Utilization of Industrial Waste and Wastewater for

Nutrient Removal in Municipal Effluent treatment

Markku Huhtamäki
Juurocon Oy, Alitalontie 11, 21110 Naantali, Finland (e-mail: juurocon.oy@dnainternet.net)

Abstract: Especially food industry effluents are known to improve nitrogen removal from
wastewaters. Reducing the industrial effluent pre-treatment increases soluble BOD-load to the
wastewater treatment which, if well managed, brings savings for both partners. The
municipality saves in methanol costs and the industry in reduced investment and operational
costs. At the same time natural resources are spared. There are promising experiences also
for use of other industrial effluents and waste liquids. One major obstacle to utilizing of
industrial wastewater and waste liquids is biases. Utilization requires co-operation and
willingness between municipality, industry and local authorities as well as tests and
understanding of the integrity. Conventional wastewater taxation models (high taxes for BOD)
prevent this kind of co-operation. In this report potential ways for utilization of industrial
effluents, control of them and needed tests as well as cost influences are described.

Content
Content ................................................................................................................................1
Introduction .........................................................................................................................2
Principles of nitrogen removal.............................................................................................2
Alternative ways for utilization of industrial effluents ........................................................3
Industrial wastes and wastewaters in nitrogen removal.......................................................4
Risk factors in nitrogen removal..........................................................................................4
Normal operational risks..............................................................................................4
Inhibition .....................................................................................................................5
Other potential risks.....................................................................................................6
Testing the impacts of industrial effluents...........................................................................6
Nitrification tests .........................................................................................................6
Inhbition tests ..............................................................................................................7
Denitrification tests......................................................................................................7
Modelling and simulation ..................................................................................................11
Criteria for wastewater taxation between the partners.......................................................14
Economic and environmental benefits...............................................................................14
References .........................................................................................................................15

With the contribution of the LIFE financial instrument of the European Community

Project-LIFE03 ENV/FIN/000237; Raisio, Finland; www.raisio.fi/ripesca

2 Markku Huhtamäki

Introduction
In Europe 70% nitrogen removal is required for municipal effluent treatment plants more
than 10 000 pe in sensitive areas (Directive 91/271 for municipal effluent treatment). With
the implementation of the Water Framework directive (2000/60/EU) the requirements are
going to be tighter. In the Netherlands purification systems are now developed to reach 2.2
mg N/l and 0.15 mg P/l (Uijterlinde et al 2005) which are the maximum allowable risk
requirements for N and P for the receiving surface water.
Biological nutrient removal requires easily biodegradable carbon source (soluble BOD).
For municipal effluent treatment BOD has to be added in order to achieve efficient nitrogen
removal – usually methanol is the cheapest commercial alternative and it is used.
Industrial effluents could be utilized much more than today is used. The cheapest carbon
sources could be industrial waste liquids or industrial effluents, which have not been treated
biologically. The biological pre-treatment removes soluble BOD and as a result the
municipal sewage treatment plant has to buy alternatively carbon sources. The both parties
could save money and environment.
The water temperature is significant for nitrogen removal. Often the maximum effluent
temperature is limited to 35 - 40 oC. However, cooling of effluents should be required only to
the tolerable limits of the sewerage system, unless the fraction of hot waters is so high that
there is a risk that the process temperature at the municipal plant exceeds 35 oC.

Principles of nitrogen removal

Typical municipal nitrogen load is about 14 g/pe/d, corresponding 40 - 60 mg/l effluent
nitrogen concentration. Most of the urea and proteins (kitchen and toilet effluents) are
decomposed already in the sewerage system to ammonia. At the effluent treatment about 25
% of nitrogen is removed in primary and secondary sludge. A biological nitrification-
denitrification process is typically applied for more efficient nitrogen removal.
Nitrification is a slow, sensitive and temperature depending process. The basin volumes
are determined principally based on the nitrogen removal (kg/d). The sludge age has to be
longer than the reproduction time for the nitrifying bacteria. As a thumb rule at 10 oC and 10
days aerobic sludge age is the minimum. For each degree oC the requirement for sludge age
and basin volume is changed by 10%. If the dimensioning is done to 4 oC instead of 10 oC a
70% bigger aerated volume is needed.
Under anoxic conditions bacteria can utilize the oxygen from nitrate in their metabolism.
This takes place when soluble oxygen is first utilized and providing that soluble carbon
source is available there. In the metabolism nitrogen gases and carbon dioxide are released
and biomass is generated. The conversion of nitrate-nitrogen to nitrogen gas requires 5 g
soluble biodegradable COD/ g reduced nitrogen. The relation depends slightly on the
available carbon source.
In practice, nitrogen removal can be implemented in several ways. One alternative is a
post-denitrification (fig 1) where nitrogen compounds are first oxidized to nitrate
(nitrification) and then under anoxic conditions, with the aid of carbon source, reduced to
nitrogen gas (denitrification). Pre-nitrification (fig 2) utilises the carbon source from the
incoming wastewater. At the beginning of the process there is an anoxic stage where influent
is taken and to which nitrified water is recycled for nitrogen removal. The operational costs
are higher in the post-denitrification alternative but better purification results are possible to
 Markku Huhtamäki 3

