Bioresource Technology 96 (2005) 1650–1657

Potential treatment alternative for laboratory effluents

Larissa C. Alves a, Humberto M. Henrique a, Alcina M.F. Xavier a,
Magali C. Cammarota b,*
a
Department of Chemical Engineering, Federal University of Uberlândia, P.O. Box 593, 38400-902, Uberlândia, MG, Brazil
b
Department of Biochemical Engineering, Federal University of Rio de Janeiro, 21945-970, Rio de Janeiro, RJ, Brazil

Received 19 June 2003; received in revised form 17 December 2004; accepted 31 December 2004
Available online 2 March 2005

Abstract

The Chemical Analysis Laboratory under study weekly generates 46.5 L effluent with low pH (0.7), high COD concentration
(6535 mg O2/L), sulphate (10390 mg/L) and heavy metals (213 mg Hg/L, 55 mg Cr/L, 28 mg Al/L, 22 mg Fe/L, 10 mg Cu/L,
4 mg Ag/L). A treatment sequence has been proposed using a physical chemical step (coagulation/flocculation or chemical precip-
itation) followed by a biological step (anaerobic treatment). Removals of COD (18%), turbidity (76%) and heavy metals (64–99%)
were attained only after adjusting pH to 6.5, without requiring the addition of Al2(SO4)3 and FeCl3. Due to the low COD:sulphate
ratio (0.9–1.3), it was possible to efficiently operate the UASB reactor (at the biological step) only upon mixing the effluent with
household wastewater. COD, sulphate and heavy metals removals of 60%, 23% and 78% to 100%, respectively, were attained for
30% effluent in the reactor feed. The results pointed to the need of a pretreatment step and mixing the effluent in household waste-
water prior to the biological step. This alternative is feasible as this can be achieved using sanitary wastewater generated in the uni-
versity campus.

2005 Elsevier Ltd. All rights reserved.

Keywords: Anaerobic treatment; Chemical precipitation; Laboratory effluents; Sulphate; UASB

1. Introduction Every laboratory trial generates some type of waste,

Universities have been requested by the manufactur-
ing sector to develop research on industrial effluent
treatment and recovery of contaminated soils. However,
in the search for solving or mitigating problems like en-
ergy saving, rationalization of water consumption and
waste recycling, the universities were also responsible
for releasing pollutants. Therefore, considering that uni-
versities should be examples of pollution prevention and
environmental control, some studies have approached
the treatment of effluents generated in university labora-
tories (Alves, 2002; Benatti, 2000).
*
Corresponding author: Tel.: +21 2562 7568; fax: +21 2562 7567.
E-mail address: christe@eq.ufrj.br (M.C. Cammarota).
for example, filtering (paper filter, filtration aids) and
other similar materials, aqueous solutions, organic sol-
vents, and hazardous chemicals (National Research
Council, 1995). At pollution control laboratories, rou-
tine analyses to characterize effluents and to monitor
treatment reactors use concentrated H2SO4 solutions
and reagents containing heavy metals such as Cr6+,
Ag+, and Hg+, among others. Additionally, handling
different types of effluents lead to high concentrations
of organic matter in the laboratory effluents. As result,
the effluents generated in these laboratories are charac-
terized by extremely low pH, high COD, heavy metals
and sulphate (Alves, 2002).
Such characteristics make these effluents highly toxic,
necessitating prior treatment before its discharge into
the sewerage system. Most studies reported in literature

