PRACTICE REPORT

LABORATORY & PROCESS ANALYSIS

WASTEWATER TREATMENT
NUTRIENTS

Optimal nutrient ratios for

wastewater treatment
To be able to comply with the legal requirements on treated wastewater, plant
operators must control the treatment process carefully, so that they can intervene promptly to prevent limit values from being exceeded. Besides
chemical and physical methods, wastewater treatment is essentially based
on biological treatment by microorganisms in activated sludge.
Knowledge of the nutrient requirements and the composition of the
activated sludge are therefore needed if the plant is to operate at maximum
efficiency. The causes and effects of unfavourable nutrient ratios, and
the measures to be taken to deal with them, are described in this report.

Author:
Dipl.-Ing. Michael Winkler
- Project Leader, Product Development and Customer Service
- BIOSERVE GmbH, Mainz

NUTRIENTS ACTIVATED SLUDGE

Nutrients in activated sludge

A balanced nutrient ratio is essential if
the microorganisms are to function at
maximum efficiency. The most important
of these nutrients are carbon, nitrogen
and phosphorus.

Laboratory analysis and process

measurement technology support
compliance with the limit values.

Carbon
Carbon is the principal component of the
organic substances found in wastewater.
It is biodegraded by the microorganisms
in activated sludge under anaerobic conditions (bio-P), in an anoxic environment
(denitrification zone) and in the aerated
part of the biological stage (nitrification
zone). The microorganisms use the carbon compounds to build their cell structures and to generate energy.
Carbon compounds are determined
as COD, BOD5 or TOC

The workplace for laboratory

analysis consists of a photometer,
reagents and depending on the
parameter a thermostat.

Nitrogen
In the inflow of wastewater treatment
plants, nitrogen is present in organically
bonded form (organic N) and as ammonium nitrogen (NH4-N). During biological

wastewater treatment, organic N is converted to NH4-N by the bacteria in the

activated sludge. This NH4-N and the
NH4-N from the inflow are converted to
nitrite, which in turn is converted to
nitrate (nitrification).
The nitrogen compounds that are not
biodegraded in the activated sludge are
converted under anoxic conditions
(absence of dissolved O2) to elementary
nitrogen (denitrification). This escapes
into the atmosphere as N2.
Nitrogen compounds are determined
as NH4-N, NO2-N, NO3-N and TN
(total nitrogen, which is important for
balancing and outflow checks).
Phosphorus
The P load in the inflow of a wastewater
treatment plant is made up of
orthophosphate-phosphorus (PO4-P),
polyphosphates and organic phosphorus
compounds. Together, they give the sum
parameter total phosphorus (Ptot).

Organic compounds + O2 + Nutrients

Microorganisms

New cell material + CO2 + H2O

Table 1: Important sum parameters for wastewater treatment

COD (Chemical Oxygen Demand); this corresponds approximately to the amount of oxygen
required to completely oxidise the carbon compounds, including reduced inorganic compounds.
BOD5 (Biological Oxygen Demand); this indicates how much elementary oxygen is consumed during
five days of biodegradation by microorganisms under standard conditions.
TOC (Total Organic Carbon) is a measure of organically bonded carbon; in contrast to BOD5, TOC
also includes the carbon in poorly biodegradable compounds.
TKN (Kjeldahl nitrogen) is a measure of organically bonded nitrogen (organic N) and ammonium
nitrogen (NH4-N).
Total nitrogen TN (LATON) includes organically bonded nitrogen, ammonium nitrogen (NH4-N),
nitrite (NO2-N) and nitrate (NO3-N).

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Nitrification

Denitrification

Organic N compounds
(urea, proteins, etc.)
Hydrolysis and ammonification
Ammonium-nitrogen NH4-N

Nitrate-nitrogen NO3-N
Nitrate reductase
- Oxygen
Nitrite-nitrogen NO2-N

Nitrosomonas
+ Oxygen
Nitrite-nitrogen NO2-N

Nitrite reductase
- Oxygen

Nitrate-nitrogen NO3-N

Oxygen
Carbon dioxide CO2

NO, N2O

Nitrobacter
+ Oxygen

Organic C compounds

NO, N2O reductase

- Oxygen
Elementary nitrogen N2

Fig. 1: Degradation processes during nitrification and denitrification

During biological wastewater treatment,

polyphosphates and organically bonded
phosphorus are converted to orthophosphate.
The P demand of the organisms is
due to the special role of phosphorus in
their energy metabolism. P is needed to
form the cell membrane and DNA.
Some of the phosphorus in wastewater is eliminated biologically (bio-P).
The rest can be removed by chemicophysical phosphate precipitation.
Phosphorus compounds are determined as ortho-PO4-P (control of
precipitation) and as Ptot (balancing,
outflow monitoring)
Trace elements
Other trace elements needed to build
cells e.g. potassium, magnesium,
manganese, iron, copper, zinc and nickel, and vitamins and growth factors are
usually present in municipal wastewater,
or the microorganisms in the activated
sludge provide them themselves.