be reached. Processes, in which these both alternatives (fig 2) are integrated, are more
flexible and allow the optimization between the efficiency and operational costs.

Post-denitrification; ND-process Pre-denitrification; DN-process

Figure 1. Basic processes for nitrogen removal

Carbon Source
Nitrate cycle
Me3+ Me3+

Anoxic/ Anoxic/
Anaerobic Anoxic Aerobic Aerobic Aer
Aerobic Aerobic

Return sludge

Figure 2. Modified 5-stage Bardenpho-process is suitable for efficient biological nitrogen and
phosphorus removal

Alternative ways for utilization of industrial effluents

The differences of industrial and municipal effluents have been utilized successfully in
several cases. The utilization is based on different factors depending on temperature, the load
fractions at the treatment and how they are transported to the sewage treatment plant.
Carbon source: Typically the industrial soluble BOD reduces the needed amount of
commercial carbon source and results in better purification. In the simplest case when the
industrial load factor is of minor importance, its BODsol reduces the methanol dosage. There
are cases where industry has been required to build biological pre-treatment which is later
by-passed in order to avoid a commercial carbon source addition at the municipal effluent
treatment plant.
Denitrification rate: In wwtps where the process volumes are limited, the denitrification
rate can be increased by using industrial soluble BOD. This can be critical for the results. If a
carbon source can be replaced with another one having a double denitrification rate, it means
that denitrification step can be performed in half of the earlier volume.
Nitrification rate: Denitrification rate increases by about 10% for each oC. If the fraction
of industrial effluent is 20% and its temperature is 20 oC higher than other effluents´ when
reaching the wwtp, it increases the temperature of combined effluents by 4 oC. This means
about 50 % higher nitrification rate and reflects in smaller need for process volumes and/or
improved purification results.
4 Markku Huhtamäki

Assimilation: If the load fraction of industrial effluents is high, the biomass growth is
able bind so much nitrogen (assimilation) that denitrification is not needed. (In Finland e.g.
Huittinen + foodstuff industry and Kotka + paper industry). Also the co-operation can be
arranged so that the municipal effluents are taken to the industrial effluent treatment plant.
The industry can save in nutrient dosage and the total environmental load can be reduced
more than before with lower costs. (Examples in Finland: UPM/Rauma + Rauma, Metsä-
Botnia/Mänttä + local municipalities, Enocell Oy + Eno and Raisio Oyj/Vihanti + Vihanti).
Other cost saving potentials: The BOD:N:P- relation in many industrial effluents is such
that if these waters would be treated separately, nitrogen (urea) and phosphor (phosphoric
acid) should be added. Using combined treatment with municipal effluents, the nutrient
addition for industrial effluents may be avoided. Also the addition of carbon source and
precipitation chemicals needed for separate municipal effluent treatment may be avoided.
The combined treatment saves also in labour costs but first of all it is more sustainable
environmental management.

Industrial wastes and wastewaters in nitrogen removal

The influences of industrial effluents to municipal effluent treatment are studied widely and
there are a lot of practical examples too. The most problematic effluents are typically from
industry having low effluent volumes and loads but which may contain solvents or heavy
metals. These are e.g. metal industry service stations, printing houses, landfills etc. Industry
having high effluent volumes and load are seldom causing problems, if the solid and fat
separation and pH-regulation are taken care of.
Cappai et al (2004) have confirmed the positive impact e.g. for ice cream factory and
sugar beet factory effluents especially due to the increased denitrification speed.
Mokhayeri et al (2006) have measured e.g. the corn syrup to have higher denitrification
rate than acetate and more than double compared to methanol. The results were similar in
lower (13 oC) and higher (19 oC) temperatures, although the denitrification rates were of
course higher at higher temperatures.
Peng et al (2002) have measured in their studies that denitrification using a brewery
effluent was about 5,5-times compared to methanol and respectively 40-time more efficient
than using the sludge endogenous respiration. The denitrification rates were respectively for
brewery effluent, methanol and endogenous respiration 22.4, 4.1 and 0.534 (mg NO3-N/h ) /
g MLSS.

