flowrate of 4 l.h1was used for the ozonation trials.
The effect of hydrogen peroxide (H2O2) addition to the oxidation treatments was also
investigated by adding 1% H2O2 to the bioreactor effluent before ozonation. The different
continuous mode treatment combinations studied are summarized in Table 1.
330
Table 1 Summary of the different treatment conditions studied in the treatment of UASB treated effluents

Treatment description

Continuous mode (cannery and winery effluent treated by UASB)

1 UASB effluent + 5 min ozonation
2 UASB effluent + 10 min ozonation
3 UASB effluent + 15 min ozonation
4 UASB effluent + 30 min ozonation

G.O. Sigge et al.

5 UASB effluent + 1% H2O2 (v/v) + 5 min ozonation immediately
6 UASB effluent + 1% H2O2 (v/v) + 15 min ozonation immediately

Analytical methods
The ozone production was measured using an iodiometric titration (Standard Methods,
1992) and residual ozone concentrations in the effluent were determined using the DPD
Method (Hach Co., Loveland, CO). COD was determined colorimetrically using a DR2000
spectrophotometer (Hach Co., Loveland, CO) and standardised procedures (Standard
Methods, 1992). Colour removal in the effluent was determined by monitoring the
absorbance of the effluent at 288 nm using a Spectronic 20 Genesys spectrophotometer
(Spectronic Instruments, USA).

Results and discussion

Anaerobic digestion
During the anaerobic treatment of the cannery effluent the COD was lowered by 9093%.
The bioreactor effluent had a pH of 7.07.2 and a COD concentration of 525750 mg.l1.
The effluent from the bioreactor treating the winery effluent had a pH of 7.27.4 and a COD
concentration of 148370 mg.l1, constituting COD reductions of 9096%. These bioreac-
tor effluents were used in the oxidation studies.

Oxidation
Oxidation treatments resulted in significant colour reductions, as can be seen from Table 2.
Increases in the treatment time led to increases in colour reduction of 66% after 5 min to
90% after 30 min. The addition of 1% H2O2 (v/v) to the 5 and 15 min oxidation treatments
led to slight increases in colour reduction (from 66 to 70% and 87 to 90%, respectively) for
the effluent from the bioreactor treating cannery wastewater. The same tendency was found
for the effluent from the bioreactor treating a winery wastewater. Increases in ozonation
time increased colour reduction from 68% (5 min O3) to 87% (30 min O3), with increases
from 68 to 71% and 83 to 88% when adding 1% H2O2 (v/v) to the 5 and 15 min oxidation
treatments, respectively. These results compare favourably with previous studies on the
reduction of UASB bioreactor effluent colour with O3 and H2O2 (Sigge et al., 2001). The
colour reductions achieved in this study were, however, somewhat higher. This could pos-
sibly be due to the inclusion of a GAC contacting column in the continuous mode oxidation
used in this study. Beltrn et al. (1997, 1999) also found that H2O2 alone was not an
effective oxidizing agent in the treatment of tomato processing wastewaters and distillery
wastewaters.
The oxidation treatments were also effective in reducing the COD of the effluents.
Increases in the ozonation time led to increases in COD removals from 27 and 30% after
5 min to 53 and 55% after 30 min for effluents from bioreactors treating cannery and winery
wastewaters, respectively (Figure 1). Similar increases in COD reduction with increased
reaction time were also found when treating UASB treated alkaline cannery effluent (Sigge
et al., 2001), debittering table olive and (Beltrn et al., 1999), yeast-production industry 331
 60
Cannery UASB Effluent
Winery UASB Effluent
50

40
COD Removal (%)
G.O. Sigge et al.

30

20

10

0
5 min O3 10 min O3 15 min O3 30 min O3 1% H2O2 + 1% H2O2 +
5 min O3 15 min O3
Treatment Conditions

Figure 1 COD removal during the different treatment conditions used in the post-UASB treatment of alka-
line fruit cannery effluent

wastewaters (Filipovc-Kovacevic and Sipos, 1995), chlorinated aromatics (Schmitt and