0960-8524/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2004.12.028
 L.C. Alves et al. / Bioresource Technology 96 (2005) 1650–1657
emphasize the management of wastes generated in labo-
ratories, recommending techniques for source reduction,
recycling, reuse and recovery (Davis et al., 1996; Na-
tional Research Council, 1995). The treatment of efflu-
ents with such aggressive characteristics is not reported
in literature and studies about the effect of components
present in these effluents on the efficiency of the treat-
ment systems should be conducted.
This work investigated the treatment of the effluent
generated through several analytical investigations and
in the operation of treatment reactors conducted in the
Effluent Treatment Laboratory at the Federal Univer-
sity of Uberlândia Faculty of Chemical Engineering.
Firstly, the effluent was characterized by the volume
produced and chemical composition. Secondly, physical
chemical treatment was studied in order to reduce the
inhibitory effects exerted by extremely low pH, high
COD, heavy metals and sulphate present in this effluent.
Afterwards, a treatment sequence (physical–chemical/
biological) was evaluated with the objective of verifying
the effect of the discharge of this effluent on the effi-
ciency of the effluent treatment workstation of the
university.
2. Methods
2.1. Effluent collecting and characterization
The effluent generated by chemical analyses con-
ducted at the Effluent Treatment Laboratory at Federal
University of Uberlândia Faculty of Chemical Engineer-
ing from March to May 2001 was characterized. The
waste collected every week was disposed in plastic con-
tainers together with wastewater generated by triple
washing procedure with tap water adopted for cleaning
of laboratory materials. In another tank all volumes col-
lected weekly were deposited in order to make a com-
posite sample, which was employed in the experiments
performed. Aliquots of the volumes collected weekly
and the composite sample were stored under refrigera-
tion at 4 C until analysis.
2.2. Physical chemical treatment
Jar tests were conducted under the following condi-
tions: 120 rpm stirring for 3 min (coagulation), 75 rpm
stirring for 12 min (flocculation) and sedimentation for
30 min. The experiments were conducted in two steps
in order to analyze the effect of the variables pH (3.0–
10.0), type (ferric chloride and aluminum sulphate)
and concentration (60–160 mg/L) of the coagulant agent
on the turbidity and COD removal efficiency. In a first
step, coagulants concentration was set at 60 mg/L and
the initial pH was adjusted into a range of 3.0–10.0 as
previously mentioned. In the second step, pH and coag-
1651
ulant type selected in the first step were used to determi-
nate the best coagulant concentration. Samples of the
raw effluent, the supernatant following pH correction
to 6.5 using NaOH (40%) and the sludge generated in
the chemical precipitation, were collected for the deter-
mination of Hg, Cr-total, Cu, Ag, Fe-total, Al and P
contents.
2.3. Biological treatment
The upflow anaerobic sludge blanket reactor (UASB)
was built in acrylic fiber (1.45 L usable volume) and the
dimensions were 8.5 cm diameter · 33.0 cm height. A
perforated plate with holes of 1.0 mm diameter was
placed above the conical area in the bottom of the reac-
tor to better distribute the feed flow and to prevent the
formation of preferential channels.
The biogas outlet canalization was directed to upper
part of the reactor after passing through a non-conven-
tional triphase separation system, which consisted of
four 10.5 cm height · 7.0 cm diameter deflecting plates
fastened to a central stem. Each plate was positioned
alternately at an angle of 30 (Caixeta et al., 2002).
The gas volume produced in the reactor was measured
in a gas meter by liquid displacement.
Reactor outlet was on one side, coupled to a sedimen-
tation tank for retaining particles not trapped by the tri-
phase separation system. Considering the strong odor
from H2S produced in the reactor, the gas retention by
the system was improved by immersing the sedimenta-
tion tank discharge into a cadmium hydroxide solution.
The experimental system used in this study is shown in
Fig. 1.
The reactor was inoculated with sludge from
an anaerobic reactor of a cigarette factory (VSS =
24,000 mg/L) and fed with a mixture of laboratory efflu-
ent and household wastewater (after pH correction to
7.5–8.0) at a 1.1 mL/min rate of flow giving a hydraulic
retention time (HRT) of 22 h. The reactor operated at
room temperature (29.5 ± 2.3 C) for 157 days.
2.4. Analytical methods
Turbidity, expressed as NTU or FTU, was measured
on a Polylab turbidimeter or using a Hach DR/2000
equipment, respectively. COD was measured according
to HachÕs closed reflux method. The parameters used
for effluent characterization (listed in Table 1) and bio-
reactor handling (sulphate, sulphide, oil and grease)
were determined according to Standard Methods
(Greenberg et al., 1992). The elements Hg, Cr-total,
Cu, Ag, Fe-total, Al and P were determined by mass
spectrometry with inductively coupled plasma (MS-
ICP).
1652 L.C. Alves et al. / Bioresource Technology 96 (2005) 1650–1657

Fig. 1. Schematic drawing of the experimental system used in the biological treatment step. Indexes: 1 = refrigerator, 2 = feed, 3 = gas meter,
4 = peristaltic pump, 5 = UASB reactor, 6 = sedimentation tank, 7 and 8 = H2S absorption.