Risk factors in nitrogen removal

Normal operational risks

Independently of industrial effluents a successful nitrogen removal demands the following:
- Sufficiently easily biodegradable BOD in anoxic sections
- Sufficiently nitrate flow to anoxic sections
- Sufficiently oxygen in the aerated sections
- pH in the range of 7,0 – 8,5
- Sufficiently biomass to retain the required sludge age in the activated sludge
and/or enough biofilm media in which the sludge can grow
- Toxic (inhibiting) substances are not allowed (e.g. solvents and heavy
metals)
 Markku Huhtamäki 5

All this fields have to be taken care of in order to reach efficient nitrogen removal.

Inhibition
Nitrifying bacteria are more sensitive for chemicals than heterothrophs which are responsible
for the BOD removal.
Often the inhibition problems are caused by unconscious and careless behaviour.
Somebody can just drain e.g. solvents used for machine cleaning and thinking that such a
small amount can not be harmful. However, e.g. 0,1 – 1 litres of chlorinated solvents in 1000
m3 of effluent (0,1 – 1 mg/l) can be toxic for the nitrifying bacteria. Such spills can stop the
nitrification at the effluent treatment plant and the growing of these bacteria has to be
restarted. Due to the low growth rate of the nitrifyers a “small” spill once a month may have
a substantial effect on nitrogen removal. In such cases general information and education is
needed. Understanding of the consequences and alternative operation ways as well as control
may improve the situation.
Some biotoxic concentrations for nitrifyers are given in table 1. Especially chlorinated
solvents, dyes and heavy metals can be very poisonous. The chemicals having a chloro-,
amino- or nitrate- group can be remarkably more toxic than the corresponding chemicals
without this group.
Regressive inhibition can occur under some situations like high ammonium
concentrations especially when combined with low (pH < 7,0) or high (pH > 8,5) pH. It
means that when the conditions are normal again, the nitrification rate is restored unless the
situation has not been prolonged too long (more than 20 % of the sludge age).

Table 1. Toxity data (EC50 mg/l) for heterothrophs and Nitrosomonas (Eckenfelder 2000).
Heterothrophs Nitrosomonas BOD /
COD
Methanol 20000 880 >50%
Ethanol 24000 3900 >50%
Acetone 16000 1200 25.50%
Toluene 110 84 >50%
Benzene 520 13 >50%
Chlorobenzene 310 0,7 <10%
Nitrobenzene 370 0,92 >50%
Phenol 1100 21 >50%
4-chlorophenol 98 0,73
Nitrophenol 160 2,6
Aminophenol 0,27 0,04
2-chloropropionic acid 0,18 0,04
1,1-dichloroethane 620 0,91
Trichloroethylene 130 0,81 >50%
Methylchloride 320 1,2 <10%
Thoreau 2,8
Allylthiourea 0,1

Copper 1 0,005
Chrome (VI) 1.10 0,25
Nickel 1…2,5 0,25
Zink 0,08…10 0,08.0,5
6 Markku Huhtamäki

Other potential risks

In addition to toxic and inhibiting substances also high solid and fat concentrations can result
in poor nitrification and effluent quality.
Fat attaches on the microbes covering them and limiting their oxygen supply and
especially nitrification. Excessive fraction of fats from the total load (more than 10% of
organic material) causes often light or filamentous sludge with poor sedimentation
properties. Fat consumes also high amount of oxygen (1 g fats = 3 g COD).
Antifoaming agents reduce oxygen solubility in the process and may also limit
nitrification. Dispergation agents cause poor sludge settling properties, which may prevent
keeping the required sludge ages (and also the effluent solid concentration increases).
Wastewater fraction rich in these components should be pre-treated separately (like paper
industry often does for their coating colour kitchen effluents).
High incoming solid loads (to the biological section) reduce the fraction of nitrifyers in
the sludge. If the solid concentration is high compared to BOD (> 1,5), a pre-clarifier is
recommended to be installed either at the industrial pre-treatment or at the municipal plant.
In case the wwtp has difficulties in winter-time nitrification, a pre-clarifier improves the
biological process.
The temporary very high solid loads are even a higher risk for an activated sludge process
than a constant high load. The peaks can reduce the sludge age so much that nitrifyers are
flushed away resulting in a rather long period with poor nitrogen removal. If the risk for such
a load is high, a control (e.g. based on turbidity) and removal possibility should be arranged.