Sulphur
Septic domestic wastewater and some
industrial wastewater contain reduced
sulphur compounds (hydrogen sulphide,
sulphides and thiosulphates). Sulphur is
an indispensable component of proteins.
In wastewater treatment plants, reduced
sulphur compounds are not only oxidised
chemically to sulphate but are also oxidised by some bacteria to form sulphur
and, since this process generates energy,
are stored inside cells as food reserves.
High concentrations of reduced
sulphur compounds in wastewater can,
however, cause a number of problems
(Table 2).
C:N:P ratio (BOD5:TN:Ptot)
The content of the individual nutrients in
wastewater should correspond to the
needs of the bacteria in the activated
sludge, and there should be a balanced
relationship between C, N and P. This is
crucial to the effectiveness of the biodegradation processes. During aerobic wastewater treatment, the C:N:P ratio should
be in the range between 100:10:1 and
100:5:1.

Reagent-free probes are used for

continuous monitoring.

Modern analysers are mounted

directly on the edge of the tank
and do not need a protective
housing.

NUTRIENTS_CALCULATION

Favourable and unfavourable

nutrient ratios

SC 1000 controller for up to eight

sensors also suitable for use
as a network with, for example,
Profibus

However, all sorts of industrial plants,

regional differences in eating habits (disposal of different kitchen wastes through
the drains), and the nature of the soil and
drinking water cause wastewater to vary
widely in its composition. Experience has
shown that the C:N:P ratio in municipal
wastewater is about 100:20:5.
The excess N and P compounds can
usually be eliminated from the wastewater without any great difficulty using
modern methods.

If the wastewater in the inflow to the biological stage is deficient in one of the
main nutrients, a wide range of problems
may occur (Table 3).
For efficient denitrification, a certain
proportion of readily biodegradable C
compounds must be present. After
municipal wastewater has passed
through the primary settling tank, it has a
BOD5:N ratio of 100:25 (=5). If the ratio
falls below 100:40 (=2.5), the efficiency
of the denitrification process is impaired,
resulting in higher nitrate values in the
outflow. If bypassing the primary treatment and increasing the denitrification
volume fail to bring about any improve-

Table 2: Causes and effects of high sulphur concentrations

Partially immersed NITRATAX sc

probe for online nitrate
measurement

Causes/Origin of wastewater
High concentrations of sulphur compounds from chemical and protein processing
industries (meat and poultry
processing)
Anaerobic processes in the
sewerage system, which
cause sulphur compounds
to be reduced to hydrogen
sulphide

Possible consequences
Corrective action
Avoid blockages in the
Corrosion in sewers and
sewerage network
tank walls in wastewater
Add iron salts to the sewer
treatment plants
(e.g. at the pumping stations)
Neighbours suffer odour
nuisance
Increased growth of
sulphur oxidising filamentous
bacteria (Type 021 N)

Table 3: Causes and effects of nutrient deficiencies in the biological stage of wastewater treatment
Shortage of
Carbon

Nitrogen

Phosphorus

Causes/Origin of the wastewater

Long dwell time in the sewerage
network
Far-reaching primary treatment of
the wastewater
Industrial wastewater with a high
nitrogen content, e.g. from milk and
meat processing
Low-nitrogen wastewater from:
Paper industry
Fruit and vegetable processing

Possible consequences
Profuse development of filamentous
bacteria (sludge bulking and foam)
Insufficient denitrification

Corrective action
Bypass the primary treatment
Increase the denitrification volume while
retaining sufficient volume for the nitrification
(minimum sludge age of 9 days)

High COD/TOC values in the inflow

of the wastewater treatment plant
Filamentous bacteria

Landfill leachate, wastewater from

fruit and vegetable processing

Increased COD/TOC values in the

outflow
Filamentous bacteria

Balance the nutrient ratio by:

Addition of N compounds
(good-value industrial products such as urea)
Addition of domestic wastewater, turbid water
from digester
Balance the nutrient ratio by:
Addition of P compounds (good-value industrial
products such as phosphoric acid or phosphate
fertilisers for the agricultural sector)
Addition of domestic wastewater

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ment, the addition of a readily degradable substrate (external source of carbon)

should be considered.
Carbon sources for nutrient balancing
include:
- Internal C = hydrolysed or acidified primary sludge
- External C = industrial residues (from
breweries, dairies, sugar industry) and
industrial products (methanol, ethanol,
acetic acid).
COD:BOD5 ratio
The ratio of these two sum parameters
is a measure of the biodegradability of
the wastewater pollution load. If the
COD:BOD5 ratio does not exceed 2:1,
the biodegradability is said to be good.
Higher values indicate the presence of
poorly biodegradable substances.