Table 1 x1 þ x2 þ x3 þ x4 þ   
Characteristics of the effluent generated in the laboratory x ¼ ð1Þ
n
Parametera Week Mixb
The standard deviation is a measure of how precise the
pH 0.37 ± 0.28 0.70 ± 0.23
average is, that is, how well the individual numbers
Total suspended solids 3697 ± 2109 4208 ± 1311
Volatile suspended solids 2824 ± 1744 3405 ± 1475 agree with each other. It is a measure of a type of error
Fixed suspended solids 873 ± 367 803 ± 262 called random error, that is calculated as follows:
COD 4400 ± 2350 6535 ± 3165 sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Oil and grease 222.3 ± 83.7 408.9 ± 111.9 2 2 2
ðx1  xÞ þ ðx2  xÞ þ ðx3  xÞ þ   
Total Kjeldahl nitrogen 189.0 ± 118.9 295.5 ± 38.4 S¼ ð2Þ
Ammoniacal nitrogen 124.5 ± 11.6 108.6 ± 10.3
n1
Total phosphorus 17.4 ± 12.7 23.4 ± 8.8
Anionic surfactants 1.6 ± 0.1 0.1 ± 0.1
Acidity (as acetic acid) 430 ± 148 650 ± 125
Alkalinity (as CaCO3) 287 ± 99 433 ± 83 3. Results
Turbidity 296 ± 83 283 ± 90
Sulphate – 10390 ± 1127 3.1. Collecting and characterizing the effluent
Mercury – 213.5
Total chromium – 55.4
Copper – 9.7
The effluent sampled from March to May 2001 had
Silver – 4.0 seasonal characteristics in accordance with the labora-
Total iron – 222.1 tory and research work underway. The physical and
Aluminum – 27.7 chemical characteristics of the effluent are presented in
Cumulative weekly volume (L) 46.54 ± 16.55 Table 1. The effluent has low pH values, high-suspended
Metal analyses had been carried through a single sample. Values solids (80.9% of which corresponding to organic sub-
represent average ± standard deviation of 12 replicates. stances in the mix), organic compounds (COD), nutri-
a
All parameter values are in mg/L, except for pH and turbidity.
Turbidity is in NTU.
ents (N and P), oil and grease and heavy metals
b
Mix correspond to values obtained for the composite sample. contents. The high content of suspended solids, COD,
nutrients and oil and grease found in the effluent was
due to the fact that the laboratory was conducting re-
2.5. Calculation of average and standard deviation values search studies on dairy effluents and cheese whey.
The COD:sulphate ratio is an important parameter in
In the determination of the characteristics of the ef- the regulation of the competition between methanogenic
fluent and interpretation of the results obtained during and sulphate-reducing bacteria (SRB). COD:sulphate
bioreactor monitoring, were calculated average and ratios higher than 10 are recommended for a successful
standard deviation values of the replicates. Both values anaerobic treatment, and lower ratios would be inhibi-
were calculated using Microsoft Excel software. The tory for methanogenesis because of the high sulphide
average result, x, is calculated by summing the individ- concentrations in the system (Colleran et al., 1994).
ual results and dividing this sum by the number (n) of However, in other studies methanogenesis was success-
individual values (Eq. (1)). ful at COD:sulphate ratios of 5–8 (Hilton and Archer,
 L.C. Alves et al. / Bioresource Technology 96 (2005) 1650–1657
1988; Méndez et al., 1989). The effluentÕs low COD:sul-
phate ratio (0.63) indicates that organic matter used by
SRB is more important and a complete sulphidogenic
system can be developed with COD removal carried
out only by SRB (Lima et al., 2000; Visser et al., 1996).
3.2. Physical chemical treatment
Physical chemical treatment was not successful as low
COD removal efficiencies were obtained: 23–37% and 8–
29% for ferric chloride and aluminum sulphate (both at
60 mg/L), respectively. The condition which presented
higher COD removal (37%) was pH adjustment to 5.0
followed by the addition of ferric chloride (60 mg/L).
However, similar results (15–30% COD removal) were
obtained without the addition of the coagulants but only
with pH adjustment.
Physical chemical treatment provided better turbidity
removal efficiencies than COD: 66–92% and 76–92% for
ferric chloride and aluminum sulphate (both at 60 mg/
L), respectively. The optimum condition was pH adjust-