Testing the impacts of industrial effluents

Standardized tests are used for evaluation the influence of industrial effluents to nitrification
and denitrification. Waters consisting of several compounds are not behaving linearly like
pure chemicals. A relevant test performance needs several time points for each test like e.g.
in figures 3 and 4. Applying the tests for industrial effluents and waters requires experience
and knowledge for the background factors, which may influence in results. In the following
is highlighted some points which should be taken into account when using and testing
industrial effluents.

Nitrification tests
In a nitrification test the conversion of ammonium to nitrate is followed by using test sludge.
In the example shown in figure 3 high oxygen consumption during the first hour and increase
of ammonium due to hydrolyses can be seen. In full scale treatment this very quickly usable
organic material is excellent for denitrification. It would give excellent denitrification rates
and would probably be consumed already before the water enters the nitrification zone. After
this, in this example, the ammonium removal has been doubled compared to the generated
nitrite and nitrate, which may be due to exceptional biomass generation and nitrogen
assimilation. If the difference between ammonium removal and nitrate generation in the tests
is more than 20%, the reason for that should be evaluated.
The nitrification tests may take several hours and the pH buffering and temperature
stabilization has to be done. The practice has shown that when testing industrial effluents, the
oxygen concentration, pH, temperature and nitrite should be followed up.
 Markku Huhtamäki 7

Figure 3. A nitrification test. (Science traveller Int. 2006)

Inhbition tests
Nitrification inhibition tests are corresponding to nitrification tests. As a reference sludge has
to be used a nitrifying sludge (capacity 2 – 4 g NO3-N/g MLVSS,h). The nitrification rate of
test samples are proportioned to the reference sample and the difference is given as
percentage. For the test procedure applies the same notes as were given for nitrification tests.

Denitrification tests
The heterogeneity of carbon sources have a remarkable influence on denitrification tests,
while the reaction rates change during consumption of the carbon source fractions and due to
that also the dosage amount has an impact. Also the sludge history and redox-potential
reflect to the results (Lie and Welander 1995; Figure 6). E.g. when sludge is stored its redox-
potential decreases and if pre-aerated it increases. It is increased also if the sludge is adapted
to chemicals with repeated nitrification – denitrification periods.

70

60
Nitraattipitoisuus [mg NO3-N/l]

50

40

30

20 F0
Fi
B1 Testi pvm 10.11.2006
10
K1 Liete 250 ml/l; n 0,8 g MLVSS/l
o
K5 T 12 C; pH 7,0 -8,0
0
0:00 1:00 2:00 3:00 4:00 5:00 6:00 7:00 8:00
Aika [h]

Figure 4. Influence of some industrial effluents on denitrification.

8 Markku Huhtamäki

Denitrification rates for some industrial effluents are shown in figure 4. In these tests the
effluents are added so that the BODtot is on the same level in all samples and the results
visualize the effect of BOD quality on denitrification. A common feature for these samples is
that they include a fraction of very useable BOD and when it is consumed, the denitrification
rate reduces. Sample F0 is industrial, mechanically treated effluent and Fi is a corresponding
sample from the aeration tank (12 hours residence time; no sludge circulation). The aeration
has reduced the amount of good carbon source remarkably. The denitrification rate for the
non-aerated sample was at the beginning 40 (mg NO3-N /h)/g MLVSS, from which it
reduces to the level of 5 (mg NO3-N /h)/g MLVSS. The denitrification rate for the aerated
sample is only 20% of that.

Table 2. Industrial wastes and waste-products for denitrification (Eckenfelder 2000)

Substrate (at 13 - 16 oC) COD [mg/l] (mg NO3-N /h)/ g MLSS
Common substrates
Acetic acid 1 056 000 3,4
Endogenous 0,2 - 0,6
Food industry
Yeast industry 28 800 3,0
Wine industry 210 000 5,4
Slaughterhouse 250 000 1,4
Plant and vegetable processing 26 000 4,3
Chemical industry
Pharmaceutical industry I 188 000 4,1
Pharmaceutical industry II 320 000 1,3
Glue production I 280 000 1,0
Photographic industry 690 000 1,6

Table 3. Denitrification rates 15 oC 2 Nyberg et al. (1996)