Hempel, 1993), tomato and distillery wastewaters (Beltrn et al., 1997). It is also clear from
the data in Figure 1 that the increases in COD reduction over time are not linear. Initially the
rate of COD degradation is rapid, but the rate decreases with time. This can probably be
ascribed to the fact that some organic compounds are more susceptible to oxidation than
others, while some are only partially oxidized (Camel and Bermond, 1998). This indicates
that the UASB effluents contain a considerable amount of difficult to oxidize compounds
that require a stronger oxidizing system.
The slightly higher reductions in the bioreactor effluent COD achieved in this study,
using ozone in the continuous mode compared to the batch method (Sigge et al., 2001) are
probably the result of the GAC contacting column. Certain molecules are only partially oxi-
dized by ozone, forming lower molecular weight compounds, which are better adsorbed on
the GAC column (Camel and Bermond, 1998), thus lowering the effluent COD.

Table 2 The effect of oxidation treatments on the colour of effluents from UASB bioreactors treating fruit
cannery and winery wastewaters

Treatment Absorbance (288 nm) Colour reduction (%)

Bioreactor effluent (cannery) 1.522

5 min O3 0.516 66
10 min O3 0.258 83
15 min O3 0.196 87
30 min O3 0.153 90
1% H2O2 (v/v) + 5 min O3 0.457 70
1% H2O2 (v/v) + 15 min O3 0.152 90

Bioreactor effluent (winery) 0.520

5 min O3 0.166 68
10 min O3 0.104 80
15 min O3 0.088 83
30 min O3 0.068 87
1% H2O2 (v/v) + 5 min O3 0.151 71
1% H2O2 (v/v) + 15 min O3 0.062 88
332
 Addition of 1% H2O2 (v/v) to oxidation treatments resulted in slight increases in COD
reductions over treatments only being ozonated (Figure 1). With the 1% H2O2 (v/v) addi-
tion to the 5 min ozonation, the COD reduction increased from 32 to 34%, while an increase
from 48 to 50% was achieved with the 15 min ozonation. The increase in COD reduction
with increased ozonation time and addition of H2O2 were expected as both lead to forma-
tion of more hydroxyl radicals, and thus create a stronger oxidizing capability (Beltrn et
al., 1997; Hughes, 1992). The same tendency was found by Sigge et al. (2001) when

G.O. Sigge et al.

ozonating an UASB treated fruit cannery effluent. Slightly higher COD reductions were,
however, achieved in this study using the continuous mode of oxidation and 1% H2O2 (v/v)
additions (i.e. 48 and 50% compared to 45% for a 15 min O3 treatment). Hydrogen peroxide
on its own is expected to be less effective due to its lower oxidation potential in comparison
to ozone and the hydroxyl radical (Hughes, 1992; Mourand et al., 1995).

Conclusions
Advanced oxidation processes and the use of GAC can be successfully used in combination
to lower the COD of UASB treated cannery and winery effluents. The use of a continuous
mode of oxidation (inclusion of a GAC contacting column through which the effluent is re-
circulated during ozonation) resulted in an improvement in colour and COD reduction.
These increases can probably be ascribed to the GAC contacting column, where adsorption
of organic molecules is taking place. A longer contact time with the GAC would, however,
seem to be beneficial in lowering the COD even further. This is deduced from the fact that
batch ozonated effluents filtered by GAC with long retention times (812 h) resulted in sig-
nificantly higher COD reductions. In the continuous mode oxidation process the total GAC
surface area is also considerably smaller than the GAC filter used in the batch method.
Ozone, hydrogen peroxide and GAC can nevertheless be succesfully applied in combination
treatment processes to lower the COD of UASB treated fruit cannery and winery effluents.

Acknowledgements
The support of the ARC-INFRUITEC, Ashton Canning Co Pty Ltd, Langeberg Food
Processors Ltd Paarl, Rhodes Fruit Farms, SA Preserving Company and the University of
Stellenbosch is gratefully acknowledged.

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