ment to 4.0 or 5.0 followed by the addition of aluminum
sulphate or ferric chloride (92%). A higher turbidity re-
moval (68–98%) was obtained only with pH adjustment,
without the addition of the coagulants.
Since ferric chloride appeared to be the best coagu-
lant, especially at pH 5.0, further experiments should
be conducted with this coagulant agent. However, this
low pH value would not be indicated because the activ-
ity of anaerobic bacteria would be limited by acidity of
the medium. At higher pH values, residual COD did not
virtually change (COD removals of 32% and 29% at pH
7.0 and 8.0, respectively, compared to 37% at pH 5.0)
but turbidity removal decreased from 92% (pH 5.0) to
66% (pH 7.0) and 78% (pH 8.0). For the choice of the
ideal pH for the process, the recommended values for
further biological treatment were also taken into ac-
count. At pH 6.0 the pretreatment with ferric chloride
presented residual COD and turbidity slightly lower
than those obtained at pH 5.0 and the increment of
0.5 brought pH close to neutrality, making further bio-
logical treatment feasible. Therefore, pH 6.5 was
adopted in the experiments carried out in the second
step.
Table 2
Heavy metals and phosphorus concentrations in the effluent (before and after chemical precipitation (pH = 6.5)) and in the generated sludge
Element Raw effluent (mg/L) Effluent after pH adjustment to 6.5 (mg/L)
Mercury 213.5 52.5
Total chromium 55.4 7.7
Copper 9.7 3.5
Silver 4.0 0.06
Total iron 222.1 27.3
Aluminum 27.7 4.4
Phosphorus – –
The analyses were conducted in the mix (composed of all weekly collected effluents).
1653
Even considering that the removal of COD and tur-
bidity with or without the addition of FeCl3 was similar,
the effect of higher concentrations of this coagulant on
the physical–chemical process was evaluated, once the
concentration adopted at the first step (60 mg/L) could
be insufficient to promote a more significant precipita-
tion. The results obtained only with pH correction or
with pH correction and addition of increasing concen-
trations of ferric chloride did not present marked differ-
ences. COD and turbidity removals of 18% and 76%
were obtained only with pH adjustment, while average
values around 16% and 76% were obtained with pH
adjustment and ferric chloride concentration varying
from 60 to 160 mg/L. Therefore, there was no need to
add coagulant to the effluent and the physical chemical
treatment was only restricted to pH adjustment to 6.5
by means of sodium hydroxide addition.
The results obtained for heavy metals and phospho-
rus in the raw effluent, in the supernatant following
pH adjustment to 6.5 and in the sludge generated after
chemical precipitation are presented in Table 2. One
can see that by merely correcting pH, high metal re-
moval rates (63.9–98.5%) were possible.
The heavy metals concentrations in the treated efflu-
ent would be less toxic and/or inhibitor of microbial
flora in the biological treatment (Speece, 1996; Wong
and Cheung, 1995) as indicated by BOD5:COD ratios
shown in Table 3 for two different samples. The increase
of BOD5 detected after physical chemical treatment (un-
like the reduction observed with COD) was due to the
removal of inhibitory constituents (by precipitation, as
shown in Table 2). These constituents would be inhibit-
ing the action of microorganisms on the biodegradable
organic matter present in the effluent during the incuba-
tion at 20 C for 5 days (standard conditions of the
BOD test). Therefore, the increase of the BOD5 and
BOD5:COD ratio on the effluent after physical chemical
treatment indicates an increase of the degree of biode-
gradability (Eckenfelder, 2000).
Also shown in the table is that the raw effluent (be-
fore physical chemical treatment) exhibited different
BOD5:COD ratios (0.157 and 0.069) because of the
quantitative and qualitative variability of the analyses
carried out in the laboratory, which resulted in different
Removal (%) Sludge (mg/kg)
75.4 173
86.1 10,472
63.9 1187
98.5 2358
87.7 47,094
84.1 4850
– 1899
1654 L.C. Alves et al. / Bioresource Technology 96 (2005) 1650–1657