(mg NO3-N /h)/ g VSS

Municipal effluent 0,5 - 2
Methanol 4 - 5,5
Ethanol 10 - 17

Several industrial waste liquids can be suitable to be used as carbon source at municipal
effluent treatment as can be seen comparing tables 2 and 3. The disposal of these by using
conventional methods would be costly.
In figure 5 can be seen than the fraction of easily biodegradable BOD in municipal
effluent treatment reflects on the denitrification rate (15% of the incoming effluent was
mechanically treated foodstuff industry effluent; the rest typical municipal effluent). In the
figure 5 is shown also denitrification rates for commercial methanol and a by-product
methanol. The by-product methanol was earlier disposed in a hazardous waste disposal plant.
However, it was more efficient for denitrification than the corresponding commercial
product. The tests were performed also with a sludge adapted to methanol. In that case the
difference was also clear but smaller (4.1 g NO3-N/h/g MLSS and 5.2 g NO3-N/h/g MLSS).
 Markku Huhtamäki 9

Also in the tests can be seen that the biofilm media used at the wwtp (efficient specific
surface area 388 m2/m3) with 26 %:n filling ratio had the same denitrification rate as 1.5 g/l
activated sludge.

40

Carriers (L1) 100 m2/m3 C-source:

35 Influent 33 vol-%

Carriers (L2) 100 m2/m3 . C-source:

30
Nitrate concentration [mg NO 3-N/l]

Influent 33 vol-%

25
Activated sludge 3 g/l 67% + Treated
effluent 33% (endogen. respir.)

20 Activated sludge 3 g/l 67% + Influent

33%

15 Activated sludge 3 g/l 33% + Influent

33%

10 Activated sludge 3 g/l 50% +

methanol
5 Test date 18.7.2006 Activated sludge 3 g/l 50% + by-
T 20-21 oC; pH 7,0 -8,0 product methanol
0
0:00 1:00 2:00 3:00 4:00 5:00 6:00 7:00 8:00

Time [h]

Figure 5. Denitrification test examples

Figure 6. Relation between redox-potential and denitrification rate

 10 Markku Huhtamäki

Practical experiences
Typical municipal wastewater does not contain enough carbon source. To achieve
efficient nitrogen removal (> 70%) external carbon source, like methanol, ethanol or
acetate has to be added.

90% Normal load

1.1.2001 - 1.6.2002
80% Test period B
1.8.2002 - 9.12.2002
70% Test period D
27.6.2003 - 30.11.2003
Nitrogen reduction

60%
- Normal load: At the wwtp both lines in
50% operation. At the industry an efficient
biological pre-treatment.
40% - Test periods B and D: Only line 2 in use in
which a 30 volume-% unaerated zone was
30% created by closing the aerator valves.
- During period B more soluble BOD was
discharged to the wwtp than during period
20% D. During period B the redox-potential in
the unaerated zone was all the time
10% negative but during period D it was
between -100 ... + 100 mV.
0%
0 5 10 15 20 25
Influent BOD7(ATU) /N-tot ratio

Figure 7. Wastewater quality and nitrogen removal in selected periods

In figures 7 and 8 can be noticed that every time unaerated food industry wastewater was led
to the town treatment plant so that the process included an unaerated section (DN-process)
and pH was maintained > 7.0 pH in the process, the required 70% nitrogen removal was
reached. Positive effect of soluble BOD coming from industrial effluents can be noticed
during all periods.
Nitrogen removal bound to sludge kg/month
Nitrogen removal to/from air (= influent - effluent - sludge N) kg/month
Environmental load NO3-N kg/month
Environmental load NH4-N kg/month
kg N/ IFAS, Fully aerated MBBR; DN
month Line 1
AS; Fully aerated AS; DN-process - IFAS; DN Line 2
25 000
Normal load B D

20 000

15 000

10 000

5 000

-5 000
1 2001
2 2001
3 2001
4 2001
5 2001
6 2001
7 2001
8 2001
9 2001
10 2001
11 2001
12 2001
1 2002
2 2002
3 2002
4 2002
5 2002
6 2002
7 2002
8 2002
9 2002
10 2002
11 2002
12 2002
1 2003
2 2003
3 2003
4 2003
5 2003
6 2003
7 2003
8 2003
9 2003
10 2003
11 2003
12 2003
1 2004
2 2004
3 2004
4 2004
5 2004
6 2004
7 2004
8 2004
9 2004
10 2004
11 2004
12 2004
1 2005
2 2005
3 2005
4 2005
5 2005
6 2005
7 2005
8 2005
9 2005
10 2005
11 2005
12 2005
1 2006
2 2006
3 2006
4 2006
5 2006
6 2006
7 2006
8 2006
9 2006
10 2006
11 2006
12 2006