Example
A municipal wastewater treatment
plant with a high proportion of industrial
wastewater has the following nutrient
parameters in the inflow to the biological
treatment stage (Table 5).
The BOD5:N ratio of 2.45 is too low for
adequate denitrification to occur. External carbon compounds should therefore
be added. However, a number of calculations have to be carried out before this
is done:

The practical LANGE cuvette tests

are available for all key parameters.

1. Amount of nitrogen that is not

to be denitrified (UNn.z.d.):
see Table 6
2. Calculate the amount of nitrogen that can be denitrified with
the wastewater:
With upstream denitrification and a
VD:VAT ratio of 0.5, the denitrification
capacity (according to Table 7) is
CDeni = 0.15 kg NO3-ND/kg BOD5.
SNO3-N, D = CDeni BOD5 infl aer
= 0.15 110 mg/L = 16.5 mg/L

In combination with analytical

quality assurance, the measurement results are officially
approved.

This means that 16.5 mg/L NO3-N can

be denitrified with the existing biological
treatment.

Table 4: Causes and effects of unfavourable COD:BOD5 ratios

Causes/Origin of wastewater
Landfill leachate, wastewater
from composting and residual
waste treatment facilities and
the chemical industry
Considerable reduction in
BOD5 in the long sewage network in summer
Intensive primary treatment
of the wastewater

Possible consequences
Inadequate denitrification
(high nitrate values in the
outflow)
High COD in the outflow of
the wastewater treatment
plant
Deterioration of bio-P

Corrective action
Addition of C sources to
improve denitrification
Use chemicophysical methods
(ozone treatment, activated
carbon filter, membrane technology) for poorly biodegradable and non-biodegradable
substances

If large numbers of samples have

to be analysed, the automatic
laboratory analysers offer valuable
support.

NUTRIENTS_CONTROL

Regulating the substrate dosage by

means of NO3-N measurements
Table 5: Average daily values of a municipal wastewater treatment plant
Average daily values
Inflow [m3/d]
BOD5 infl aer [mg/L]
TNinfl aer LATON [mg/L]
Ptot infl aer [mg/L]
BOD5 infl aer. : TNinfl aer = 110:45 =

10,000
110
45
3,5
2.45

3. Calculating the external

substrate requirement
The still to be denitrified N content is the
total added nitrogen minus the amount
of nitrogen that is not to be denitrified
minus the amount of nitrogen that the
plant can denitrify:
SNO3-N, D, Ext = TNInflow- UNn.d. - SNO3-N, D
= 45 mg/L - 15.5 mg/L - 16.5 mg/L
= 13 mg/L

Table 6: Calculation of amount of nitrogen that is not to be denitrified (Nn.d.)

N incorporated in biomass (5 % of BOD5 infl aer)
Norg.e (e = assumed target quantity in the outflow)
NH4-Ne (e = target quantity in the outflow)
NO3-Ne (e = target quantity in the outflow)
Sum

5.5mg/L
2mg/L
0mg/L
8mg/L
15.5mg/L

Table 7: Denitrification capacity in accordance with ATV-A131

(guideline values for dry weather and temperatures from 10 to 12C)
VD/VAT
Volume Deni/Volume Aeration

CDeni (Denitrification capacity in kg NO3-ND/kg BOD5)

Upstream denitrification
Simultaneous and intermittent
denitrification
0.2
0.11
0.06
0.3
0.13
0.09
0.4
0.14
0.12
0.5
0.15
0.15
VD: Volume of the aeration tank used for denitrification
VAT: Volume of the aeration tank

Table 8: External carbon sources for calculating the necessary dosage

Acetic acid
Methanol
COD
kg/kg
1.07
1.50
TOC
kg/kg
0.40
0.38
BOD5 kg/kg
0.70
0.96
Density kg/m3
1,060
790
In this example, 1 kg acetic acid is equivalent to 1.07 kg COD.

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Ethanol
2.09
0.52
1.35
780

To denitrify the remaining 13 mg/L nitrogen, the microorganisms in the activated sludge must be provided with
an additional source of carbon. A daily
wastewater volume of 10,000 m3 has a
nitrogen load of 130 kg. According to
DWA Work Sheet A131, the external
carbon requirement is 5 kg COD/1 kg
NO3-N. This means that, for complete
denitrification to occur, 650 kg COD are
needed per day. If the additional carbon
is provided in the form of acetic acid,
the data provided in Table 8indicate that
607 kg would have to be added each
day. The targeted dosage is based on
the NO3-N values.