Table 3
Effluent BOD5 and COD values before and after physical chemical treatment (adjustment pH to 6.5)
Effluent Before physical chemical treatment After physical chemical treatment
Sample 1 Sample 2 Sample 1 Sample 2
BOD5 (mgO2/L) 1449 1056 4398 2594
COD (mgO2/L) 9230 15,220 6750 9860
BOD5:COD 0.157 0.069 0.652 0.263
Sample 1 = mix composed of all weekly collected effluents between March and September 2001.
Sample 2 = mix composed of all weekly collected effluents between October and December 2001.

effluent compositions. Therefore, effluents after physical
chemical treatment sometimes presented high bio-
degradability degree (BOD5:COD ratio = 0.652) and
other times refractory characteristics (BOD5:COD ra-
tio = 0.263) thus making any further anaerobic treat-
ment more difficult.
However, the effect of the physical chemical treat-
ment on toxicity reduction was maintained because the
increase of the BOD5:COD ratio was around four times
in the two samples analyzed. One therefore perceives the
importance of the physical chemical treatment, consi-
dering that besides fostering sedimentation of suspended
solids and metal precipitation, it also contributes to a
higher effluent biodegradability thus making anaerobic
treatment feasible.
3.3. Anaerobic biological treatment
The UASB reactor operated under continuous regime
(22 h HRT) for 157 days. The initial feed was 10% efflu-
ent (in household wastewater) for 10 days, 20% for
16 days, 30% for 14 days, 40% for 12 days, and 50%
for 33 days.
The progress of the soluble COD removal efficiency
during the operational period studied is presented in
Fig. 2. The reactor supported the increase of the per-
centage of the effluent (up to 50%), keeping the COD re-
moval efficiency within the range of 30–70%. However,
when the effluent was replaced by a more concentrated
one with higher SO2
4 and COD contents, removal effi-
ciency dropped abruptly nearly to zero for several days.
soluble COD removal (%)
Reactor efficiency recovery was only possible by reduc-
ing the percentage of the effluent in the feed to values
of 30% again. The use of an effluent with very distinct
characteristics took place in view of changes in the labo-
ratoryÕs routine works. While the first effluent samplings
(March to September 2001) presented turbidity of 280
NTU and COD of 9200 mg O2/L on the average, the
effluent collected at the end of the study (October to
December 2001) presented turbidity of 540 NTU and
COD of 15,200 mg O2/L. As a result of the change in
these parameters, the percentage of the effluent in the
feed was maintained at 30% for 5 days, increasing to
40% for 6 days, and 50% for 6 days. Because of a consi-
derable drop in COD removal efficiency, which in some
cases increased (CODdischarge > CODfeed), it was decided
to return to the 30% effluent composition operating the
reactor under that condition for 55 more days. During
that period, soluble COD removal values were observed
to be less variable and removal efficiency was found to
stabilize at 60% with an average residual COD around
1600 mg/L.
Anaerobic bacteria exhibit an optimum growth over
the pH range of 6.6–7.4 (Lettinga et al., 1996). At pH
8.0 sulphide formed from the reaction of effluent sul-
phate by sulphate reducing bacteria (SRB) is in the form
of HS, less toxic than H2S (Freeman, 1997). Thus, it
was opted by using pH values higher than the estab-
lished one at physical chemical step (6.5) in the reactor
feed. Average pH values at reactor feed and discharge
were 7.6 ± 0.7 and 7.7 ± 0.6, respectively.
Acidity and alkalinity values obtained did not present
satisfactory results during operational period. The acid-
ity increased with the percentage of effluent in the feed.