Aver 2004
Aver 2005
Aver 2006
Aver 02 tests
2001 - 2002

Nitrogen fixation from air Yellow: Nitrogen removal >60% Raisio Plc pre-treatment by-
Green: Nitrogen removal >70% pass partly or totally

Figure 8. Nitrogen balance and operation modes of the Raisio wwtp 2001 - 2006
 Markku Huhtamäki 11

The optimal addition of soluble BOD is the amount of methanol (mg/l) which would
otherwise be needed for the municipal effluent. In such cases, industrial load replaces
methanol and does not increase sludge production. Better nitrogen removal can be achieved
if the load is higher. If it is lower, some additional carbon source has to be added. The pre-
aeration with 12 hours residence time removed in practice all the soluble BOD. If pre-
aeration is needed for odour removal, residence time should be shorter.

Modelling and simulation

Process simulation and complementary tests can be used for evaluation how the pre-
treatment alternatives of the industrial effluent affect on the nutrient removal, excess sludge
production, energy requirements and upgrading needs at municipal effluent treatment plant.
In the following text a case is described where an industrial unit is connected to a
municipal wwtp and how the pre-treatment alternatives and load changes affect on the
results.

Table 4. Basic data for the simulations

Ind. Mechanical Ind. Aa+ aer. pre-
Fraction Municipal fraction Ind. Pre-aerated
pre-treatment treatment
Name kg/d mg/l kg/d mg/l kg/d mg/l kg/d mg/l
Flow norm m3/d 11800 1700 1700 1700
Temperature oC * 8 15 * 15 * 15 *
COD-tot 7400 627 2810 1653 2213 1302 2213 1302
COD-sol 870 74 1645 968 247 145 71 42
BOD7-tot 2960 251 1555 915 942 554 43 25
BOD7-sol 300 25 1168 687 112 66 2 1
TSS 5000 424 1001 589 1311 771 85 50
VSS 3750 318 951 559 1245 733 68 40
N-tot 550 47 90 53 90 53 70 41
NH4-N 413 35 25 15 3 2 70 41
P-tot 105 9 51 30 52 31 2 1
PO4-P 63 5 31 18 27 16 1 0
*
Based on the effective temperature influent after drainage to the wwtp (winter time).
** o
Mech pre-treatment = fine screening; pre-aerated = flow equalization and aeration 12 h 30 C; Aa+ aer.
Pre-treatment = anaerobic + aerobic treatment and sludge separation

The process volume 3600 m3, MLSS concentration 3 g/l and the process configuration, a 4-
stage Bardenpho-process in which the post-anoxic section can also be aerated, are fixed for
this comparison.
In figure 10 the key simulation results are shown in the case where industrial effluent is
discharged after screening. Due to the water quality 39% of nitrogen is bound to the sludge
and there is no nitrogen removal in the post-anoxic department. From this can be concluded
that to reach less than 10 mg/l residual nitrogen, more carbon source would be needed (or
more recycle flow, but the simulation shows that it would not improve the result enough).
In figure 11 the process is evaluated for a higher load (municipal load 135% and flow
150%; industry 150%). It can be noticed (fig 11a) that the basic solution (the post-anoxic
section is non-aerated) is at a risk level, where the ammonium concentration is increased and
the process is sensitive for load peaks and disturbances. Aeration of the post-anoxic section
(11 b), nitrification and total nitrogen removal improve and 70 % nitrogen removal can be
reached also at winter time. If the industrial effluents would be pre-treated efficiently with an
12 Markku Huhtamäki

anaerobic process, the nitrogen removal would drop below 50% without additional carbon
source (fig 11 c). Additional carbon should be dosed (fig. 11 d) about 90 mg/l for 70 %
nitrogen removal. That dosage would mean for this effluent amount (15500 m3/d) 450 t/a
methanol (about 200 000 €/a). In addition there would be the industrial pre-treatment costs.