Conclusions
Unfavourable nutrient ratios and high
concentrations of individual substances
reduce the degradation efficiency of
biological wastewater treatment processes. Early recognition and continuous
monitoring of critical parameters is therefore essential in order to enable plant
operators to take rapid corrective action
when necessary. Only in this way can
compliance with legal outflow values be
ensured and unnecessarily high wastewater levies be avoided. LANGE cuvette
tests and continuously operating process
measurement devices have demonstrated that they are indispensable aids
to achieving greater transparency and
reliability.

Typical measurement locations

for the monitoring of nutrients in
wastewater treatment plants

The analysed nutrient parameter are

(depending on the self-monitoring regulations):

Inflow to primary settling tank: deter-

COD (ggf. TOC)

BOD5
ortho PO4-P
Ptot
NH4-N
TKN (Kjeldahl nitrogen: sum of NH4-N
and organic N)
Ntot.inorg. (inorganic N: sum of NH4-N,
NO3-N and NO2-N)
TNb (total nitrogen: sum of organic
and inorganic N)

mination and monitoring of the plant

loading
Inflow to aeration tank: optimisation of
nutrient supply
Outflow from aeration tank: monitoring and optimisation of C degradation
performance, nitrification/denitrification and P elimination
Outflow from WWTP: monitoring of
limit values, control of the WWTP

Filter
Final sedimentation

Thickener

Aeration
Primary settling

Screen/grit chamber

Digester

Channel
Storm-water tank

Sludge dewatering

Laboratory/Main control centre

Fig. 2: Schematic representation of a wastewater treatment plant with measurement locations for nutrient monitoring

NUTRIENTS_MEASUREMENT SOLUTIONS

Optimal nutrient ratios with modern

measurement technology
Measuring station for laboratory analysis
DR 3900

LT 200

Alternative
HT 200S

Cuvette tests

Compact and powerful spectrophotometer (3201100 nm) with RFID

technology for reliable and traceable measurement results in routine
analyses and user applications; barcode reader (IBR) for automatic
evaluation of LANGE cuvette tests; backlit graphic display with touchscreen
Dry thermostat for standard and special digestions; preprogrammed
digestions for the analysis of COD, total N, total P, TOC, organic acids,
metals
High-temperature thermostat for fast digestion for the analysis of COD,
total N, total P, metals in just 35 minutes; standard digestions for
analysis of TOC
Ready-to-use reagents with maximum user safety; highly precise;
approved method; more than 50 parameters and measuring ranges

Systems for online measurement

PHOSPHAX sc

AISE sc
AN-ISE sc
NISE sc

NITRATAX sc

SC1000 Controller

Alternative
SC200 Controller

Process measuring instrument for continuous determination of the

ammonium concentration in water and wastewater samples with a
low solids content. The measurement is carried out by a gas-sensitive
electrode.
Process measuring instrument for continuous determination of
the ammonium concentration in water and wastewater samples
with a low solids content. The measurement is carried out using the
vanadate-molybdate method.
ISE probe for continuous in-fluid determination of the ammonium concentration (AISE sc, AN-ISE sc) and nitrate concentration (NISE sc, ANISE sc). The measurement is carried out using an ion-selective electrode
(ISE) with automatic potassium and chloride compensation. Especially
easy handling thanks to the CARTRICAL plus sensor cartridge.
Process probe for determining the nitrate content directly in water,
wastewater or activated sludge; no sampling required; self-cleaning;
reagent-free method; variety of measuring ranges
A SC1000 controller system consists of a single display module and
one or more probe modules. It is configured modularly to suit the
customers specific requirements and can be expanded at any time to
include additional measurement locations, sensors, inputs, outputs and
bus interfaces. Each module controls up to eight sensors.
Controls up to two sensors (not for AMTAX sc or PHOSPHAX sc).

Measurement station for laboratory analysis,

with DR3900 photometer, LT200 thermostat
and LANGE cuvette tests

Literature
1. ATV-Handbuch: Biologische und weitergehende Abwasserreinigung, Ernst & SohnVerlag 1997
2. K. Hnel: Biologische Abwasserreinigung mit
Belebtschlamm, VEB Gustav Fischer Verlag,
1986
3. K. Mudrack, S. Kunst: Biologie der Abwasserreinigung, Gustav Fischer Verlag, 1994
4. Arbeitsblatt DWA A 131
5. S. Kunst, C. Helmer, S. Knoop: Betriebsprobleme auf Klranlagen durch Blhschlamm,
Schwimmschlamm, Schaum, Springer-Verlag
2000
6. D. Jenkins, M. G. Richard, G. T. Daigger:
Manual on the causes and control of activated sludge bulking, foaming, and other solids
separation problems, Lewis Publishers 2004
7. Poster Betriebssicherheit und Kosteneinsparung mit HACH LANGE, DOC140.72.00449

DOC040.52.10005.Oct12

AMTAX sc