100 The acidity:alkalinity ratio (1.9–7.2) was also far above

80 the recommended value (0.5). The high acidity at reactor
discharge was probably due to inhibition of methano-
60 genic archaeas and sulphate reducing bacteria by the
40 high concentration of sulphides and metals in the med-
ium (Speece, 1996; Visser et al., 1996).
20
The relationship between volumetric organic load
0 (VOL) and soluble COD at reactor discharge is pre-
0 20 40 60 80 100 120 140 160 sented in Fig. 3a. The increase of VOL introduced in
Time of operation (days) the reactor up to approximately 5.0 kg COD/m3 day
Fig. 2. Soluble COD removal at the UASB reactor throughout the raised the level of the soluble COD in the reactor dis-
operational period. charge at constant and low rate of 0.35 day1. At higher
 L.C. Alves et al. / Bioresource Technology 96 (2005) 1650–1657 1655

8000 m3 day. From this value, efficiency dropped

COD (mgO2/L)

6000 substantially.
4000 Biogas production was between 0 and 0.5 mL/h (mea-
2000
sured at 29.5 ± 2.3 C), except for the last regime (with
30% of effluent) in which production increased to
0
0 1 2 3 4 5 6 7 8 achieve values around 1.0 mL/h and then dropped to
values close to zero. These low values were already
Volumetric organic loading (kgCOD/m3.d)
expected because of the excessive amount of sulphate
(a)
in the effluent. According to Colleran et al. (1994), the
100
reduction of 1.5 g SO24 requires the oxidation of 1.0 g
COD removal (%)

COD, resulting in a 0.233 m3 decrease in the methane

80
60
40
20
0 average COD removal of 2244 mg/L the expected meth-
0 1 2 3 4 5
Volumetric organic loading (kgCOD/m3.d)
(b)
Fig. 3. Relationships between volumetric organic load applied and
soluble COD in the UASB reactor effluent (a) and soluble COD
removal efficiency (b).
VOL, the rate increased drastically showing an average
value of 1.30 day1. Therefore, the maximum VOL sup-
ported by the reactor would be 5.0 kg CODs/m3 day.
Soluble COD removal efficiency as a function of the vol-
umetric organic load applied to the reactor is shown in
Fig. 3b. The data show that reactor efficiency remained
in a range of 40–70% up to approximately 5.0 kg COD/
production for each kg of reduced SO2 4 . Considering
that, in the last regime, the reduced sulphate concentra-
tion in the reactor was of 760 mg/L, the methane de-
crease would be around 13 mL/h (at 29.5 C). For an
6 7 8 ane production would be of 44 mL/h. Therefore, beyond
the sulphate reduction contributing for a lesser methane
production, probably it also had an accented inhibition
of the methanogenic activity in function of high sulphide
concentrations formed in the medium.
When the reactor feed contained 40% effluent, analy-
ses of heavy metals were performed and the results are
presented in Table 4. The heavy metals removal oc-
curred efficiently and, probably, it was due to the forma-
tion of insoluble metallic sulphides, which precipitated
and incorporated into the biomass, being trapped in
the reactor.
Sulphate, sulphide and oil and grease concentrations
in the reactor feed and discharge were determined
to examine their removal in the last two weeks of

Table 4
Heavy metals concentration in reactor influent and effluent during operation with 40% effluent (Sample 1 = effluent collected between March and
September 2001)
Sample Fetotal (mg/L) Cu (mg/L) Crtotal (mg/L) Crhexavalent (mg/L)
Effluent pH adjusted to 6.5 67.25 ± 6.22 9.64 ± 3.18 0.18 ± 0.04 0.15 ± 0.03
Influent 34.50 ± 6.20 3.25 ± 1.52 0.09 ± 0.02 0.07 ± 0.02
Effluent 3.33 ± 0.52 nd 0.02 ± 0.01 0.01 ± 0.01
Removal (%) 90.3 ± 0.35 100.0 ± 0.00 77.8 ± 0.59 85.7 ± 0.84
nd = not detected; values represent average ± standard deviation of four replicates.