Carbon Source
Nitrate cycle
Me3+ Me3+

Anoxic/ Anoxic/ Anoxic/

Anoxic Aerobic Aerobic Aer
Aerobic Aerobic Aerobic

Return sludge

Figure 9. 4-stage Bardenpho-process

Eff SCODbio Eff NH4N Eff NO3N Flow

NH4N Uptake in Biofilm and MLVSS (kg/d)
b) Flow, m3/h
SCODbio, NH4N, NO3N conc, mg/L

12 mg/l 16 000
NH4-N 0,2 200
NO3-N 9,6 mg/l
TN-out
14 000
10 11,50 mg/l 180
TN-in 54,7 mg/l 12 000
160 Mixed Liquor VSS
8
Biofilm
NH4N Uptake, kg/d

10 000
140
6 8 000
120
6 000
4 100
4 000
80
2 2 000
60
0 0
40
10 12 14 16 18 20 22 0 2 4 6 8 10
Time of the day N to prim. sludge 11960 m3/d
20
20 %
N to secondary sludge 19 % 0
AA

Anox

Anox

Aer

Aer

Aer

Anox

Anox

Aer

Aer
N as gas to air
-

-
79 %

Load Munic. Ind Sum clarif. out Denitrification in Biofilm and MLVSS

3
Q m /d 10000 1700 11700 11965 11700 200
180 Mixed Liquor VSS
SS kg/d 5000 1001 6001 1214 117 Biofilm
Oxidized N Denitrified, kg/d

160

VSS kg/d 3750 951 4701 928 88 140

120
COD kg/d 7400 2810 10210 3536 123 100
80
BOD kg/d 2960 1555 4515 1775 35
60

P-tot kg/d 105 51 156 36 16 40

20
N-tot kg/d 550 90 640 508 136 0
AA

Anox

Anox

Aer

Aer

Aer

Anox

Anox

Aer

Aer
-

NH4-N kg/d 413 25 438 450 3

NO3-N kg/d 1 0 1 1 112

Figure 10. Effluent quality. Conditions: Load 100% basic load; Industr. Mech. pre-treated;
Basin: 25% pre-anoxic, 52,5% aerobic, 20% post-anoxic and 2,5 % post-aeration; RAS 125%;
NR 75%; Media 200 m2/m3 in each cell except in the first post-anoxic cell.

Further it can be seen that the flow and the industrial load could be increased remarkably
if the existing process volumes would be fully utilized (fig.12). In the situation nitrogen load
of the biological section is 0.2 (kg N/d)/m3, HRT 4 hours, temperature 9 oC and aerobic
sludge age 2,5 days. Under these conditions the sludge treatment and hydraulic capacities are
exceeded although the biological treatment would have the possibilities for the required
reduction.
 Markku Huhtamäki 13

Eff SCODbio Eff NH4N Eff NO3N Flow Eff SCODbio Eff NH4N Eff NO3N Flow
a) Flow, m3/h b) Flow, m3/h

SCODbio, NH4N, NO3N conc, mg/L

SCODbio, NH4N, NO3N conc, mg/L 9 NH4-N 4,5
mg/l 900 12 NH4-N 2,7
m g/l 900
8 NO3-N 7,4 mg/l 800 NO3-N 8,8 m g/l 800
TN-out 15,72 mg/l 10 TN-out 14,78 m g/l
7 TN-in 54,7 mg/l 700 TN-in 54,7 m g/l 700
6 600 8 600
5 500 500
6
4 400 400
3 300 4 300
2 200 200
2
1 100 100
0 0 0 0
10 12 14 16 18 20 22 0 2 4 6 8 10 10 12 14 16 18 20 22 0 2 4 6 8 10
Tim e of the day
Time of the day N to prim. sludge 19 % 15955 m3/d N to prim. s ludge 19 % 15986 m3/d
N to secondary sludge 23 % N to secondary s ludge 21 %
N as gas to air N as gas to air
71 % 73 %

Eff SCODbio Eff NH4N Eff NO3N Flow Eff SCODbio Eff NH4N Eff NO3N Flow
c) Flow, m3/h d) Flow, m3/h
SCODbio, NH4N, NO3N conc, mg/L

SCODbio, NH4N, NO3N conc, mg/L

35 mg/l 900 20 mg/l 900
NH4-N 2,1 NH4-N 3,2
NO3-N 23,1 mg/l 800 18 NO3-N 11,8 mg/l 800
30 TN-out 28,53 mg/l TN-out 19,13 mg/l
TN-in 700 16 TN-in 700
52,8 mg/l 52,8 mg/l
25 14
600 600
20 12
500 500
10
15 400 400
8
300 300
10 6
200 4 200
5 100 100
2
0 0 0 0
10 12 14 16 18 20 22 0 2 4 6 8 10 10 12 14 16 18 20 22 0 2 4 6 8 10
Time of the day 15788 m3/d Time of the day N to prim. s ludge 15823 m 3/d
N to prim. sludge 12 % 12 %
N to secondary sludge 13 % N to secondary sludge 16 %
N as gas to air N as gas to air
46 % 64 %

Figure 11. Effluent quality. Conditions: Municipal 130%; Industry 150%. a) and b) Ind. ww
mech. pre-treated; c) and d) Ind. anaerobically pre-treated; Conditions like in fig 5 except in
6b) post anoxic section is aerated; NR=0; RAS=180% and in 6d) 60 g/m3 methanol is added.

Eff SCODbio Eff NH4N Eff NO3N Flow

Load Munic. Ind Sum clarif. out b) Flow, m3/h
SCODbio, NH4N, NO3N conc, mg/L

3
Q m /d 17700 3400 21100 21673 21100 9 NH4-N
NO3-N
2,0
6,9 mg/l
mg/l 1 200
8
TN-out 11,35 mg/l 1 000
SS kg/d 6750 2002 8752 2854 211 7 TN-in 43,8 mg/l
6 800

VSS kg/d 5063 1902 6964 2176 158 5

600
4
COD kg/d 9990 5620 15610 7254 222 3 400
2
200
BOD kg/d 3996 3110 7106 3662 63 1
0 0
P-tot kg/d 142 102 244 80 29 10 12 14 16 18 20 22 0 2 4 6 8 10
Time of the day 21672 m3/d
N to prim. sludge 18 %
N-tot kg/d 743 181 923 755 239 N to secondary sludge 28 %
N as gas to air
74 %
NH4-N kg/d 557 50 607 637 42
NO3-N kg/d 1 0 1 1 146

Figure 12. Effluent quality. Munic. load 135% and flow 150%; Industry 200% mech. pre-
treated. Post-anox aerated; carrier filling ratio 50%.
14 Markku Huhtamäki

Criteria for wastewater taxation between the partners

The requirements for nitrogen removal change the effluent cost structure. In typical
municipal effluent treatment efficient nitrogen removal requires external carbon source like
methanol, ethanol, liquid sugars, syrups or salts of organic acids. When there was no
requirement for nitrogen removal, the reactor volumes and aeration efficiency were
determined based on the BOD-load. For plants having nitrogen requirements, the volumes
are in practice determined based on the nitrogen-load.
Conventional wastewater taxation models are based on high taxes for BOD. To save costs,
industry may invest in biological pre-treatment resulting in need of external carbon source at
the municipal wwtp. In cases, when nitrogen removal is required, the effluent taxation based
for nitrogen instead of BOD would result in a more sustainable solution.
The taxation criteria for effluent quality could include only suspended solids and soluble
nitrogen (ammonium) and perhaps also phosphorus. A simple model would reduce the
amount of expensive analyses and the basic quality might be controlled more frequently.
The weight in taxation for suspended solids should be notable, while in effluent treatment
the sludge disposal costs are nowadays often more than 50% of the variable costs. The solids
are typically inert solids or biomass having about 40% BOD, 8% nitrogen and 2% P. The
separation of suspended solids reduces also the BOD and nutrient load. The solids should be
easily separated at the industry - and in many cases the improvement can be done by
reducing the raw material losses. The waste disposal costs are increasing.

Economic and environmental benefits

Typically, depending on the case, 10 – 30 mg NO3-N/l has to be removed using external
carbon source. Methanol is often the most economic commercial carbon source (e.g. Jonsson
2004). Denitrification requires 3,5 kg methanol/ kg N ~ 3,5 kg BOD/ kg N. The optimal
addition of soluble BOD is the amount of methanol (mg/l) which would otherwise be needed.
In such cases, industrial load replaces methanol and does not increase sludge production.
Better nitrogen removal can be achieved if the load is higher but in such cases also the sludge
production increases. If it is lower, some additional carbon source has still to be added but
less than otherwise.
The market price for methanol + transportation is 300 – 600 €/t depending on place.
Utilizing the soluble BOD of industrial effluents 2 – 5 ct/m3 cost savings can be achieved. In
a medium size municipal effluent treatment plant treating 5 million m3/a effluent, the
potential is for 200 000 €/a cost saving. When the nitrogen removal requirements are
becoming more common, the market price of methanol is going to increase.
When utilizing industrial carbon sources, the municipality can save costs but so does also
the industry in investing to pre-treatment and operating it. Alternatively, when the waste
liquids can be used, the disposal costs are going to be saved. At its best the co-operation is
sustainable by reducing the environmental load: less chemical production, less waste and
sludge disposal and less transportation is needed and natural resources are spared.
 Markku Huhtamäki 15

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