Table 5
Sulphate and sulphide concentrations obtained in the last two weeks of operation, when the reactor feed contained 30% effluent (Sample 2 = effluent
collected between October and December 2001)
Sample Sulphate Sulphide
Reactor feed (mg/L) Reactor discharge (mg/L) Removal (%) Reactor feed (mg/L) Reactor discharge (mg/L) Removal (%)
1 3400 2900 14.7 37.4 8.2 78.1
2 3500 2300 34.3 85.3 34.1 60.0
3 3200 2500 21.9 65.6 35.4 46.0
4 2800 2100 25.0 88.2 37.9 57.0
5 3400 2700 20.6 87.2 29.9 65.7
Average 3260 2500 23.3 72.7 29.1 61.4
SD 279 316 7.2 21.8 12.0 11.8
Average and standard deviation (SD) calculated of the five replicates.
1656 L.C. Alves et al. / Bioresource Technology 96 (2005) 1650–1657
Table 6
Oil and grease obtained in the last two weeks of operation, when the
reactor feed contained 30% effluent (Sample 2 = effluent collected
between October and December 2001)
Sample Oil and grease
Reactor Reactor Removal
feed (mg/L) discharge (mg/L) (%)
1 165.6 75.0 54.7
2 102.0 42.0 58.8
3 124.0 76.0 38.7
4 292.0 29.5 89.9
Average 170.9 55.6 60.5
SD 84.9 23.5 21.4
Average and standard deviation (SD) calculated of the four replicates.
operation. Average removals of 23.3% and 60.5% for
sulphate and oil and grease are shown in Tables 5 and
6, respectively. The increased removal of oil and grease
observed probably did not occur by means of the bio-
degradation processes, but through the retention of
these compounds in the sludge blanket. Meanwhile,
the soluble sulphide (HS) concentration decreased after
passing into the reactor. A higher total sulphide concen-
tration in the reactor discharge was expected due to sul-
phate reduction promoted by SRB. Possibly, sulphur
element could be present in the effluent in other forms
such as H2Sliquid, H2Sgas, S2, which are not quantified
in the methodology adopted. Sulphur would be also
assimilated by the bacteria since it is one of the neces-
sary nutrients for organic matter degradation (Speece,
1996). Moreover, the high metals removal in the reactor
points to metallic sulphides formation, which would re-
duce the soluble sulphide concentration in the medium.
4. Conclusions
In the physical chemical treatment of the effluent gen-
erated in the laboratory, low COD removals with both
coagulants (up to 37%) were obtained. However, only
the adjustment of pH for 6.5 resulted in high metal re-
moval (64–99%), improving the effluent biodegradabil-
ity. After adjustment of pH, the effluent BOD5:COD
ratio increased four times.
During the operation of the UASB reactor the influ-
ence of the low COD:sulphate ratios on anaerobic activ-
ity was confirmed. In this study the COD:sulphate ratio
varied from 0.9 to 1.3 and the anaerobic treatment of the
laboratory effluent was not possible. Reduction of sul-
phate concentration in the feed and consequently sul-
phide generation in the reactor was attained after mix
of the effluent with household wastewater. Satisfactory
results were obtained with 30% effluent (4.1 kg COD/
m3 day) in the mixture fed to the reactor to obtain solu-
ble COD (60%), sulphate (23%), oil and grease (60%)
and heavy metals (78–100%) removal.
This study showed the importance of the physical
chemical step prior to the biological step in the laboratory
effluent treatment in order to reduce the inhibitory effects
exerted by extremely low pH, high COD, heavy metals
and sulphate present in this effluent. Even after pretreat-
ment, the anaerobic reactor only presented moderate effi-
ciencies when fed with mixtures of effluent (in small
proportions) and household wastewater. These results
indicate that other alternatives should be investigated,
such as the development of specific treatment methods
for sulphate removal, considering that SRB action ham-
pers the process efficiency and results in the release of
unpleasant odors and the equipment corrosion; and the
post-treatment of effluents is necessary in order to in-
crease dissolved oxygen levels and to reduce the organic
load (polishing) for direct disposal into receiving bodies.
Acknowledgements
The authors thank CAPES/PROCAD, FUJB, and
FAPERJ for the funding granted to their research
project.
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